F R ITZ R

P R O F E S S O R O F P H Y S IC S IN T HE U N IV E R S IT Y 0 B R E S LA U

BY H . S .

H E N RY L. B RO S E , MA . .

W IT H

CO . L TD

36 ESSEX STRE E T W . C .

L O N D O N
 CO N T E N T S

CH A P .

I . THE OF H E
O RI G IN T Q U AN TU M HY P O T H E SIS
II . T H E FAI LU R E OF C LA S SICA L ST A T IS TI CS

III . T H E D E E LO M E N
V P T AN D T HE RA MI FI A I O NS
C T OF

IV . T HE E X T E NSI O N OF H E D O RIN E OF Q UA N A O H E M
T CT T T T O

LE CU LA R T H E O R OF SOL I B O I E S
Y D D

T H E IN R U SI O N OF Q U A N A IN O H E T H E O R OF G A S S
T T T T Y E

T H E Q U A N U M T H E O R OF H E O I A L S E I E S T H E
T Y T PT C R .

VE LOP ME NT OF H E QUA N U M T H E O R FO R
T T Y

D EGREE S OF F R EE O M D

T H E QU A N U M T H E O R OF
T Y

P H E N O M E N A OF M OL E U LA R M O E LS “
C D

M A T H E M A T I CA L NO E S
T A ND

IN D E X
 T H E Q U A N T U M T H E O RY

I NTRODU CTI ON
HE Ol d s a y in g t h at s m a ll c a u se s gi v e r i s e to gr ea t e ffe ct s
has b ee n co n fir m e d m or e th a n o n c e i n t h e h i st o r y o f
phys i c s For v e ry fr e qu e n tl y i n c o n sp i cu ou s d i ffe r e n c e s b e
.
, ,

t w ee n t h e ory a n d e x p e r i m e n t ( wh i ch d i d n ot h ow e ve r e sc a p e
, ,

th e vi g il a n t e ye of t h e i n v e s t i g a tor ) h a v e b e c o m e s t ar t i n g
i n t o f n e w a n d i mp ort a n t r e s e a r ch e s
p o s .

Ou t of t he w e ll k n o w n Mi chel son Mor l ey e x p e r i m e n t

- -

whi ch i n sp it e of th e a ppl i c a t i o n of the m o s t p o w e rful

,

m e t h o ds of exa c t O pt i c a l m e a s u re m e n t f a il e d t o sh ow a n
,

i n flu e n c e of th e e a r t h s m o v e m e n t o n t he p r op a g a t i o n of
’

l igh t a s w as p r e d i c t e d b y cl a s s i c a l t h e ory t h e re a ro s e t he
,

gr e a t s tr uc tu re o f E in s tei n s Th eor y of Re l a tiv i t y In the

’
.

s a m e w a y th e t r i fl in g d i ffe re n c e b et w e e n t he m ea su re d a n d
c a lcul at e d va lu e s of bl a ck b ody r a d i at ion ga v e r i s e to the
-

Qu a n tum Th eor y wh i ch for mul a t e d by Ma n: P l a nck w a s

, ,

d e s ti n e d t o r e volu t i on i s e i n the c ou r s e of t i m e a lm o s t a l l
d e p a rt m e n t s of phys i cs .

Th e qu a n t um t h e ory i s y et c o mp ar a ti v ely y ou n g . It i s
t h e r e f ore n o t su rp r i s i n g t h at w e ar e c o n f r o n te d wi t h a n
u n fi n i sh e d t h e ory sti ll i n p r o c e s s of de v e l opm e nt wh i ch ,

ch a n gi n g c on s ta n tly i n m a n y d ire c t i on s must Oft e n d e s tro y

,

wh a t i t ha s bu i l t up a S h ort t i m e b e f or e Bu t u n der such

.

c ircums t a n c es a s t h e s e i n wh i ch the t h eor y i s c on t i nu a lly

,

d e r i vi n g n e w n o u r i shm e n t fr o m a fr e s h s t r ea m of i d e a s a n d
sugge sti o n s t h e r e i s a p e cul ia r fa sc i n a tion i n atte mp t in g t o
,

r e vi e w t h e l i f e h i s t ory o f t he qu a n t um t h e ory t o t he p r e s e n t
-

t i m e a n d i n d i scl o s i n g t he k e r n e l w h i ch w i ll c ert ai n ly ou t
l a st c h a n ge s o f f o r m.
 CHAP TE R I

T he O r i g i n of t he Q u a nt u m Hy p ot he s i s
I . Bl a ck B ody Ra d ia ti on
-
a nd it s Rea l isa ti on in P ra ct i c e

HE Q u a n t um Th eory fi r st l i ght i n 1 9 00 W he n i n
sa w .
,

t he ye a r s i mm e d i a t e ly p r e c e d i n g ( 1 89 7 L u mmer
n d P r i ngshei m m a d e t h e i r fu n d a m e n t a l m e as u r e m e n t s 1 o f
f

b l a ck b ody r a diat i on at th e R eic hsa ns ta l t t h e y co uld h a v e ,

h a d n o p r e m o n i t ion t h a t t h e i r c ar eful e x p e ri m e n t s would

b e c o m e th e s t a r t i n g p o i n t of a r e v olu ti on s uch a s h a s se ld o m
o ccu rr e d In phy si cs .

In t he fi e ld o f h e a t r a d i a t i o n chi e f i n t e r e s t a t t h a t t im e w a s
c e n t r e d i n th e r a d i a t i on o f a bl a c k b o dy ( b r i e fly c a ll e d bl a ck
b o dy r a d i a t ion ) t h a t i s of a b ody whi ch a b sorb s c o mpl et e ly
, ,

a l l r a d i a t i on wh i c h f a lls o n i t a n d wh i ch t hu s r e fl e c t s t r a n s ,

m it s a n d s c a t e s n on e We m a y s h or tly c a ll t o m i n d
,
t r 2 .

t he foll o wi n g f a c t s It i s k nown t h at a n y b o dy a t a gi v e n
.

t e mp e r a t u r e s e n ds o u t e n e r gy i n the for m of ra di a tio n i n to

the s u rr o u n d i n g sp a c e Th i s r a d i a tion i s n ot e n e r gy i n a
.

s i n gl e s i mpl e for m b u t i s m a de up of a n umb er of s i n gl e

r a d i at i on s of d iff e r e n t c o l o u r s i e of d iffe r e n t w a v e l e n gt hs A
, . .
-

o r of d i fie r e n t fr e qu e n c i e S S v In o t h e r w or ds i t fo r m s i n
.
,

ge n e ra l a Sp e ctrum i n whi ch ra d i a t ion s of a ll f r e qu e n c i e s

b e t w ee n v 0 and v co a re r e p r e s e n t e d F u rt h e r t h ese
.
,

ra d i a ti on s a r e p r e s en t i n va r yi n g i n t e n s it i e s We d e fin e
.

t h i s t e r m t hu s Con si d e r th e r a di a t i o n e m i t te d fro m u n i t
.

su rf a c e of the b ody p er se c on d i n a c erta i n di r e ction ; b r e a k

i t up sp e c t r a lly a n d cu t o ut of t he s p e c t r um a sm a ll fr e qu e n cy
i n t e r va l d v such t ha t i t c on t ai n s a ll fr e qu e n c i e s b etwe e n v a n d
v d v. Th e e n e r gy of r a d i a t ion E th us S l i c e d ou t ( n a m e ly
, ,

the emissi vi ty of the bod y f or t he fr equ ency v) m a y b e d e fi n e d

i n th e fo ll o wi n g t er m s : 4
E0 27 K d
2
 B LA C K B O D Y R A D I A T I O N
-
8

p rovi d e d th a t— a s w e sh a ll a s s um e fo r the s a k e of s i mpl i c i t y

— t he su r f a c e o f t he b o dy e m i t s u n i for m a n d u n p ol a ri s e d

r a d i a t i o n i n a ll d i r e c ti o n s .

Th e m a gn i t ud e K t hus d e fi n e d i s ca ll e d t he i n te n sit y of
y

r a d i a t i o n o f t h e b o dy for t he f r e qu e n cy i It i s i n g e n e ra l af.

m o r e or l e s s c o mpl i c a t e d fu n c ti on o f the f r e qu e n cy v of the ,

a b s olu t e t e mp e r a t u r e o f t he b ody T a n d o f t he i n h e r e n t,

p r o pe rt i e s of the b ody The bl a ck b o dy a l on e i s u n i qu e i n

.

t h i s r e sp e c t . F o r i t s r a d i a t i o n a n d t h e r e fo r e i t s K i s a s _ ,, ,

K w as t he fi r st t o p o i n t o u t d e p e n d e n t o n ly
'

G . i r c h fi
h o 5
,

o n t h e fr e qu e n cy v a nd t he a bs o lu t e t e mp e r a t u r e T t h a t i s , ,

m a t h e m a t i c a lly ,

K )
7
y f( V’ 1 ( 2)
Th i s f ormul a wh i ch gi ve s the r e l a t i on b etwe e n the i n t e n s ity
o f r a d i a t i on f r o m a b l a c k b o dy t h e t e mp e ra t u r e a n d t he
, ,

c ol o u r i s c a ll e d t h e r a d i a t i o n fo r mul a o r th e l a w o f ra d ia
“

t i o n of a bl a c k b o dy .

To c a l c ul a t e t h i s r e l a ti on shi p o n t h e o n e h a n d a n d t o
m e a su re i t on the o t h e r we r e u n s olv e d p rob l e ms a t t h a t
ti m e . U n i mp e a ch a bl e m e a su r e m e n t s w e r e o f c ou r s e p o s s ibl e
o n ly i f o n e co uld s ucc e e d i n c on s t r uc ti n g a bl a c k b o dy whi c h

a pp r o a ch e d su ffic i e n t ly n e ar th e t h e o r e t i c a l i d e a l Th i s i m .

p ort a n t ste p the r e a l i sa t io n of t he bl a ck b ody w a s t ak e n b y

, ,

0 L u m mer a n d W TVi en 6 o n th e b a s i s o f Ki r chhof s 7

’
/
. .

La w o f Ca vi t y Ra d i a t i o n wh i ch sta t e s : In a n enclo su r e
,

or a ca vi ty w hi c h i s enc l osed on a l l sid e s by r efl ec ti n g w a l l s ,

e x ter na l ly p r otected fr om ex cha ngi ng hea t w i th i ts su r r ou nd i ngs ,

a nd ev acu a ted , the cond i ti on of bl ac k r a d i a ti on is a u to

ma tic a l l y se t up if a l l the emi tti ng a nd a bsor bi ng bod i es a t the

w a l l s or i n the enc losu r e a r e a t the sa m e temp er a tu r e In a .

S p a c e t h e r e f o r e wh i ch i s h e r m e ti c a lly s u r r o u n d e d by b od i e s
, ,

a t t h e s a m e te mp e r a t ur e T a n d whi ch i s p r e v e n te d fr o m e x

c h a n g in g h e a t wi t h i t s s u r r o u n d i n gs , e v e r y b ea m o f ra d i a t i o n

i s i d e n t i c a l i n qu a l it y a n d i n t e n si t y w i t h t h a t wh i ch wo uld b e
e m i tt e d by a b l a c k b o dy a t t h e t e mp e ra t u r e T .

L u m rner a n d Wi en t h e re fo r e ha d o n ly t o co n s t ru c t a
, ,

u n i f or mly h e a ted e n cl o su r e wi t h bl a ck e n e d w a lls h a vi n g a .

s m a ll o p e n i n g The r a d i a ti o n e m itt e d f r o m t h i s O p e n i n g w a s
.

t he n bl a ck to a n a pp r ox i m at ion wh i ch w a s th e c l o s er
4 T HE Q U AN T U M T HE O R Y
th e sm a ll e r the op en in g t h a t i s the l e s s the c o mpl e t e ne ss Of
, ,

th e e n cl o su r e w as d i st u r be d Th e m a n n e r i n wh i ch t he .

i n t e n s it y K of the bl a c k ra d ia t i on t hu s r e a l i sed d e p en d e d
,

o n t h e fr e qu e n cy v a n d t he t e m p e r a t u re T ha d n e x t t o b e

d eterm ine d The ab o v e m e n t ion e d i n v e s t i ga t io n of m

.
-
er

a n d P r i ngshei m w a s d e v ot e d t o t h i s pu r p os e .

§ 2 . The S tefa n B ol tzmann La w o f Rad ia ti on

-
a nd W ien s
’

D i s pla c emen t L a w

W h i l e e x p er i m ent a l r e s e a r ch w a s p ro c e e din g on i t s w a y ,

th e or y w a s n ot i dl e fo r v a lu a bl e p i o n e e r w ork w a s b e i n g
,

don e in a smuch a s tw o fu n d a m e n ta l l a ws w e r e s e t u p In .

t he fi r s t pl a c e L B o z m a nn
l t ,
8 p r ov e d w ith t he h e lp of
.
,

t h e r m ody n a m i cs t h e l a w p r e v i ously e n u n c i at e d b y S tefa n 9

, ,

t h a t t h e sum t ota l O f t he r a d i a t i on f r o m a bl a ck b o dy
-

t aki n g a l l t h e f r e qu e n c i e s t og e t h e r n a m e ly t he qu a n t i t y , ,

K d v, i s p r op ort i on a l t o t he fou rth p o w er of i t s a bs olu te

te m p er at u r e : 10

K y T
4
(y c on st ) .
( )
3

The l a ws p r op o s e d by Wi en 11 e n t er ed m or e d e e ply i nto the

qu e st i o n Wi en i m a gi n e s the bl a ck r a di at i o n e n cl os e d i n a
.

cl o s e d S p a c e wit h a p e rf e c tly r e fl e ct i n g p i s ton as o n e w a ll ,

a n d t h e n s upp o s e s t he r a d i a t i o n to b e c o mp r e s s e d a d i a b a t i c a lly ,

as i n the c a se of g a s e s ( t h a t i s n o p as s a g e o f h ea t t o or f r o m ,

t h e c a v it y i s a ll o w e d du r i n g t he p r o c e ss ) by i n fi n it e ly sl o w ,

m ove m e n t s of the p i s ton N ow if w e ex p r e s s the ch a n ge .

,

whi ch t h i s p r o c e ss c a us e s i n th e e n e r gy of a de fi n ite c ol ou r
i n t e r v a l d v i n t w o w a ys a n d i f w e t a k e i n t o c o n s i d e r a t ion
,

t h at t h e w a v e s r e fl e c t e d a t the p i s t o n u n d e r go a ch a n g e o f
’
c ol our a c c or di n g t o D opp l er s p r i n c ipl e w e succ e e d i n l i m i t i n g ,

v e ry c on s i d e r a bly t he u n k n ow n fu n cti o n a l d e p e n d e n c e of the

qu a n t it y K o n v a n d T Th er e i s t hus ob ta in e d a r e
, .

l at io n of the f or m 12
3
v
7
0
( )
4

in wh i ch 0 i s the v e l o c ity Of l i ght i n va cu o the fu n c t ion F ,

be i n g l eft u n det e r m i n e d Fro m t h i s Wien s D i spl a c e m e nt

’
.
,

La w t he c on clus on
,
i 1 3 ma y be d ra w n t h at the fr e qu e n cy
 W IE N S LA W OF R A D I A T I O N
’
5

vmax whi ch K ( pl o tt e d a s a fu n c ti on o f v) i s
for , a m a x imum
i s d i s pl a ced t o wa r d s h i gh e r v a lu es p r op or t i on a l to T as t he
t e mp e r a t u r e i n cr ea s e s

Vma x Co n st . T ( )
4 a

If ,
as is usu a l in phys i c a l m e a s u r e m e n t , we u se t he w a ve
0
l en gth A In s te a d of the fre qu e n c y as t he v a ri a bl e Wi en s
,
’

La w ssum e s a so m e wh at d i ffe r e n t for m F o r if w e c on s i de r

a .

t he r a d i a n t e n e r gy of a n a rr o w r a n g e o f w a v e l e n gt h d A co r -

r e s p o n d i n g t o t h e fr e qu e n cy ra n g e d v a n d w r i t e i t i n the ,

for m E MA, t h e n E Ad A K d v, t h at i s
y : EA K y
9 In

pl a c e of ( )
4 and ( 4 a ) w e the n
ge t t h e l
r e a t i on s

2
0

X 5

X ma x T OO D S li . 8

§3 . W i en ’
s La w Of Ra d ia ti on

To f or mul a te t he l a w of r a di a tio n i t w a s t h er e for e n e c e s

sa r y o n ly t o e v a lu a t e t h e u n k n o w n fu n c t i o n F i n ( 4 ) o r

B u t t h i s w a s ju st t h e c e n tra l p o i n t o f t h e wh o l e qu e st io n ,

a n d t h e m o s t di ffi c ul t p a r t O f th e p r o bl e m .

H e r e too Wi en m a d e th e fi r st su c c e s s ful a tt a c k
, ,
O n t he .

b a si s of n ot e n t i re ly u n obj e ct i o n a bl e c a lcul a t io n s whi ch w er e ,

f ou n d e d On Ma x well s l a w Of di str i bu t i o n Of v el o c it i e s a m on g
’

g a s m o l e cul e s he a rr i v e d a t t he f o ll o w
,
i n g S p e c i a l i s e d f o r m 1 4

O f t he fu n c t i o n F

F a e
'

5 5 5
,
( a. a n d ,8 a re two c o n s t a n t s) .

Thu s t he l a w o f ra d i a t i on ( 4 ) a ss um e s t he fo r m

2 0.

whi c h c a ll e d Wie n s La w of Ra di a t i o n
is
’
.

H ow fa r d i d e x p e r i m e n t c o n fi r m t h e se t h eo r e ti ca l r e s ul ts ?
Wh il e the S tefa n Bol tzma nn La w a n d Wien s Di s pl a ce m e n t
-
’

La w wer e co n fir m e d to a l a r ge e xte n t b y th e ob se rv a ti o n s o f
L u mm er a n d P r i ngshei m “ b ot h e x p e r i m e n te r s f o u n d Wi en s
’

,
6 T HE Q U A N T U M THE O R Y
La w of Ra d i a t i o n fi r m e d on ly for h i gh f r e qu e n cie s t h a t i s
c on , ,

fo r s h o rt wa v e l e n gth s ( m or e p r e c i s e ly fo r l a r ge v a lu e s of
-

[i ii and d et e c te d ,
on the ot her h a n d ,
sy s tem a ti c d i scr ep a nci es

for sma l l fr equ enci es

, f lo n g w a t ha t i s,
ve l en g t h s 16 T h ey
or -
.

m a i n ta i n e d w it h u n s w er vi n g p e r s i st e n c e t h a t t he s e d i sc r e p a n
c i e s w e r e r e a l i n s p i t e Of O bj e c t i o n s f r o m a ut h o r it a t i v e qu a rt er s .

F or wh i l e F P a schen 17 i m a gi n e d t h a t h e h a d p r ov e d by hi s
.

w or k t h a t Wi en s La w of Ra d i a t i o n w a s u n i v er s ally v a l id
’
,

Ma x P l a nc k i n hi s d e t a i l ed t h e or y o f i r r e ve r s ibl e p r oc e ss e s
,

o f r a d i a t i o n 18 h a d a r r i v e d a g a i n a t Wi en s r a d i a t i o n f o r mul a
’

by a m o r e ri g or o us m et h o d St a r t i n g f r o m Ki r chhofi s La w
’

O f Ca v i t y Ra d i a t i o n a cc o r d i n g t o wh i c h t h e p r e s e n c e o f a n y
,

e m i t t i n g o r r a d i a t i n g su b st a n c e wh a t s o e v e r i n a u n if o r mly

h e a t e d e n cl o su r e p ro duc e s a n d e n s u r e s the m a i n t e n a n c e o f
the c on d it i o n o f b l a ck b o dy r a d i a t i o n P l a nc k ch o s e a s t h e
-

s i mpl e st sch e m at i c m o d e l o f s uch a sub sta n c e a s ys te m

of l i n e ar e l e c t r o m a g n e ti c o s c i ll a t o r s a n d i n v e sti ga t e d t he ,

e qu i l i b r i um o f th e r a d i a t i o n se t up b e t w e e n t h e m a n d t h e

r a d i a t i o n o f t h e e n cl o s u r e T h i s i s t o b e u n d e r s t o od a s fol
.

l o w s : E a ch o f t he P l a n ck o s c i ll at or s— a s s u c h w e m ay fo r ,

e xa mpl e a s s um e b ou n d e l e c tr o n s c a p a bl e o f v i b r a t i o n — p o s
,

s e s s e s a fi x e d n a t u r a l f r e qu e n c y v a n d r e sp o n d s o n a c c o u n t ,

O f i t s w e a k d a mp i n g o n ly t o t h o se w a v e s o f th e r a d ia t i o n i n
,

t he e n c l o s u r e wh os e f r e qu e n c i e s li e i n t h e i mm e d i a t e n e i gh
b o u r ho od O f v wh i l e a ll ot h e r w a v e s p a s s o v e r i t w it ho u t
,

e ffe c t Th e o s c i ll a t o r t hu s a c t s sel e c t i v e ly a s a r e s on a t or i n
.
, ,

j u s t t he s a m e w a y a s a t u n i n g fo r k O f d e fin i te p i tch com -

m e n c e s t o s o u n d o n ly wh e n i t s o w n p r op e r t o n e o r o n e ,

v e r y n e a r i t i s c o n t a i n e d i n the vo lum e of so u n d whi ch st r ik e s

,

it . In t h i s p r o c es s o f r e so n a n ce h o w e v e r t h e os c ill a t o r e x , ,

c h a n g e s e n e r gy w i t h t he r a d i a t i on i n a s much a s o n t h e o n e ,

h a n d i t a c t s a s a r e s o n a t or i n a b st r a c t i n g e n e r gy f ro m t h e
,

e x t e r n a l r a d i a t i o n a n d o n t h e o t h e r it a c t s a s a n o s c i ll a t o r
, , ,

a n d r a d i a t es e n e r gy b
y i t s o w n V ib ra tio n H e n c e a dy n a m ic .

e qu i l i b r i um i s se t up b e t w e e n t h e os c i ll a t o r a n d t h e r a d i a t i o n

o f t he e n cl o s u r e a n d i n d e e d b e t w e e n jus t t ho s e w a v e s o f
, , ,

t h e r a d i a ti o n wh ic h h a v e t he f r e qu e n cy v In t h i s st a t e O f .

e qu i l i b ri um t he r a d i a ti o n of f r e qu e n cy v a c qu ir e s a n i n t e n s i t y

K whic h a cc or d i n g to K ir chho17 3 La w i s equ a l to the i n tensi ty

”
y , ,
 '
T HE Q U AN T U M H Y P O T HES I S 7

b k b d d i i a t t hi s temp er a tu r e S e co n d ly , t h e
f
o l a c o -

y r a a t on .

e n e r gy U of t he o s c i ll a t o r p a ss e s i n t h e c o u r s e o f t i m e t hr o ugh

a l l po s si bl e valu e s the m ea
,
n v lu
a e 19 Hof wh ich i s fo u n d to
b e p r o p ort i o n a l t o t he i n te n s i t y X , a r e s ul t wh i ch s e e m s i m
V

m e d ia t e ly pl a u s ibl e s in c e t he e xc ita ti o n Of the os ci ll a t o r will

b e gr ea te r the m o r e i n te n se t h e r a d i a t i o n t h a t f a ll s o n i t .

Th e e xa c t ca c l ul a ti on of t h i s re l a t i on s hi p be twe e n IT an d U ,

on t he b a s i s o f c l a s s i ca l e l e t o d y
c r n a m c t h i s i s t he fi r s t
i s —

p a rt O f P la nc k s C lcul i — l e a ds t o the fu n d a m e n t a l
’
a t
a o n s

f or mul a :
(7)
In t he d p a r t P l a nc k 3° d e te r m in e d H a l th ough by a
c
se o n ,

m e th o d t h a t i s n o t fre e fr o m a mb i gu i t y a s a fu n ct i o n of v a n d
,

T o n t h e b as i s O f t he s e c o n d l a w of t h e r m od y n a m i c s He .

o b ta i n e d

The c o mb i n a tio n of ( 7 ) a n d ( 8 ) g i ve s us Wi en s ’
L aw of Ra d i a
tio n

§ 4 T h e Q u ant u m Hyp oth esi s Ra d i a tion

’
. . P l a nck s La w of

L u mmer a nd P r i ngshei m ,
h ow e v e r r e fu s e d to s u rr e n d e r
, .

In a f r e s h i n v e s t i g a t i o n 21 i n 1 9 00 t he y s h owe d t h a t i n the
r e g io n O f l o n g w a v e s Wi en s ra di a t i o n f o r mul a u n d o ub t e dl y d i d
’

not a gr e e w i t h t he r e s ul t s o f Ob se rv a t i o n A s a r es ul t o f t h i s
.
,

P la nc k i n a n i mp ort a n t p a p e r 22 wh i ch mus t b e r e ga r d e d a s
,

m a rk i n g the c r e a t ion o f the qu a n t um t heo r y de c i de d to ,

m od i fy hi s m eth o d o f d e duc i n g t he l a w of r a di a t i on n a m e ly , ,

by a l te r i n g t he e x p r e s sio n (8 ) wh i ch gi v e s t he m ea n e n er gy
O f th e o s c i ll a t o r bu t wh i ch i s n ot u n i qu e
, H e p r oc e e de d a s
.

f o ll o ws 23 In o r d e r t o di s tr i b u t e t h e wh ol e a va il a b l e e n e r gy
.

a m o n g t he o s c illa t ors he i m a g i n e d t h i s e n e r gy di vi d e d i n to
,
”
a d i s c r e t e n umb e r of fi n i t e e l e m e n t s of e n e r gy ( ener
gy
qu a n ta ) o f m a g n it ud e e a n d s upp o s e d t h e se e n e r gy qu a n ta
,

t o be d i s t r i bu t e d a t ra n d o m a m o n g t he i n di v i du a l o s c i ll a to rs
e xa c t ly a s a gi v e n n umb e r of b a ll s sa 5 m b e di s t ri bu t e d
y ,
a
y ,

a m o n g a c e r t a in n umb e r o f b o x e s sa 3 E a c h such di st r i
y , .

b u t i o n (O f 5 b a ll s a m o n g 3 bo x e s) m a y O bvi ously b e ca rr i e d
8 T HE Q U A N T U M T H E O RY
ou t in a n umb e r o f d iffe r e n t w a ys wh e r eby h owe v e r w e a r e , , ,

n o t c o n c e r n e d w it h wh i ch p a r ti cu l a r b a ll s l i e i n wh i ch p a r

ti cu l a r bo x e s b u t w i t h t he n u m ber c o n ta i n e d i n e a ch “
,
N ow .

S i n c e e a ch such d i str i bu t io n c or r e s p on d s t o a de fi n i te s ta t e
“

of the syst e m i t f o ll o ws f r o m wh a t h a s jus t b e e n s a i d t h a t

,

ea ch c on d i t i o n m a y b e r e a l i s e d i n a n umb e r o f d i ffe r e n t

wa y s t ha t i s e a ch c on d it io n i s ch a r a c t er i se d by a c ert a i n
, ,

n umb e r O f p o s s i b i l it i e s of r ea l i s a t i o n Th i s n umb er i s c a ll e d .

by P l a nck t he t h er m ody n a m i c p rob ab il it y W of t h e c on dition

i n qu e st i on Fo r i t i s obv i o us t h at t he p r o b a b il it y o f a c o n
.

d iti on o r st a t e i s the gr e at e r i e it w ill o ccu r t he m or e fr e , . .

qu e n tly the gr ea t e r t he n umb e r of w a y s i n wh i ch i t m a y

,

b e r eal i s e d B y m e a n s of th e usu a l fo r mul as of p e r mu t a

.

tio n s a n d c o mb i n ati on s of wh i ch t h e l a tt e r a l o n e c o m e i n t o
,

c on s i d e r a ti on h e re i t w as p o ss i bl e t o c alcul a t e t h e p rob a b il i t y
,

of a n y g i v e n d i s tr i bu ti on of t h e e l e m e n t s o f e n e r gy a m o n g

t he o scill a t or s a n d t hus a ls o t h e p r o b a b i l i t y of a g i v e n
,

e n e r g e t i c c o n d i t i o n of t h e sy s t e m o f o sc i ll a to r s a s a fu n c

t i on of t h e m e a n e n e r gy U o f a n o sc ill a t or a n d o f t h e e n e r gy
qu a n tum . N ow L B ol tzm a nn ?s ha s g i v e n a n e xt r e m e ly
, .

f e rtil e r ul e wh i ch c on n e c t s t he p r ob a b i l i t y o f s t a t e W of a
,

syst e m wit h i t s en tr ep g S a m a gn i tu d e wh i ch a s i s w e ll , ,

k n o wn pl ay s a s i m i l a r r Ol e i n t h e s e con d l aw of t he r m o d y n a
,

m i cs t o t ha t pl a y e d by en e r gy i n the fi r s t Thu s 8 w a s oh .

t a i n ed a s a fu n c t i on of U a n d e If n ow o n t he o t h e r h a n d
.
, ,

o n e a pl i e d t h e s e c on d l a w i t se lf w hi h t h en
p c e x
p r e sse s e ,
fi

t r opy S a s a fu n c ti o n o f t he m e a n e n er gy U a n d t he a b s olu t e
t e mp e r at u r e T t he f oll o w i n g r e sul t w a s ob t a i n e d by t h i s c i r
,

cu it on s p r o c e ss t he e n t r o py a s a n a u x il i a r y m a g n i t ude w a s
, ,

e l i m i n a t e d a n d a r el a ti on be tw een U T a n d e w a s ga i n e d
, , ,
.

T h i s fu n d a m e n t a l r e sul t fir s t o b t a i n e d by P l a nck i s a s
, ,

foll ows
e

6 ( k b e i n g a c on s t a n t)
3 157 — 1
Bu t fro m ( 7) a n d Wi en i D i sp l a c e m e nt La w ( 4) i t foll ow s
’

t h at for the m e a n e n er gy U of a n osc ill a tor a r e l a t i o n i

sh p of ,

the f oll o wi n g for m e xi s t s

U —v F .
 T HE QU AN T U M H Y PO T H ES IS 9

A
c o mp a r i son of ( 9 ) a nd ( 1 0) sh ow s t h a t U a s sum e s the
for m r e qu i r e d by ( 10) o n ly wh e n e i s s e t p ro p or t ion a l t o v the ,

f requ e n cy Th i s i s a n e s se n t i a l p o i n t o f P l a nck s Th e ory : i f

.
’

w e a r e to r ema i n i n a gr eem en t w i th Wi e n s D is l a cem en t L a w ’

p ,

the ener gy el em en t e mu st be set equ a l to hv

e ht ( )
1 1

Th e c o n s ta n t h wh ich On a cc ou n t o f i t s d i m e n s i on s ( e n er gy
, ,

x ti m e s c a ll e d P l a n ck s Q u a n tu m o
) i
’

,
f A ction ha s pl a ye d , ,

a s w e sh a ll s e e a r Ol e Of u n d r e a m e d oi i mp o rt a n c e i n t he
,
-

furt h er d e v e l opm e nt Of t h e qu a n t um t h e o ry .

B y c o m b i n i n g the f or m u l ae a nd
( )
1 1 t h e r e n o w n e d
r a d i at i o n l a w of P l a nc k f o ll ows a t o n c e

wh i ch P l a nck fir s t d e duc e d i n t he y ea r 1 900 i n t he m a n n e r

a b ov e d e sc r i b e d t h a t i s by th e hyp ot h e s i s o f e n e r gy qu a n t a
, ,
.

In t he s a m e y e a r a s w e ll a s i n the f oll o wi n g y e a r t h i s La w o f
Ra d i a ti o n w a s c on fir m e d v e r y s a t i s f a c t or i ly by H R u bens a n d .

F Ku r l ba u m 25 fo r l o n g w a v e s a n d by F P a schen 27 fo r sho rt
.
, .

w a ve s The l a t e r m ea s u r e m e n t s of r a d i a t i o n e m it t e d b y
.

bl a ck b od ie s 28 p ar t i cul a r ly the e xa c t wo rk c a r ri ed ou t by E
,
.

Wa r bu rg a n d hi s c oll a b o ra t or s a t t he Re i chs a n sta l t h a v e a ls o ,

d e m o n s tra t e d t he v a l i dit y Of P l a nck s f or mul a In O pp o s itio n ’

.

to t h i s W N er n st a n d Th Wu lf 29 a s t he r e sul t Of a c r i ti c a l
, . .
,

re v i e w O f t h e wh ol e e x p e r i m e n t a l m a t e r i a l a v a i l a bl e up t o t h a t

d a te h a ve r e c e n tly sh ow n th e e x i ste n c e o f d e vi a ti on s ( U p t o
,

7 p e r c e n t) b etwe e n th e m e a su r e d a n d t he c a lcul a t e d v a lu e s
a cc or d i n g t o P l a nc k s f or mul a a n d h e n c e f e e l t h e m s e lv e s
’

co n str a i n e d t o d e c i d e a ga i n st the e x a c t va l i di ty O f P l a nck s

’

for mul a Wh a t e v e r v i e w i s t a k e n Of t hi s c ri t i ci s m i t i s a t a n y
.
,

r a t e a p o w e rful i n c e n t i v e t o t a k e up a n e w t h e m e a s u r e m e n t

of the ra d i a t i o n e m i t t e d by bl a c k b o d i e s wi t h a l l t he fin e s s e

a n d p r e c a u t i on s Of m o d e r n e x p e r i m e n t a l sc i e n c e a n d t h e r e by ,

e sti o n wh e t h e r P la nc k s
’
t o d e c i d e fi n a lly th e i mp ort a n t u
q
La w i s e xa c tly va l i d or n ot ;

F or s hort wa v e l e ngt hs i s h igh fr e qu e n ci e s ( m or e e x a c t ly

-

,
. .
,
10 T HE Q U ANT U M TH E O R Y
fo r h i gh va lu e s of P l a nc k
’
s for mul a a ssum e s t he for m

and t hu s p a ss e s o v e r i n to Wien s La w ( of fo r mul a ’

.

wh i c h a s w e ha v e s e e n w a s c on fir m e d b y e x p e r i m e n t fo r
, ,

t h e s e f r e qu e n c i e s) In th e o t h e r l i m i ti n g c a s e i e for l o n g
.
,
. .

wa ve s l o w f re qu e n c i e s ( m o r e e x a c tly for s m a ll v a lu e s O f
,
g)
j
,

P l a nck s
’
for m ul a a ssum e s t he f or m

as is ea si ly fo u n d by d e ve l op i n g th e ex p on e n ti a l fu n c tio n
hv
eifie as a se r i e s . whi ch ha s b e e n c o n fi r m e d
Th i s l i m i t i n g l a w ,
i n th e r e g i o n o f l on g w a v e l e n gt h s ha d b e e n g i ve n p r e -

v i o u sl b
y y L o r d R a l
y g ei h 3 0 P l a nc k s f o r mul.a t hus c o n t a i n s ’

Wi en s L a w a n d R a gl ei gh s La w a s l i m i t in g c a s e s
’ ’
.

If w e u s e t h e wa v e l e n g th A i n s te a d O f the f r e qu e n cy v
-

P l a n c k s L a w t a k e s t he f o r m
’

he 2
1
5 he
A
e m 1

TO m a k e t h i s c l e a r t he i n t e n s i ty of r a d i a t i o n E , i s pl otte d
,

i n Fi g 1 a s a fu n c tion o f A for v a r i o us v a lu e s o f T
. Th e .

c u r v e s wh i ch e x h ib i t K a s a fu n c t io n o f v h a v e a qu i t e
”

S i m i l a r a pp e a r a n c e Th e m a x i mum Of t he E A c u r v e s l i e s a t
.
-

£7
0
t he po i n t at whi ch ,
h a s the va lu e 4 9 65 1 .

It fo ll o ws th a t
oh h
Am a x o 6 04 2 x 10 9
3 ( )
1 6
4 9 65 1
'
. k k
a wh i ch i s i d e n tic a l i n for m wi th Wi en s
r e a ti on ,
l ’
D i s pl a c e
m e nt La w ( 5 a ) .

F o r t he to t a l r a d i a t i o n w e ge t f r o m ( 1 2) or 1 5)
(
E MA
27 m
a
r ( 7)
4
.
4
y
‘
T 1
2 3
1 5c h
 CO N S E Q U EN C E S O F P LAN C K S TH E O RY
’
11

an e qu a t io n wh i ch giv e s ex p r e ssio n t o t he S tef a n B ol tzm a nn -

La w 31

From ( )
1 6 a nd ( 7) w e
1 gn i se t ha t t he m e a su re m e n t (a )
r e co

o f t he tot a l r a d i a t io n K
( ) a n d ( b) O f t h e

wa v e l e n gt h Of t he m a x i mum (Am ) a t
-
‘

ax ,

a fi x e d k n o w n t e mp e r at u r e a ll o w s u s t o ,

c a l c ul a t e t he t w o c o n s t a n t s h a n d k of t he

r a d i a t i o n f o r mul a 32 Fr o m Ku r l ba u m s
’
.

m e a s u r e m e n ts O f the S tefa n B ol tz m a nn -

con s ta n t
7 wh i c h w e r e a v a i l a bl e a t t h a t
,

t i m e a n d f r o m t he c o n s t a n t 8 O f Wi en s
’

D i s pl a c e m e n t L a w ( m e a s u re d by L u mm er
a n d P r i n shei m P l k f u d h f l
g ) a n c 33 o n t e o

l owi n g v a lu e s
h 6 54 8 x 10
-
27
[ e rg s ec .
]
k
522 .
( )
1 8

Corr e sp on d i n g v a ry i n g v a lu e s
to th e
wh i ch h a ve b e e n fou n d i n t h e c ou rs e Of
t i m e for t he c o n s ta n t s y a n d 8 t h e v a lu e s ,

of h a n d k h a v e u n d e r gon e c h a n g e s wh i ch

a r e n o t w o rt h wh i l e

r e c or d i n g here .

For p a rt i c ul a r ly
1 t he m e a su re m e n t O f
t h e t o t a l ra d i a t i o n
F IG 1 . .

a s w e s e e fr o m -

the s t ro n gly v a r y i n g v a lu e s g i v e n In n o t e 1 5 ha s n o t y e t -

r e ac h e d a s u ffi c i e n t d e g r e e Of c e r ta i n t y t o a ll o w a v e r y a c ,

cu ra t e c al c ul a tio n Oi th e t w o r a d ia t io n co n st a n t s h a n d k to b e
b a se d o n t he S tefa n B ol tzma nn c on s ta n t M e th o d s wh i ch
-
.

a ll o w h t o b e d e t e r m i n e d w i t h u n d o ub te dly much g r e a t e r

a ccu r a cy w i ll b e d e s c r i b e d l a t e r .

T h e or y
’
§ 5 Conse q u e nces
. of P la nc k s

T he d e du c tio n Of t he d i a ti o n for mul a a n d t he d e te r m i n a

ra

t i o n O f i t s c o n s t a n t s d i d n o t h o w e ve r e x h a us t the succ e ss e s
, ,

o f P l a nc k s n e w t h e o r y ; o n th e c o n t r a r y i mpo r t a n t r e l a t i o n
’

sh ip s O f t h i s th eo r y to o th e r d e p a r t m e n ts O f phy s i cs b e c a m e
12 T HE Q UANT U M T H E O R Y
i m m e d i a t e ly v e a l e d Fo r i t w a s fou n d 34 t h a t the c on sta n t
re .

k O f t he r a d i a t i o n f o r mul a i s n o t hi n g o t h er t h a n t he qu ot i e n t
o f t he a b so lu te ga s c o n s t a n t R ( wh i ch a pp ea r s i n th e e qu a

t i o n of s ta t e o f a n i d e a l ga s ) a n d t he S O c a ll e d A voga dr o
’

n umb e r N i s t h e n umb e r O f m ol e cul e s i n a r a m m ol e c u l e

, . .
g .

A s th e v a lu e Of R is su ffi c i e ntly a ccu r a t ely k n own fro m

t h e r m o dyn a m i c s

“ 1
8 31-
x 10 £ 33 7 .
°

d eg . d eg .

P l a nc k, ” by m ak i n g u s e o f t h e ra d i a t i o n m e a s u r e m e n ts w a s ,

a bl e to c a lcul a t e t he v alu e O f N . B y us i n g ( 1 8 ) h e f o u n d

N 6 1 75 10 23
( )
2 0
-

Th e g re e m e n t Of th i s v a lu e w ith t he va lu e s d e duc e d by
a

qu i te d i ffere n t m e thods i s v e ry s tr iki n g 36 A voga d r o s L aw .

’

f or ms the b r i d g e t o the e l e c tr o n t h eo r y F o r i t i s k n ow n .

t h a t t h e e l e c t r i c ch a r g e wh i ch t r a v e l s i n e l e c t r olys i s w i th
1 g r a mm e i o n t h a t i s w it h N i o n s i s a fu n d a m e n t a l c o n
-

, ,
-

st an t Of n a tu r e wh i ch i s c a ll e d th e F a r a da y It s v a lu e w a s
, .
,

a c c or d i n g t o t h e p o s i t i on O f m e a s u re m e n t s a t t h a t t i m e ,

9 6 5 8 3 1 0 e l e c tr o st a t i c u n i t s ( t h e v a lu e n o wa d a y s a c
10

c e t e d 3 7 i s 9 64 9 4 If n w h m o n o v al e n t
p o e a c

i o n c a r r i e s th e ch a r g e e O f t he e l e c t r o n t he e qu a t io n ,

Ne 9 6 58 3 10 10

mus t h old . Fr o m t h is , by u s i n g w e ge t

e 4 69 x 10
-
10
e e l c tr o st a ti c u n i t s ( )
2 2

The v a lu e Of the e l e c tron ch a r g e t hus c a lcul a t e d by P l a nck

fr o m the t h e ory of r a di at ion d i ffe r s O n ly by a b o u t 2 p e r c e n t
f r o m th e l a t e s t a n d m o s t e x a c t m e a su r e m e n t s O f R A . .

Mi l li ka n ” w ho fo u n d t he va lu e
,

e 4 7 74 10 1°
e e l c t r o s ta ti c u n i t s .

A t r uly a s t on i s hi n g re s ul t .
 CHAP TE R II

T he F a i l u re Of Cl as s i c a l S t a t i s t ics
T he E qui pa r t i ti on La w an d Ray l ei gh Ra d ia ti on
’
I. s La w of

F t h e s e gr e a t su c c e ss e s ha d jus t i fi e d f a i t h i n P l a nck s
’

h
T eo r y i t w as a l s o s o o n r e c o g n i s e d — a s ha d a l r ea dy b e e n
,

e mph a s i se d b y P l a n c k i n h i s fi r s t p a p e r s — t h a t t h e c e n t r a l
p oint of the th eor y l ay i n t he Q u a n t um H yp o t h e s i s , i e i n t h e . .

n ov e l a n d r e puls i v e c on c e p t i o n , t h a t t h e e n e r gy o f t he o s c ill a

t o r s Of n a t u r a l p e r i o d v w a s n o t a c on ti n u ously v a ri a bl e
m a g n itud e , bu t a lwa ys a n i nt e gr a l mul t i pl e of t he e l e m e n t o f
e n e r gy , t h a t i s e hv The r e c ogn i ti on O f t he n e c e ssi t y o f
.

t h i s hyp ot h e s i s h a s f or c e d i t s elf up on us m ore a n d m or e i n t he

c ou r s e o f ti m e a n d ha s b e c o m e e st a bl i sh e d m or e e sp e c i a lly
, ,

t h r ough i n d i r e c t e v i d e n c e i n a s much a s ever y a t temp t to w or k

,

w i th the cl a ssi ca l theor y ha s l ed logi ca l ly to a f

a l se l a w of

r a di a tion . F or wh e n P l a nck t u r n e d the r a di a ti o n p r obl e m

i n to a p r o bl e m o f p r o b a b i l i t y— for a d e fi n i t e a m o u n t of e n e r gy
w a s t o b e d i vi d e d a m on g t h e o s c i ll a t or s a cc o r d i n g t o ch a n ce ,

a n d t he m e a n v a lu e U o f t he e n e r gy o f a n o sc i ll a t or w a s t o

b e c a lcul a t e d— i t b e c a m e p o s s i bl e t o a pply t he m e t h od s Of
t he s t a t i st i c a l m e ch a n i cs f ou n d e d by Cl er k Ma x w ell L , .

B ol tz m a nn a n d Wi ll a r d Gi bbs
,
A n d t h e a ppl i c a t i on o f t h e s e
.

m e th ods to th e c a s e i n qu e st i on a pp ea r e d t o b e d e m a n d e d
fr o m t he st a rt i f the s ta n dp oi n t s e lf e v i d e n t i n cl a ss i c a l
, ,
-

phys i cs tha t the e n e r gy Of the o sc ill a tor c ould a ssum e i n

,

c on tin u ous se qu e n c e all v a lu e s b et we e n 0 a n d CO w er e

a do p t e d W h a t t h e n d i d s t a t i stic a l m e c h a n i cs r e qui r e ?
.
, ,

On e of i t s ch i e f l a w s i s th e l a w O f t he e qu i p art i t i o n o f k i n e t i c
e n e r gy 39 a ccor di ng to w hi c h i n a s ta te of s ta t is ti ca l e u i libr i um
, q
a t a bsolu te tem er a tu r e T ev er y d egr ee of fr eedo m o a mecha n
p f
i ca l sy stem , how ever comp l i ca ted , p ossesses the m ea n ki ne tic
13
l 4 T HE Q UANT U M THE O RY
ener gy i k T In
. t h i s e x pr e s s i o n t h e c o n st a n t k i s d e fi n e d by
a n d i s t hu s t h e s a m e c o n s t a n t a s t h a t wh i ch a pp e a r s

i n t h e La w Of Ra d i a t i o nsy s t e m o f f d e gr e e s Of fr e e d o m
. A ,

t h e r e f o re p o s s e s s e s a t a te mp e r a t u r e T a m e a n k i n e t i c e n e r gy
,

f l
.
a
k T . F o r e x a mpl e t h e a t o m, O f a m o n a to m i c ga s i s a

c o n figu r a t i on wh i ch p o ss e s se s t h r e e d e g r e es o f fr e e d o m i f w e ,

r e g a r d i t fr o m t h e p o i n t O f V i e w O f m e ch a n i c s a s a m a ss

p oi n t It s k i n et i c en e r gy at t he t e mp e r a t u r e T h a s t h e r e for e
.

a m e a n v a lu e 40 n i n d e p e n d e n t o f i t s m a s s a r e sul t whi ch
, ,

h a s b e e n k n ow n i n t h e k i n e t i c t h e or y O f g a s e s s i n c e t h e t i m e
o f Ma x w el l a n d wh i c h i s d e duc e d a s a c o n s e qu e n c e o f hi s
,

l a w O f d i s t r i bu ti o n O f v e l o c i t i e s .

P l a nck s l i n e a r o s c i ll a tor wh i ch i s e ss e n ti a lly i d e n t i c a l

’

w i t h a n e l e c tr o n v i b ra ti n g i n a s tra i gh t l i ne p o s se ss e s o n e ,

d e gre e Of f re e d o m ; i t s ki n e ti c e n er gy a t t he te mp erat u r e T
ha s t h e r efor e t h e m e a n v a lu e é k T N o w t h e m e a n p o te n t i a l
.

e n e r gy o f t h e o sc i ll a t o r i s e qu a l t o i t s m ea n k i n e t i c e n e r gy 1 1
‘
.

A s a r e sul t i t s m e a n t ota l e n e r gy (k i n e t i c plus p ot e n t ia l ) ha s

,

t h e v a lu e
U = hT ( )2 4

Th i s r e sul t Of cl as s i c a l s t a t i s t i cs wh e n c o m b i n e d wi t h th e
,

r e l a ti on
( )
7 d e duc e d f r o m c l a s s i c a l e l e c t r o dyn a m i cs g i v es ,

R a y l ei gh s La w O f Ra d i a t i o n
’

K . ( )
2 5

Of
’
wh i ch , as we sa w
( cf . is c o n ta i n e d i n P l a nc k s La w

iT
b
Radi at i o n as a l i m i ti n g c a s e fo r sm a ll v a lu e s of ’
t hat is ,
l
fo r l on g w a ve s or h i gh t e mp e r a t ur e s .

Th i s La w O f Ra d i a t i o n o f R a y l ei gh whi ch d e du c e d a s i t ,

i s f r o m the fu n d a m e n t a l p ri n c ipl e s Of c l a s s i c a l st a t i st i c s a n d
e l e c t r o dy n a m i cs sh o uld b e a bl e to cl a i m g e n e r a l v a l i d i t y fo r
,

a ll f r e qu e n c i e s a n d a ll t e mp e r a t u r e s s t a n d s n o n e t h e l e ss i n ,

gl a ri n g c on tr a d i cti o n t o Ob s e r va ti on For whi l e a l l O b s e rve d .

cu r ve s Of di stri bu t ion O f e n e rgy O f a b l a ck bo dy ( i s K pl o tte d . .

,

a s a fu n c t i on O f v T b ei n g c o n s t a n t) a l w a ys s how a m a x i m u m
, ,

t h e c u rv e e x p r e ss e d by ( 2 5) ri se s wi th ou t l i m it fo r r i s i n g .

v a lu e s of v a n d t h e re for e giv e s for the sum K 2

,

i n fi n ite ly l a r ge va lu e .
K dv an
f: y
FR UIT L E S S ATTEM PT S AT IM PR O VE MENT 15

§ 2 . Fru i tl ess A tt empts at Impr ovem e nt

Fr o m ver y diffe re n t qu a rt e r s a nd i n the m ost v a ri e d wa y s

a t t e mp t s w e re m ad e a s t i m e we n t o n to e s ca p e fro m
, ,

R a y lei gh s La w wi t h o u t d i s c a r d i n g c l a s s i c a l sta t i s t i ca l
’

m e c han ic s All i n v a i n
. Thu s J H Jea n s 42 wi th o u t. . .
,

m a ki n g u se O f a m a t e ri a l o s c ill a t o r co n s i de re d o n ly the
“
,

ra di a ti o n a s su ch i n a n e n cl o su r e a n d di s t r i bu t e d t h e wh o l e ,

e n e r gy Of r a d i a t io n a c c o r di n g t o t he L a w O f E qui pa rt i t i o n
”
o v e r t h e i n d i v i du a l d e gr e e s of fr e e do m Of r a d i a ti on ( whi ch
a r e h e r e t h e i n d i vi du a l vi b r a t i o n s t h a t a r e p o s s i b l e i n a n e n

cl o su r e ) F u rt h e r H A Lor en tz “ d e duc e d i n a p e n e tr a ti n g
.
, . .

i n v e s ti ga ti o n t h e t h e rm a l ra d i a t io n Of t he m e t a l s st a rt i n g f r o m ,

t he c on c e p t i o n t h a t t h e f r e e c o n duc t io n e l e c t r o n s
“
whi c h ,

c a rr y t he c ur r e n t
p r o duc e t h e r a d i a t i on by t h e i r c o ll i s i o n s
,

wi t h the a t o m s a n d a p p l yi ng the La w O f E qu ipa rt it ion to

,
'

t he m otio n O f t h e s e e l e c tro n s The p robl e m w a s a tt a c ke d.

i n a s o m e wh a t d i ff e r e n t fa sh io n by A E i n stei n a n d L Hopf “ . . .

Th e y i m a gi n e d t he P l a nc k o s c ill a tor fir mly a tt a ch e d to a

m ol e cul e a n d t h e n c on s i d e r e d t h i s c o mpl ex e x p o s e d to t he
,

ra d i a t io n a n d t he i mp a c t s O f o t h e r m o l e cul e s Th e L a w O f .

Ra d i a t io n c o uld t he n b e d e duc e d fr o m t h e c on d i ti on t h a t t he
i mpul se wh i ch t h e i mp a c t s o f t h e m ol e cul e s gi v e t o th e co m
,

pl ex mus t n ot o n t he a v e r a ge b e ch a n ge d by the i mpul se s

, ,

wh i ch t he ra dia tio n gi ve s t o the o sc ill a tor We m a y a lso .

m e n t ion a p a p er of A D F okker 45 wh i ch w a s suppl e m e n t e d

. .

b y M P l a nc k m In t hi s by t he a i d of a g e n e r a l l a w d u e to
. .
,

E i n stei n the sta ti sti c a l e qu i l i b r i u m be t we e n t he ra d ia t i o n

,

a n d a l a r g e n umb e r o f o s c i ll a to r s w a s e xa m i n e d o n t he b a s i s

Of th e cl as s i c al t h eori e s Al l th e s e d i ffe r e n t wa y s e n d e d
.
,

h owe v e r a t t he sa m e p o i n t ; t h e y a ll l e d t o Ra y l ei gh s La w
,
’
.

A n d fin a lly a t t h e So lva y Co n gr es s i n B r u ss e ls in 1 9 1 1
, ,

H A Lor en tz 47 S how e d i n t he m o s t ge n e ra l m a n n e r
. .
,

i m a g i n abl e t h a t w e a rr i v e o f n e c e s s it y a t t h i s wr o n g l a w
, ,

if w e a s s um e th e v a l i di ty Of Ha m i l ton s P r in c ipl e a n d o f
’

the P ri n c i pl e o f E qu i p a r t i t i o n for the to t a l i t y o f the ph e n o

m e n a ( o f m e ch a n i ca l a n d e l e c tr o m a gn e ti c n a t u r e ) whi ch
ta k e pl ac e i n a n e n cl o sur e co n t a in in g ra di a t i o n m a tte r a n d , ,

e l e c tr o n s On ly i n t he l i m i t i n g ca se O f h i gh te mpe ra t ure s o r
.

sm all fr eq ue n c i e s d o th e r es ul t s of t he cl a ssi ca l t h eo ry a gr ee
wi th the r es ul ts Of Ob se r va t io n 48 .
 CHAP TE R III

T h e D e v e l o p me nt a ndt he R a mi fica t i ons of the

Q u a nt u m T he o ry

§ I . Th e A b s orp ti on a nd E mi ssi on of Qu ant a

S stat e d b ove the c on v i ctio n w as b ou n d t o e s t a bl i sh
a ,

it s elf t h a t e v e ry a t t e mp t to d e duc e t he l a ws Of ra d i a t ion

O n t h e b a s i s of cl a ssi c a l s t a t i s ti c s a n d e l e c tr ody n a m i c s w a s

doo m e d f r o m t he o u t s e t t o f a ilu r e a n d i t w as n e c e s sa r y to ,

i n t r oduc e a h i t h e r t o u n k n o w n di sc on tin u i ty in to the t h e o r y .

It w a s of c o u rs e cl e a r t h a t t h i s a t o m i si n g Of e n er gy would
, ,

c on fl i ct sh a r ply wi th e x i stin g a n d a pp a r e n tly we ll fou n d e d -

t h e or i e s F or if t he e n e r gy o f the P l a nc k o s c i ll a t or w a s o n ly
.

t o a m ou n t t o i n t e gr a l mul tipl e s Of 6 hr a n d t h er e fo r e w a s ,

o n ly t o b e a bl e t o h a v e t he v a lu e s 0 e 2 c 3 6 t h e n Sin c e , , , ,

t he o scill a to r o n ly ch a n g e s it s e n e r gy by 6 111 18 8 101) a n d a b

s or p ti on the c on clus i on w a s i n evit abl e t h at o scill a tor s c a n n o t
,

a bs orb a n d e m i t a m o u n t s of e n e r gy of a ny m a gn i tud e b u t on ly

whol e mul t ipl e s of e ( Qu a n tu m emissio n a nd qu a n tu m

.

a bsorp ti on ) Th i s con clus i on i s i n a bsolu t e c o n t r a di c ti on t o

.

cl a s si c al el e c tr ody n a m ics For a cc or d i n g t o the e l e c tr on

.
,

t h eor y a n e l e c tr o m a g n et i c o sc i ll a t or for i n s ta n c e a v i b r a t
, ,

i n g e l e c tr on e m it s a n d a bs o r bs i n a fi e ld O f r a d i a t ion p erf e c t ly
,

c on ti n u o usly t h a t i s t o s a y i n su ffic i e n t ly sh ort t i m e s i t e m it s

, ,

O r a bs or bs i n d e fi n i t ely sm a ll a m o u n t s O f e n e r gy .

Ei ns tei n L i g h t q ua nta ; P h e nome na

’
§ 2 . s -

Of F l u ct ua ti on in a F i e ld
of R a d i a ti on

Thus v e r y e n t r a n c e i n to t he n e w c o u n t r y t h e r e
at t he
ya wn ed a gulf wh i ch ha d e ith er i n vi e w of t he p re vi ous
, ,

succ es s Of the cl a ssi c al th e or y to b e b r i dge d o v e r by a co m ,

p r o m i se ; Or fa il i n g t hi s t ra d it ion would h a ve t o b e d i sc a r de d
, ,

a n d th e ga w o uld b r e l e n tl e s sly e n l a r g e d E i t i f l t h i m
p e ns e n e .

16
 EI N S T E I N S LI G H T QU ANTA
’ '
- l7

se l f c o mp e ll ed t o ta k e the l a t te r r a dic a l co u rs e On the b a s i s .

O f v e r y Or i gi n a l c o n s i d e ra t i o n s 49 h e se t up t he hyp o t h e s i s t ha t
,

t he e n e r gy qu a n t a n o t o n ly pl a y e d a p a rt a s P l a nc k h e ld i n
, ,

t he i n te ra c t io n b e t w e e n ra d i a t io n a n d m a t te r ( r e s on a t o rs o r
os c ill a t o r s u t t ha t r a d i a ti on d
) b
, w h,en o
p p g
r a a te t h r o u g h a

va cu u m or a nym edi u m , p ossesses a qu a n tu m l ike s tr u c twre -

( g q
Li h t -
u a n tu m h yp oth es i s) .A cc o r d i n gly
”
a l l r a d i,a t i o n w a s

to co n si s t O f i n di vi s i bl e r a d i a ti o n qu a n t a wh e n th e e n e r gy
i s b e i n g p r op a g a t e d f r o m t h e e x c i t i n g c e n t r e i t i s n o t di v i d e d
,

e v e n ly i n t he for m o f s ph e r i c a l w a v e s o v e r e v e r i n c r e a s i n g -

vo lum e s o f sp a c e , b u t r e m a i n s c on c e n tr a t e d i n a fi n i t e n umb e r
Of e n e r gy c o mpl e x e s ,
wh i c h m o v e l ik e m a te ri al st r uc t ur es ,

a n d c a n o n ly b e e m itt e d a n d a b so r b e d a s wh ol e i n d i vi du a ls .

E i nstei n b e l i e v e d h i m s e lf f o r c e d t o t h i s s t ra n g e c o n c e p t ion ,

whic h b r e a k s wit h a l l the Ob se rv a t io n s th a t a pp e a r to

s uppo rt th e u n d ul a tor y t h eo r y , b y s e v e r a l i n v es t i g a t i on s ,

a l l o f wh i c h l e d t o t h e sa m e c o n clu s i o n He w a s pe r
.

su a d e d to t hi s vi e w b y t h e r e sul t O f c a l c ul a t i o n s d e a l i n g

wi t h c e rt ain ph e n o m e n a Of fluc tu at i o n ph e n o m e n a wh ich ,

a r e fa m il i ar t o us i n s t a t i st i c s a n d p a rt i c ul a r ly i n t h e ki n e t i c

th e o r y o f g a s e s . It i s w e ll k n o wn t h a t i n a ga s wh i ch
co n t a in s n m ol e cul e s i n a v olum e v0 the S p a ti a l d i stribution
,

Of t h e se m ol e cul e s i s fa r f r o m c o n s t a n t, b e i n g s ubj e c t t o v ar i

a t i o n on a c c o u n t of t h e m ot i on O f t h e m o l e c ul es In d e e d i n .
,

p r i n c ipl e , e x tre m e c a se s a r e po ss i bl e a s th at for e x a mpl e i n , ,

whi ch all n m ol e cul e s a r e c oll e cte d a t a g i ve n m o m e nt in a

"

f ra ct io n a l p a rt v (< v0) of th e volum e Th e p r ob a b i l i ty O f

.

t h i s ra r e co n s t e ll a t ion i s k n o wn t o b e

w :

an e x trao r di n a ri ly s m a ll n umb e r wh e n n i s gr ea t ; t ha t i s to
sa y t he e v e n t i n qu e s t i o n o ccu r s e x t r e m e ly ra r e ly
,
.

N o w th e S p a t i a l d e n s it y Of t h e ra d i a t i o n e n c l os e d wi t hi n a
,

volum e v0 i s s ubj e c t t o qu i t e a n a l o gous va ri a ti o n s If E i s .

t he t ota l e n e r gy o f t he ra d ia t i o n ( s upp o s ed t o be m o n oc h r o
m a t i c) a n d if i t s fr e qu e n cy v i s S O gr e a t or i t s t e mp e r a tur e
,

so l o w t h a t Wi en s L a w o f Ra di a t i o n h o ld s fo r i t t h e n t h e
’

, ,

proba b il i ty t h at t he wh ol e r a di a t i on o ccup i e s the p a rt i a l

v olum e v ( < v0) i s ac co d g ,
r in t o E i n s t ei n 80
,

2
18 T HE Q U AN T U M TH E ORY
w 2
( 7)
A c o mp a r i s on w i t h ( )
2 6 h ows t h a t the ra d iation wi thi n
S ,

the l i mi ts of va l idi ty of W i e n s L a w beha ves a s if i t w er e m ad e

’

up o f n
53) -

1
i ndep end en t comp l ex es o f ener gy , ea c h o f ma g

n i tu d e hv .

Tw o oti n v e s ti g a t i o n s 5 1 of E i n stei n l e d t o the s a m e

her
c o n clus i on In t h e fi r s t a v e r y l a r ge v olum e fil l e d w i t h
.
,

b l a c k b o dy r a d i a ti on i s c on s i d e r e d wh i ch c o mmu n i c a t e s wi t h
-

a sm a ll v o lum e v If E i s the m o m e n t ar y e n e r gy of t he
.

r a d i a t i o n of f r e qu e n cy v i n t he v olum e v , t h i s e n e r gy v a r i e s ,

a s i s k n o w n ir r e gul a r ly w i t h t he t i m e a b o u t a m e a n v a lu e
,

E t he m a gnitude c all e d the fluc tu a ti on of

e E E is the
e n e r gy N ow th e g e n e r a l t h e o ry of s t a ti s t i cs l ea ds t o
.
,
t he
2
foll owi n g v a lu e for t he m e a n squ a r e th at i s for 5
53
, , ,

dE
3 w ( )
2 8
dT
If we re by the va lu e Ob t a in e d f r o m P l a nck s La w of
pl a c e E
’

Rad i a t io n w e Ob t ai n for t he m e a n squ ar e o f fluc tu a t i o n a n

,

ex p r e s s io n w i t h t w o t e r m s } 33 i n wh i ch o n ly o n e t e r m c a n b e

c alcul a t e d on t he b a si s of the cl a ss i c a l u n dul a tory t h e ory ;

t h e s e c o n d wh i ch g r ea tly e x c e e d s th e fir s t i n m a g nit ud e
,

wh e n the d e n s i ty of r a d ia n t e n er gy i s l ow (th a t i s a t h i gh ,

fr e qu e n ci e s o r a t l ow t e mp e ra tu r e s i n short wh e n Wi en s
'

, ,

La w i s v a l i d) c a n o n ly b e u n d e r s too d wh e n w e a g a i n p i c tu r e
,

t he r a d i a t i on a s c o mp ose d of i n d i v i s ibl e e n e r gy qu a n t a -
.

Th e s e c o n d o f E i n stei n s t w o i n ve st i ga t i o n s t o wh i ch w e
’

r e f e rr e d a b o v e d e a ls w i t h t h e fluc t u a t i o n s o f i mpul se wh i ch
,

a f r e e ly m o v a bl e r e fl e c ti n g pl a t e i s su b j e c t e d t o i n a fi e ld o f

bl a c k b ody r a di a tio n o n a ccou n t of the i rr e gul a r fluc tu ati o n s

-

Of t h e p r e s s u r e of r a d i a t i o n If i n a dd i tio n the pl a t e i s su b
.
, ,

r r e gul a r bl ows O f m l ul u n d er t h e
j e c t e d t o t h e i g as o e c e s -

i n flu e n c e of wh i ch i t e x e cu t es B ro w n i a n m o ve m e n t s th e r e ,

mu st be e qu i l i b r iu m b e tw e e n the i mpul s e s wh i ch t h e m ol e
cul e s on t h e o n e h a n d a nd t h e r a di a tion on t he o th er i m
, ,

p ar t to the pl a t e If n o w w e a ssum e P l a nck s La w to h old

.
, ,
’

for the ra d i at io n th e r e a g a i n foll ows for t he m e a n squ ar e o f

,

t h e v a r i a ti o n s i n i mpul s e d u e to th e r a d ia ti o n a n e x p r e ss i o n
 T R A N S FO R MAT I O N OF LI G H T Q U A N T A -
19

i n t w o t e r ms on ly ,
pl a in e d by the u n
one of wh i ch is ex

d u l a t o r y t h e or y o f l i gh t T he o t h e r t e r m p o i n t s t o a
.

qu a n tum l ik e s tructu r e of the r a d i a tio n a n d t h i s sugge s t s the

-

i n t r odu c t i o n of t he l i gh t qu a n tum hyp ot h e s i s -

.

§3 . T ra ns forma ti o n of Li gh t— qu a n ta int o ot her Li gh t qu a nta

-
or

El ect r oni c E ner gy

H ow e ve r s tr a n g e th i s hyp o t h e si s a pp ea r e d i t w a s n o t to b e ,

d e n i e d t h a t i t w a s c a p a bl e of e x pl a i n i n g s i mply a n d n a t ura lly

a n umb e r o f ph e n o m e n a wh i ch c o mpl e t e ly b a fll ed t he u n

d u l a to ry t h eo ry A v e r y s tri k i n g e x a mpl e o f t h i s i s a ffor d e d

.

b y t he l a ws of p hO Sp ho r e s c e n ce i n v e s t i g a t e d by P L ena r d ,
.

a n d hi s c o w o rk e r s a n d e s p e c ia lly b F
’
-

, y S to k es L a w o r if .

v
p
i s t h e f r e qu e n c y o f t h e ph o sph o r e sc e n t l i gh t e m i t t e d ,

a n d v t h e f r e qu e n c y o f t h e l i gh t e xc i ti n g ph o sph o r e s c e n c e
, ,

t h e n a c c or d i n g t o E i n stei n s c on c e p ti o n “ o n e qu a n t um hv
’

, , ,

o f t h e ex c i t i n g r a d i a t i o n i s c h a n g e d t h r o ugh a b s or p t i o n by

the a t o m o f t he ph o sph o r e sc e n t s u b sta n c e i n to o n e qu a n t um

hvp o f th e l i ght of ph o s ph o r e s c e n c e A c c o r d i n g t o t he p r i n .

c i l e o f e n e r gy mus h v h h i > A d
p w e t,
a e v
Z p v e v v
p
n e , . .
e .

t h i s i s S to kes L a w
’

Furt h e r a n o th e r f a c t i n t he r e a lm of ph o s ph or e s c e n c e
,

ph e n o m e n a S p e ak s a ga i n s t t h e u n dul a ti o n hyp o t h e si s a n d i n
f a vo u r o f t h a t of l i ght qu a n ta A cc o r din g to th e cl a s sica l
-
.

u n dul a t or y t h eor y a l l m ol e cul e s o f a ph o s p ho r e s c e n t bo dy

,

o n w hi ch a l i gh t w a v e i mp i n g e s S h o uld a bs o r b e n e r gy f r o m
-

t he w a v e a n d t hu s a ll s i mul t a n eo u sly b e c o m e a bl e to e m i t
,

pho spho r e sc e n t l i gh t In r e a l i t y r e l a ti v e ly o n ly v e ry fe w
.
,

m o l e c ul e s a r e e x c i t e d to phosphor e s c e n c e a t the sa m e ti m e ,

a n d o n ly g r a du a l y In t h e c ou r s e o f t i m e d o e s th e n umb e r o f
l , ,

m o l e cul e s e x ci t e d In c r ea se It wo uld t hu s a pp e a r a s i f the .

l i ght wa ve fa l li n g o n th e ph os pho r e sc e n t b ody ha s n o t e qu al

-

i n t e n s it y a l o n g i t s wh ol e fr o n t — a s t h e c l a s s i c a l t h eo r y
a s s um e s — b u t r a t h e r a s i f i t c o n s i s t s o f S i n gl e e n e r gy c o m -

p l e x e s t hr o w n o u t by t he s ou r c e o f l i gh t so t h a t t he w a v e p o i n t
,
-

po s se s se s a s i t w e r e a he a d y s t ruc t u r e i n wh i ch a c ti v e
, ,
“
,

p o rt i on s (l i ght qu a n t a) al te r n a te w i t h i n a c ti v e ga p s
-

Th i s c o n c e p t i o n o f t h e b e a d y wa v e fr o n t had pl a ye d a -

p a rt be fo re t he a dv e n t of E i ns tei n s hyp o t he s is of li ght qu a n ta ’

-
.

J J Thomson “ had t ri ed to m a k e u se o f i t to e xpla i n t he

. .
20 T HE Q UA N T U M TH E O RY
f a c t t ha t whe n a ga s i s i o n i s e d b y ul t r a v iol e t l i ght o r Ro n tge n
,
-

rays o n ly a r e l a t i v e ly e x t r e m e ly s m a ll n umb e r o f a s m ole

g
-

c ul e s a r e i o n i s e d T hi s i s a ph e n o m e n o n wh i c h i s qu i te
.

a n a l o go u s t o t h e a b o v e n a m e d ph e n o m e n o n-
o f ph o s ph o r

e s c e n c e ; fo r t h e s e t oo a c c or d i n g t o L en a r d s v i e w t h e e x c i
’

, , ,

t a t i o n c o n s is t s i n t h e d i sju n c ti o n t h r o ugh t he a g e n cy o f t he ,

r a di a tio n o f e l e c tr o n s f r o m t h e m o l e cul e s o f t h e ph o sph o r

,

e s c e n t b o dy a n d t h es e e l e c t r o n s a t t a c h t h e m s e lv e s t o
,
st o r a g e

a t o ms . On t h e r e t u r n o f t h e se e l e c t r o n s t o t he p a r e n t
m ol e c ul e s e n e r gy i s se t fr e e a n d s e n t o u t a s ph o sph o r e sc e n t
,

l igh t Th e i o n i s a tio n o f ga s e s b y ul tr a v i ol e t l i ght o r ROn t

.
-

n r a ys 5 6 i s a ls o c a p a bl e o f b e i n g e x pl a i n e d n a t u r a lly by t h e
g e

l i gh t qu a n tum hyp ot h e s i s
-
If w e s upp o s e w i t h E i n s tei n
.
,

t h a t o n e l i gh t qu a n t um hv i s u s e d u p i n i o n i s i n g o n e m o l e
-

c ul e ,
th e n wh e r e J i s the work r e qu i r e d to i o n ise
o n e m ol e c ul e t h a t i s t o s a t o r e m o v e a n e l e c tr o n f r o m i t
, y ,
.

We h a ve u n d e r c on si d e ra ti o n h e r e a ph e n om e n o n wh i c h b e
l o n g s t o t he gr e a t b ra n c h O f p hoto elec tr i c p henom en a 57 i e -

, . .

t h e l i b e r a t i on o f e l e c t r o n s f r o m g a s e s m e t a l s a n d o t h e r s u b , ,

s t a n c e s by t he a c ti on O f l i gh t A c c or d i n g to t he hyp ot h e s i s .

o f l i gh t qu a n t a i n a ll t h e s e p r o c e s se s l i gh t qu a n t a a r e c h a n ge d
-

,
-

i n to ki n e t i c e n e r gy o f t h e e l e c t r o n s hu r l e d o ff fr o m t he b ody .

If w e a gain a do p t E i nstei n s s t a n dp oi n t a c c or d i n g t o whi ch ’

o n e l i gh t qu a n t um hv i s t r a n sf o r m e d i n t o t he k i n e t i c e n e r gy
-

of o n e p r o j e c t e d e l e c tr o n w e mu st h a v e t he f oll o w i n g r e
,

l at ion 58 for t he e n e r gy o f e m i s s i on o f the e m itte d e l e c tr on s ,

e a ch h a v i n g a m a s s m :

s
a nt a P .
( )
2 9
’
Th i s i s c a ll e d E i n stei n s L aw of t h e P h o t o -
l
e e c t ri c E ffe c t . In
t hi s , P i s t he w or k t h a t h a s to be d o n e to t e a r t he e l e c tr o n
a w a y f r o m t he a t o m a n d t o p r oj e c t i t f r o m t he p o i n t a t
,

wh i ch i t i s t o r n f r o m t he a t o m up t o the p oint a t wh i ch i t
l e a v e s th e s u rf a c e o f t he b o dy For t he e n e r gy of t he e m i tt e d .

e l e c tr o n s w e t hu s o b t a i n a l i n e a r i n cr e a s e wi t h t h e p e r i od i c i t y

o f t he l i gh t wh i c h r e l e a s e s t h e m Thi s l a w wh i c h m a n y i n .
,

v e st i ga t or s h a v e a tt e mp t e d t o p r o v e w i t h v a ry in g suc c e s s , ,

h a s r e c e n tly b e e n v e r i fi e d by R A Mi l l i ka n 9 fo r t h e n o r m a l
5 . .

ph oto e l e c tr c e ffe c t of the m e t a ls N a a n d Li with s uch a

-
i 60

d e gr e e of a ccu ra c y th at w e c a n a c tu a lly u se th i s m e tho d for

 E LE C T R O N I C ENE RG Y 21

t he e xa c t d e t e rm i n a t i o n of v a lu e f ou n d b y Mi l l i ka n
h . Th e ,

h 6 5 7 x 10 27 , i s i n g o o d a gr e e m e n t wi t h t he v a lu e
-

h 6 54 8 x 10
‘ 27
f o u n d b y P l a nc k f r o m r a d i a t i o n m e a s u r e
m e nts .

In an e n t ir e ly Si m il a r m a n n e r as was used fo r t he
phe n o m e n a of p h ph e no m e n a of fl uor es
O S ho r e s c e n ce
p ,
t he
ce nc e i n t h e r e g i o n s o f t h e ROn t e n a n d vi s i bl e ra d i a t i on s m a y
g
be e x pl a i n e d by t he hyp o t he s i s o f l i gh t qu a n t a Th e i n -
.

ve s t i ga t i o n s of S a d l er M d e B r ogl i e, a n d
Oh . B a r kl a , ,
.

E Wa gner 6 1 h a v e s h o w n t he fo ll o w i n g : if a b o dy i s i n u n
.

da t e d wi t h Ro n t ge n r a y s a n d i f the a b sor pt i o n of t h e se ra ys b y
,

t h e bo dy i s m e a s u re d wh i l st th e h a r d n e ss (i e the fr e qu e n c y . .

r a ys i s var ie d a b s or p t i o n p a s s fr o m
v
)
e o f t h e t he a s w e
, ,

l o we r t o hi gh er w s udd e n ly i n c r e a se s t o a h igh v a lu e fo r a
e,

c e r t a i n v a lu e o f v A t t he s a m e m o m e n t t he b o dy b e g i n s
6. ,

a t t h e e x p e n s e o f t h e e n e r gy a b s o r b e d t o e m i t a second a r y ,

Ron tgen r a d i a ti on cha r a c ter i sti c of the bod y i tself i n th e f or m

o f a l i n e S p e c t r um It fu r t h e r a pp e a r s t h a t a l l l i n e s e m itte d
.

h a v e a l o w e r v t h a n t h a t o f t he e x c i t i n g r a d i a t i o n AS a .

m a t t e r o f fa ct t he hyp oth e s i s O f l i ght qu a n t a r e qui r e s t h a t th e

,
-

r a d i a t i o n qu a n t um h
-
o f a l l r a y s e m it t e d a s s e c o n d a ry r a d i a
v

t i o n s h ould b e s m a ll e r t h a n th e qu a n t u m hv o f t he p r i m a r y
e x c i t i n g ra y s F or e x a mpl e t he r e g i o n o f fr e qu e n c i e s wh i c h
.
,
”
s e r v e s t o e x c i t e t he K s e r ie s s t r e t ch e s f r o m a s h a r ply
“ -

d efi n ed l i m it uh (t he s o c a ll e d e dge of the a b s orp t i on b a n d

upw ar d s t o wa r d s highe r fr e qu e n c i e s ; wh e r e by vk i s s o m e
wh a t l ar ge r t ha n the h a r d e s t k n o wn l in e ( y ) of the K S e r i e s -
.

In o t h e r wo r d s the e x c it a t i o n o f s e c o n d a r y ROn t ge n ra d i a t i o n
,

b y p r i m a ry ROn t ge n r a y s a l so o b e y s S tokes La w
’
.

54 . T h e T r a n sfor ma ti on of E l e ct ronic E n e r gy i nto L igh t q u a n ta -

It i s ver y
g fic a nt sit h a tni t h e t ra n s f o r m a ti o n o f l i gh t
,

qu a n ta i nto ki n e ti c e n e r gy o f e l e c t r o n s i s a l so a s i t we r e , ,

r e v e r s ib l e t h a t i s t he O ppo s i te p r o c e s s a l so oc c u r s i n
“
, ,

n atur e b whi c h l i gh t qu n t ul t f r o m t he ki n e t i c e n e r gy
y a a r e s -

of c h a r ge d p a rt i c l e s A g o od ex a mpl e o f p r o c e s s e s o f t h i s
.

ki n d i s a ffo r d e d by th e ge n e ra t i o n o f ROn t ge n ra y s by t he
i mp a c t o f qu i c k ly m o v i n g e l e c tr on s ( ca t ho d e ra y s ) o n m a tt e r
-
.

If sa y the cha ra ct e ri s t i c K se ri e s of a ce rt a i n e l e m e n t i s to
, ,
-
22 T HE Q U A NT U M TH E O RY '

be ge n e r a t e d by the i mp a c t o f c a tho d e r a ys upo n a n a n ti

c a t h o d e f orm e d o f t h e s a i d e l e m e n t t h e n t he ki n et i c e n e r gy ,

E o f a n i mpi n gi n g e l e c tr o n mus t e x c e e d a c r it i c a l v a lu e E X .

F or if w e i m a g i n e E ch a n g e d i n t o a l i gh t qu a n t um hv t h e n -

e,

v6 mu st f a ll w i th in the r e gion o f e x c it at i on of t he K s erie s a n d -

K ( K
mu st t hus b e v V b e i n g t h e f r e qu e n cy o f t h e e dg e O f t h e

a b so r p t i o n b a n d f oll o w s t h a t E
xl
) It .
2 t ( E F r o m t hi s

th e r e f o ll o w s a n i mp o r t a n t r e l a t io n b e t w e e n t h e f re qu e n cy VK
o f t h e e dg e o f t h e a b s o r p t i o n b a n d a n d t he c r i t i c a l v a lu e E K

of t h e e l e c t r o n i c e n e r gy i e t he sm a ll e s t v a lu e o f t he e n e r gy
,
. .

a t wh i c h t he e l e c t r o n i s j u s t a b l e t o ge n e r a t e t h e r e qu i r e d

s e c on d a r y r a d i a t i o n Th i s qu a n tum r e l a t i o n E K
.
t h a s -

p r ov e d qu it e c orr e c t a c co r d i n g t o m e a su r e m e n t s c a r r i e d ou t
b y D L Webs ter 62 a n d E Wa gn er 63 a n d c on v e r se ly p r e s e n t s
. . .
, ,

wh e n E K a n d vK a r e su ffic i e n t ly a ccu r a t e ly k n o w n a m e t h o d ,

fo r the d e t e r m i n a t i o n o f h “ .

N o w i t i s k n o wn t h a t t he c a t ho d e r a y s o n s t r i ki n g the
, ,

a n t i c a th o d e d o n o t m e r e ly e x c i t e t h e ch a r a c t e r i s t i c R On t ge n
-

r a d i a ti on t h a t i s a l i n e s p e c t r um b u t e x c i t e a c o n t i n u o u s
, ,

sp ec tr um a s w ell th e s o c all e d i mpul se r a d i at i on (B r em s

,
-
“

s tr a hl u n g) If w e t h ere for e s e l e ct a n y f r e qu e n c y v O f t hi s
.

Con t i n u o us s p e c tr um t h e i d e a s o f t h e hyp ot h e s i s o f l i gh t
,

qu a n t a i mm e d i at ely s ugge st t he c o n c lu si o n t h a t a d e fi n i te
m i n i mum e n e r gy E m O f t he i mp i n gi n g e l e ctr on s i s n e c e s s a ry
t o e x c i t e t h i s f r e qu e n c y a n d t h a t w e mu s t h a v e E
v,
m
h v .

The i n ve st i ga t i on s of D L Webster 62 W D u a ne a n d F L. .
, . . .

Hu n t 55
,
A W H u ll a d
. . n M Ri c e 66 E W a gn er 6 7 F D essa u er
.
, .
,
.

and E . B a ck 68 h a ve c on fi r m e d t h e s e for mul ae w i t h t he

gr e a t e st a c cu r a c y a n d t hu s f or m t he fo u n d a t io n o f o n e o f
,

t h e m os t t ru st w o r t hy m e th od s for t h e p r e c i s e m ea su r e m e n t
o f t h e m a g n i t ud e h The f oll o wi n g v a lu e s w e r e O b t a i n e d
.

h x
( D u a ne Hu n t ; h
) -
x
( W ebs ter ;
)
h x
( W a gn er ) .

W e a l so m e e t wi th s i m i l a r ph e n o m e n a i n th e v i s i bl e a n d
n e i ghb ou r i n g r e g i o n s of t h e s p e c t rum Thu s J F r a n ck . .

a d G
n . H er tz s h ow e d t h a t t he i mp a c t o f e l e ctro n s up o n
6 9

m e rcu r y va p ou r m ol e c ul e s c a n b e u s e d t o e x ci te a d efi n i t e
ch a r a c te ri st i c flu or e sc e n c e l i n e o f m e r c u ry of w av e l e n gt h -

A, 2 53 62 (i e t , . . i f t he ki n e ti c e n er gy of the
 H Y P O T H E S I S OF LI G H T -
Q UAN T A 28

l c t r on
e e c ds a c e rt a in c r iti ca l v a lu e E 0 In th i s con
e x ee .

n exi on t h e y fo u n d t h a t t he r e l a t i o n E 0 kr o w a s a g a i n
fulfill e d wi t h gr e at a ccu ra cy ” W e Sh a ll r et u rn to t h e se
.

e x p e ri m e n t s a n d o t h e r s c on n e c t e d wi t h t h e m l a te r S i n c e t h e y ,

pl a y a n i mp ort an t p a rt i n c o n fi r m i n g the m o s t r e c e nt m o d e l
of t he a to m .

5 O ther A p p li ca ti o ns
. of th e Hyp oth e si s of Li gh t q ua nta-

In a c on s i d e r ab l e n u m b e r O f ot h e r ca se s wh i ch sha ll only ,

b e n ot i c e d s h or t ly a t t h i s p o i n t t h e hyp o t h e s i s of l i ght q u a n ta
,
-

ha s p r ov e d o f v a lu e e sp e c a ly i,
l i n t h e ha d
n s o J S ar k
f t 71 and .

E i ns tei n T
. hus S ta r k 72 ha s m a d e u s e of thi s hypo t h e s i s t o
i n te r p r e t t he fa c t t ha t th e ca n a l ra y p a rt i cl e s e m i t t h e ir -

”
“
k i n e ti c r a di a t ion o n ly wh e n t h e i r s p e e d e x c ee ds a c e rt ain

va lu e H e ha s a l s o p r op o u n d e d g e n e r a l l aw s for the p o sit i on

.

o f b a n d s p e c t ra o f c h e m i c a l c o mp o u n d s b y a r gu in g O n t h e b a s i s
-

o f t he hyp ot h es i s o f l i gh t qu a n t a " 3 Fi n a lly E i ns tei n 74 a n d

-
.
,

S ta r k 75 h a v e c o n s i d e r e d ph o t o ch e m i ca l r e a c t i on s f r o m t h e
-

st a n dpo in t o f the hyp ot he si s o f l i gh t qu a n ta a n d h a ve e n u n -

c i s t e d a fu n d a m e nt a l l a w wh i ch h a s b e e n v e r ifi e d a t l ea s t
, ,

p a rt ially b y th e d e t a i l e d i n v e s t i gat i on s of E Wa r bu r g "6

, . .

§6 P lanck S e c ond T h eo ry
’
. s

In S p it e of a l l the succe sse s whi c h the qu a n t um hyp oth e si s

O f l i gh t i s a bl e t o s h o w w e mu st n o t l e a ve o u t o f c o n s i d e ra t i o n
,

t h a t t h i s ra di c a l vi e w a t l e a st i n i t s e x i st i n g fo r m i s v e r y
, ,

d i ffi c ul t t o b r i n g i n to a gr e e m e n t wi t h the c l a s si c a l u n dul a t ory

t h eo ry . S i n c e o n the o n e h a n d t h e ph en o m e n a o f i n t e r f e r e n ce
a n d d i fir a c ti o n i n a l l t h e i r ob s e rv e d m i n u t i ae a r e e x c e ll e n t ly
, ,

d e sc ri b e d by t he w a v e th eo r y bu t o ffe r a lm o st i n sup e r a bl e
-

di fficul tie s to t he qu a n tum t h e o r y o f l i gh t it i s e a s y to u n d e r ,

s ta n d t h a t fe w sci e n t i sts c oul d m a k e u p t h e i r m i n ds to a p

pr o ve of s uch a fa r r e a c hi n g ch a n ge i n t he o l d a n d w e ll t e s t e d
- -

c o n c e p t i o n O f t h e p r o p a ga t i o n o f l i gh t a cha n g e t h a t e n ta i l e d ,

p e r ha p s it s co mpl e t e a b a n d o n m e n t Th i s m o r e c a u t io u s a n d .

c on se rv ati v e s ta n dp oi nt w a s t a k e n up by M P l a nc k who .
,

r e ta i n s i t t o t h i s d a i n as much a s h e p r e f e r r e d to l o ca t e th e
y ,

qu a n tum p ro p e rt y i n m a t t e r ( t h e o sc i ll a tors) — o r a t l e a s t tO »

co n fin e it to the p r oc e s s of in t e ra c tion b e t w e e n m a tt e r a nd
24 T HE QU ANT U M T H E O RY
ra di a ti o n — wh il e e n de a vo u rin g to r e t a i n the c l a ss i c a l wa ve
t h e ory for the p r o p a g a ti o n o f r a d i a t i o n i n s p a c e N o n e the .

l e ss s eri ous h i n d r a n c e s h a d a l re a dy i n tr ud e d t h e m s e lve s i n

,

t he d e v e l o pm e n t of hi s fi r s t qu a n tum hyp ot h e s i s ( qu a n t um
e m i s sio n a n d qu a n t um a b s o r p t i o n ) Fo r H A Lor en tz 77 . . .

p o in t e d o u t qu i t e r i gh tly t h at the c o n c e p ti on e s p e ci a lly O f ,

qu a ntum a b so r p t io n l e a ds t o p e cul i a r d ifficul t i e s H e S how e d

, .

t h a t t h e t i m e wh i ch a n o s c i ll a t or r e qu i r e s fo r t h e a b s o r p t i o n
of a qu a n t um o f e n e r gy t u r n s o u t t o b e l o n g to a n i mp r ob a bl e

d e g re e wh e n t h e e x t e r n a l fi e ld o f r a di a ti o n i s s uffici e n t ly w e a k .

Mo r eov e r it wo uld b e p o s si bl e to i n t e rr up t the r a d i a t i on a t

,

w i ll b e fo re t he o s c i ll a tor h a d a bs orb e d a wh o l e qu a n t um A s .

a r e sul t o f t h e se o b j e c t i o n s P l a nc k d e t e r m i n e d t o m o d i fy t he

qu a n t um hyp ot h e s i s a s f oll o ws 78 A bsorp ti on p r oceed s con .

ti n u ou sly a nd a ccor d i n g to t he l a w s of cl a ssi ca l el ec trod y n a m i cs

t he en er gy of the osci ll a tor s i s ther efor e con ti nu ou sl y va r i a bl e a nd ,

ca n a ssu m e a n y va l u e be tw een 0 a nd co On t he other ha n d ,

em i ssi on occu r s in qu a n ta , a n d the osci ll a tor ca n em i t on l y

w hen i ts ener gy a m ou n ts to j u st a w hol e m u l tip le o f e hv .

Wh ether i t then em i ts i s d e ter m i n ed by a l a w of pr ob

or no t

a bi li ty Bu t if i t does em i t, then i t l oses i ts w hol e m om en ta r y

.

f
ener gy , a nd the r e or e em i ts qu a n ta B e tw een tw o em i ssi ons i ts
.

en er gy con ten t gr ow s by a bsor p tio n con ti nu ou sl y a n d i n p r o

-

or ti on to the ti m e
p .

A cc or d in g t o t h i s s e c on d t h e o ry o f P l a nck wh i c h i s c a ll e d ,

t h e t h e or y of qu a n t um e m i s sio n ,
the m ean e n er gy U of a

l in e ar os c i ll a to r is E gr e a t er th a n i n the fir st t h eory 79 Wh il e
"
.

2
i n th e fo r m e r c ase m ea n e n e r gy of t he o sc ill at o r a t a b eo
the
lut e z e r o w as e qu a l t o z e r o ( se e e qu a t i o n ( 9 ) fr o m wh i c h ,

wh e n T 0 U ,
i n t h e c a s e o f t h i s s e c o n d t h eory it i s
hv
e qu a l to “
“ The o sc ill at o r s r e ta i n t h e r e fo r e at th e z er o
Q
1 1,
p oi n t a z e r o po i n t
-
e ner gy of v a lu e 3 as a me an ,
i n a smuch
2
as t he y ssu m e wh e n T 0 a l l p o s si bl e e n e r gi e s
a , ,
b e t we e n
0 and hv N e ve rt h el es s t h i s t h e or y a l s o whe n t h e
.
, ,
r e l a ti on

( )
7 i s c o r r e s p on di n gly m odi fi e d l e a d s t o P l a nc k s ,
’
La w of
Ra d i a t i on .

In the c our se of t i m e P l a n c k ha s m ade se ve r a l fu rt he r

 Z E R O PO I NT EN E R G Y
-
25

a tte mpt s 3° to e n l a r ge a n d m o di fy t h is s e c o n d t h eo r y too F o r .

e x a mpl e he ha s t e mpo r a r i ly a ss um e d t h e e m i s s i o n a l s o to b e
,

c o n t i n u o u s a n d r e l e ga t e d t he qu a n t um e l e m e n t t o t h e e xc i t a
,

t io n o f t h e o s c i ll a t or s by m o l e c ul a r o r e l e c t r o n i c i mp a c t s He .

h a s h o we v e r r e p e a t e dly r e t u r n e d i n e s s e n t i a l s t o t he s e co n d
, ,

f o r m of hi s t he o ry ( c o n ti n u o u s a b sorp t i o n qu a n tum e m i ss i o n ) , .

§7 . Z e r o po int E ner gy
-

In m or e t h a n o n e d i r e cti on t h i s t h e o r y ha s ha d fu rt h e r ,

r e s ul t s Th e a pp e a r a n c e o f th e m e a n z e r o p oi n t e n e r gy
.
-

wh i c h i s p e cul i a r to t hi s s e c on d t h eor y o f P l a n ck be c a m e ,

the sta r t i n g p oi n t o f a se r i e s o f r e s e a r ch e s i n wh i ch c e r t a i n
-

phy si ci st s go i n g b e yo n d P l a n c k p ost ul a t e d t he e x i ste n ce o f

, ,

a tr u e n ot m ea n
( ) z e r o p oi n t e n e r gy e qu a l fo r a ll o s c il l a t ors
-
.

O n t h i s b a s i s E i ns te i n a n d 0,
S te r n 8 1 h a ve give n a d e duc tio n .

of P l a n ck s L a w wh i ch a v o i d s a l l d i s c o n t i n u i t i e s ot h e r t h a n
’

t h e e x i st e n ce o f t h i s z e r o p o i n t e n e r gy -
.

In t h e y e a r 1 9 1 6 N er n st 82 t ook a s t i ll m o r e r a d i c a l s t e p i n
,

p os t ul a t in g the e xi s t e n c e o f a z e r o p o i n t r a d i at i o n whi c h “ -

w a s a l so t o b e p r e s e n t a t t h e a b solu t e z e r o o f t e mp e r a tu r e
a n d w a s t o e x i s t i n d e p e n d e n tly o f h e a t r a d i a t i o n fil l i n g t h e ,

whol e o f s p a c e a n d s u c h tha t t h e o s c i ll a t o r s a s w e ll a s a l l
, ,

m ol e cul a r s t ru ctu r e s set t h e m s e lves i n e qu i l ib ri um wi t h i t by

,

t a k i n g up t he z e r o p o i n t e n e r gy E v e n i f w e r e ga r d t h e s e
-
.

vi e ws m o r e or l e s s s c e p t i ca lly o n e t hi n g c a n n o t b e i gn o r e d : ,

m a n y fa c t s u n d o ub t e dly supp or t th e c o n c e p t io n t h a t a t t he
a b s o lu te z e r o by n o m e a n s a ll m ot i o n ha s c e a s e d We n e e d .

o n ly d r a w a t t e n t i o n t o t h e f a c t t h a t a c c o r d i n g t o t h e v i e w o f , ,

F B i cha r e s8 P L a n ge vi n 84 a n d a c c o r d i n g t o t he e x p e ri m e n t s
.
, .
,

o f E i n s tei n W J d e H a a s 88 a n d E B ec k 86 P a ra a n d D ia
, . . .
,

m a gne ti s m a r e p r odu c e d by r o t a ti n g e l e ctron s a n d t h a t t h i s

m a gn et is m r e m a i n s i n e xi ste n c e d o wn to the l o we s t te mp e r a
t u re s .

§8 . T he ory of the Q u a ntu m of A cti o n

In ye t a n oth e r r e s p e ct ha s P l a nc k s t h eo ry p r o v ed s t im u
’

l a t i n g i n v i rt u e o f a s p e c i a l for mul a tio n whi c h P l a nc k ga ve

,

i t s? a t t h e So lv a y Co n gr e ss i n B ru s s e l s du ri n g 1 9 11 Fo r .

h e r e P l a nc k ga v e e x p r e s s io n for the fi r st ti m e to t he i d e a
t h a t th e a pp ea ra n c e of ene r gy qu a n t a
-
is on ly a s e co n d ar y
26 T HE Q U ANT U M TH E O RY
ma t t e r b ei n g
,
on ly s qu e n c e o f a d e e p e r a n d m or e
the con e

ge n er a l l a w Th i s l a w whi ch i s t o b e r e ga r de d a s the p r e
.
,

cu r s or o f t he l ate s t d e vel o pm e n t of the do ctr i n e of qu a nt a ,

m a y b e f o r mul at e d a s foll ow s : Supp o s e t h e m om e n t a r y s tat e

o f a P l a nc k o sc i ll a t o r s a a l i n e a r ly v i b r a t i n g e l e c t r o n to b e
y , ,

d e fi n e d a c c or d i n g to Gi bb s m e tho d by it s d i sp l a cemen t q fro m

’

i t s p o si ti o n o f r e st a n d by i t s i mp u l se or m omen tu m p a n d ,

s upp o s e i t t o b e r e p r e se n t e d i n a pl h s
qp a ne
( t-
e t ate or

ph a s e pl a n e) E v e ry p oi n t of t he q p pl a n e t h at i s e v e ry
-
.
-

, ,

p h a se
p
-

o i n t c o
, rr e S p o n d s t o a d e fi n i t e m o m e n t a r y c o n d it i o n of

t h e os c ill a to r The p o stul a t e i s t h e n m a d e t ha t n ot a ll p o i n t s

.

o f t h i s pl a n e o f s t a t e s a r e e qu i v a l e n t On the con tr a r y ther e

.
,

F IG 2
. .

a r e cer ta i n s ta tes o f the di

osci ll a tor s tiw hi ch
ng u i s hed b
are
y
a
p ecu l i a r i ty T h e t o t a l i t y o f th e ph a s e p o i n t s t h a t c or
.
-

r e sp o n d t o t h es e p e cul i a r s t a t e s f or m a f a m i ly o f d i s c r e t e

c u r v e s wh i ch su r r ou n d o n e a n ot h e r In t h e c a s e o f t he.

P l a nc k o s c ill a tor t h e s e cu r v e s a r e c on c e n t r i c e ll i ps e s ( se e
F i g 2) wh i c h d i vi d e t h e ph a s e pl a n e i n t o r i n g l ik e s t r i ps
.
- -
.

The p o s t ul a te of t h e qu an t um t h e or y n o w c on s i s t s i n t h i s ,
t h a t t h e s e r i n g s t r i ps all p o ss es s t he s a m e a re a h If w e .

c a lcul a t e on t h i s ba si s t he e n e r gy p os s e sse d by a n o sc i ll a t or
in o n e o f t h e s e u n i qu e s ta t e s , w e fin d 80 t h at i t i s a who l e
mul t i pl e o f hv Th e s e s p e c i a l s t a te s ( r e p r e s e n t e d i n the
.

ph a s e pl a n e by t he p oin ts Of t he d i sc re t e e ll ip s e s) a re , t h e r e
-
 TH E O RY OF T HE QU AN T U M OF A CT I O N 27

fo re a c cor di n g t o P l a nc k s fir s t th eory the o n ly dy n a m i c ally

,
’
,

p o ssi bl e a n d sta bl e s ta t e s of t he o s c ill ato r If a n o s c ill a t o r .

e m it s o r a b s o r bs i t s ph a s e po i n t jump s f r o m o n e e ll i p s e t o
,
-

a n oth e r Th e s ta te o f a ffa ir s i s d i ffe r e n t i f w e a cc e pt P l a nc k s

’

s e c o n d th eo r y A c c o r d i n g t o t h i s a l l c o n d i t i o n s O f t h e o s c il
.
,

l a t or t h at i s a ll p o i n t s o n t he ph a se pl a n e a r e dy n a m i c a lly
,
-

p o s s i bl e On t h e o t h e r ha n d e m i ss io n t a k e s pl a c e o n ly i n
.
,

t h e s t a t e s S p e c i a lly d i s t i n gu i s h e d b y t h e e ll i p se s Se e n fr o m .

t h i s n e w p o i n t o f vi e w t h e e n e r gy qu a n t a a r e t h e r e fo r e o n ly
,
-

, ,

a r e s ul t O f t he p a r t it i on i n g o f t he ph a s e pl a n e Ma t h e -
.

m a t i c a ll y w e m a y e X p r e ss t h i s s t r uc t u r e o f t he ph a se pl a n e
,
-

t hus : t he n t h u n i qu e c u rv e e n c l o se s a s u r f a c e o f a r e a u h o r , ,

i n s ymb ol i c l a n gu a g e ,

dq = nh

Th e d o ub l e i n te gr a l i s t ak e n ove r t he s u r fa c e ; t he si n gl e
i n t e g r a l i s t a k e n a r ou n d t he bo u n d a r y cu r v e o f t he n t h
e ll i p se .

O n t h i s b a s i s fo r s ys t e ms o f o n e d e gr e e o f f r e e d o m wh i ch ,

i s c a ll e d P la n ck s t h e or y o f t he a c ti o n qu a n t um — for h ha s
“
’
-

t h e d i m e n si o n s o f a n a c ti o n — t h e m o d e r n e x t e n s i o n of t h e
qu a n t um t h e or y fo r se v e r a l d e gr e e s of f r e e do m ha s a s w e ,

s h a ll s ee b e e n e r e c t e d
, .

F u r t h e r a l i n e of a r gum e n t p r op o s e d a n d d e v e l op e d b y
,

A S om m erfel d t a k e s i t s o r i gi n h e r e
. St a r t i n g f r o m t h e f a c t .

ju s t m e n t i o n e d t h a t P l a n ck s c o n s t a n t h p osse sse s t he d i m e n
,
’

s i o n s of a c t i o n e n e r gy t i m e S omm er feld s e t up t h e hyp o

( ) -

t h e s i s 89 t h a t fo r e v e r y pu r e ly m o l e c ul a r p r o c e s s sa y t h e r e l e a s e ,

o f a n e l e c t r o n i n t h e ph o t o e l e c tr i c e ffe c t o r t h e s to pp i n g o f
-

a n e l e c tr on b t h e a n t i c a t h o d e i n t h e g e n e r a t i o n o f ROn t e n
y g
r

ra ys ,
t he qu a n ti ty c a ll e d ( L V) d t k n o wn t o , us
0

fr o m Ha m i l ton s P r i n c i pl e , h a s th e v a lu e H er e L
’

a nd V

are t he ki n e ti c and p ot e n t i a l
gi e s o f the e l e c tron r e sp e c
e n er

t i v e l y 1 i s t he du r a t ion o f th e m o l e cul a r p r o c e s s s a y fo r
,
°

, ,

e xa mpl e the t i m e wh i ch i s r e qu i r e d fo r t he r e l e a s e o f t he
,

e l e c t r o n f ro m th e a to m i c c o mpl e x du r i n g t h e ph oto e l e c t ri c -

e ffe c t o r t h e s t o p in g O f t he e l e c tr o n by t he a n ti c at hod e
p
-

, .
28 THE QU A NT U M THE O RY
Th i s f o r mul a ti on o f t he qu a n tum hyp ot h e s i s i s a s it w e r e
, ,

a n e x p r e s s i o n o f t h e w e ll k n o w n f a c t t h a t l a r g e a m o u n t s o f
-

e n e r gy a r e a b s o r b e d o r g i v e n up i n s h o rt t i m e s wh e r e a s s m a ll
,

a m o u n t s a r e a b s o r b e d o r e m i t t e d i n l o n ge r t im e s b y t he

m ol ec ul e s s o t h a t on t he wh o l e the p r o duc t O f t he e n e r gy
,

t r a n s fe r r e d a n d t h e du r a t i o n o f t h e t i m e o f e xc h a n g e i s a
c o n st a n t. In f a ct f a s t c a t h od e r a ys fo r e x a mpl e a r e s t o pp e d
, , ,

b y m a t t e r i n a s h o r te r t i m e — a n d t h e r e f o r e g e n e r a t e h a r d e r
ROn t ge n r ays — t h a n sl o w c a t h o d e r a y s . S omm erfel d ha s
a ppl i e d hi s t h e o r y s u c c e ss fully to t h e m e c h a n i s m of the
g e n e r a t io n o f ROn t ge n r a ys a n d y r a y s 9° S om m erfeld a n d
-
.

P D ebye 9 1 h a v e w or k e d o u t o n t he s a m e b a si s a t h e o r y o f
.

t he p h oto e l e c t r i c e ff e c t wh i c h l ik e t h e hyp ot h e s i s o f l i gh t
-

, ,

qu an ta a l so l e a d s to E i ns tei n s L aw
,
’
 CHAP TE R IV
T he E x t e ns io n o i t h e D o c t ri ne o f Q u a nt a t o t he
M o l e c u l a r T he ory o f S o l d B o d i e s
i 92

P e ti t
’
§ I . D u l on g a nd s La w

T w a s a p a r ti c ul a r ly f o rt u n a t e c i r c um st a n c e fo r t he c o n
s ol i d a t i o n o f t h e d o c t r i n e o f qu a n t a t h a t t h e f a i lur e o f

c l a s s i c a l s t a ti s t i c s w a s n o t c o n fi n e d t o t h e t h eo r y o f r a d i a t i o n ,

b u t , a s a pp e a r s l a t e r , e x te n d e d t o t h e m ol e cul a r t h e o ry Of s ol i d
bo d i e s . Thu s t h e r e a r o se i n qu it e a n oth er fi e ld a s tr o n g s u p
p o r t for the qu a n t um hyp ot h e s i s n a m e ly in the fi e ld o f A tom i c
, ,

H ea ts . The A t o m i c H e a t o f a s ub st a n c e ( in the c a se o f p o ly
M
”
a to m i c b odi e s w e s a l c r H ea t d fi d
y t h e o e u l a
) i s e n e a s t he

p roduc t o f i t s S p e c i fi c h e a t a n d i t s a to m i c w e i ght (or m ol e c

ul a r we ight) ; or ot h e r wi s e e x p r e s s e d i t i s t h a t a m o u n t of
, ,
”
h e a t whi ch mu st b e c o mmu n i c a t e d t o a gra mm e a to m 93 -

( o r g r a mm e m ol e c ul e
-

) o f t h e b o dy i n o r d er t h a t i t s t e mp e r a
,

t u r e m a y b e r a i se d b y o n e d e gr e e A cco r d i n g t o o u r p r e s e n t
.

c on c e p t i on s the th e r m a l c on t e n t o f a m o n a to m i c sol i d s a y
, ,

a c ry s t a l i s n o th i n g m o re t h a n t he e n e r gy of the e l a st i c
,

vi b ra t ion s of i t s a t o m s wh i ch a r e a r r a n ge d i n t he for m o f
,

a s p a c e l a t t i c e a bo u t t h e i r p o s i t i o n s of e qu i l i b r i um
-

,
If w e .

a pply cl a s si c a l s ta t i s t i c s t o t h e s e v i b r a t i o n s a n d p a r t i cul ar ly ,

the l a w o f e qu i p a rt it i o n o f k i n e t i c e n e r gy w e a rri ve a t t h e ,

foll owi n g c o n c lu si o n : The m e a n k i n e t i c e n e r gy of a n a to m

3 kT
vi b r a ti n g In S p a ce ,
i . e . wi t h t h r e e d e gr e e s o f fr e ed o m ,
is ’
2
its m e a n p ot e n t i a l e n e r gy i s e qu a l to t he s a m e a m o u n t 94 s o ,

t h a t i t s to ta l e n e r gy i s t h e r e f o r e 3k T If w e n o w c o n si de r .

1 gra mm e ato m of t h e b ody t h a t i s a s y st e m of N a to m s, ,

( w h e r e N IS t h e A v o a d ro n umbe r a pp r o x i m a t e ly 6 x 1 0
g ,

W e ge t fo r t h e m ea n e n e r gy o f t he bo dy r e m e mb e r i n g ,

E 3 k TN SE T ( )
3 1
29
30 T H E Q U A N T U M T H E O RY

wh e r e R i s t he a bs olu te ga s c o n s t a n t It f oll o w s t h a t
-
. the
a to m i c h e a t of t he b ody a t c o n s ta n t v olum e b e c o m e s :

?
at]

ET
313 6 94 ( )
3 2

Thi s i s the l a w of D u l ong and P eti t, 95 ac c or d i n g to wh i ch

t he a tomic hea t ( a t consta n t vol u m e ) f o m on a tom i c sol id bodi es
31
ha s the va l u e 9— 1
, i n d ep end en tl y o f the temp er a tu r e .
96
d eg .

Thi s l a w i s ctu ally o b e ye d b y m a n y e l e m e n t s m or e or l e s s

a

cl o s e ly 9 7 O n the o t h e r h a n d e l e m e nt s h ave l on g b ee n k n ow n
.
,

wh i ch a r e fa r fr o m follo wi n g t hi s r ul e a n d w hi ch S h o w ,

s y s t e m a t i c d i ff e r e n c e s e s p e c i a lly a t l o w t e mp e r a t u r e s
,
.

Thus a s ea r ly a s t he y e a r 1 8 7 5 F H Weber 98 fo u n d t h a t
, ,
. .

t he ato m i c h e a t of d i a m o n d a t 5 0 C i s a b ou t
°
.
ES
L . The
d eg .

ato m i c h e a t s of oth er e l e m en t s a s w e ll ( bor on b er yll i um , ,

S i l i c on ) h a ve a ls o b e e n sh o w n t o b e much t o o sm a ll a t

o r d i n a r y t e mp e r a t ur e s A n d a l to ge th er i t a pp ea r e d t h a t t he
.

d e f e c t f r o m D u long a n d P eti t s n or m a l v a lu e o c cu r s qu ite ’

ge n er a lly a t l ow t e mp e ra tu re s a n d be c o m e s t he m or e p ro ,

n ou n ce d t he l o w e r t h e t e mp e r a t u r e
,
Th e cl a s si c a l t h e o r y .

o ffe r e d n o s o lu t i o n o f t h e s e l o w va lu e s o f t h e a t o m i c h e a t 99 .

E ins t e in T h e ory A t o mi c Hea t s

’
§ 2 . s of

E i n stei n w a s th e fir s t t o r e c ogn i se 100 th a t i n thi s c a se to o , ,

t he qu an tum t h eor y w a s d e st i n e d t o s olv e t he d i fficul t y .

P r e c i s e ly a s i n th e t h e o r y of r a di a t io n t he m e t h o d o f ,

cl a ssi c a l s tati s ti c s l e a ds of n e c e s sit y to a wr o n g l a w i n t he

fi e ld o f a tom i c h e a t s Hence her e a lso w e m u st a ba n do n
.
, ,

the l a w of the equ ip a r ti ti on of en er gy In f a c t w e n e e d o n ly .

,

i m a g i n e e l e ct r i c ch a r ge s d i str i bu t e d a m on g t he a t o ms 101 a n d
t h e n w e se e t h a t e x a c t ly l i k e the P l a n ck o s c i ll a tor s th e y mus t
, ,

s e t t h e m s e lv e s i n e qu il i b r i um w i t h t h e h e a t r a d i a t i o n wh i ch -

i s a lw a ys p r e s e n t i n t he b o dy Th i s m e a n s h o w e v e r t h a t
.
, ,

t he r e a t i on
l a c cor di n g to whi ch U 9 15 mus t be s e t
172 ,

up b e t we e n t h e m ean e n er gy U o f a n a to m vi b r a t i n g l i n e a r ly
w i th fr e qu e n cy v, a nd the i n t e n s i t y of r a d i a t i on If w e
n ow ta k e P l a nck s
’
ra di a tion for mul a ( )
1 2 a s e m ir i c ally
p
 EI N ST EI N S T HE O RY OF AT O M I C H E AT S 31
’

gi ve n ,
f oll ow s i mm e d ia te ly t ha t the m e a n e ne r gy U of the
it
l i nea r ly v i b r a t i n g a t o m mu s t p o s s e s s n ot t he v a lu e kT gl v e n ,

by cl a ss i ca l st ati sti c s b u t the v a lu e g i v e n by th e qu a n tum

,

k”
th eo r y, na m e ly H, M
F or t he a to m whi c h vi b r a te s
-

e
lfT 1
in s pac e we e t t h e r e f or e— b y an O bvi ous i
ge n e r a l s a t i o n — in
g ,

3 hv
pl a c e of t he cl a ssi c a l v a lu e 3 kT t h e
, qu a n t um v a lu e

F IG . 3 .

The hea t -
co n t e n t o f th e gr a mm e -
a to m w i ll t h e r ef o r e be
3t
hv
fT
e 1
fr o m whi ch w e ge t fo r t he a to m ic hea t at c o n s ta n t vo lum e
E i n stei n s f or mul a
’

dE "
x e
f
hv
dT
3R °

2
,
wh e r e x
kT
( 3 4
D
“
( e

A ccor d i n g to thi s, t he a tom i c hea t of m ona tomi c solid bod ies

i s no t a cons ta n t w hi c h i s i n d ep end en t of the temp er a tu r e, a s

D ul o n g a nd P e ti t
’
s La w r equ i r es , bu t is a fu nction of a nd
 32 T HE QU ANT U M THE O RY
i s t her efor e i n the ca se of a d efi n i te bod y ( i e w i th v fi x ed ) . .

a fu nc ti on of t he tem p er a tu r e It s fo r m i s s u c h ( s e e F i g . .

t h a t fo r T 0 (i e x 00
) t h e a to m i c
. h.e a t i t s e lf i s

z e ro a n d t h e n i n c r e a s e s gra du a lly w i th i n c r e a s i n g t e m
,

p e ratu re ,pp r o a ch i n g a s ymp t o t i c a lly a t h i gh t e mp e r a t u r e s

a

( i s
. w i
. t h s m a ll x ) t h e c l a s si c a l v a lu e SR D u lon g a nd .

P eti t s L a w i s t h e r e fo r e o n ly t ru e i n t h e l i m i t fo r s m a ll
’

v a lu e s of ffl t ha t
’
,

’
i s , fo r l o w fre qu e n c i e s o f a to m i c vibra tion ,
kT
hi gh t e mp e r a tu r e s ctly a s i s t he c a s e w it h R a y lei gh s ’
or , exa

La w o f Ra d i a t i o n Th e d e p a r t ur e s f ro m D u lo n g a n d P e ti t s
’

L a w i n p a ssi n g f r o m h i gh t o l o w t e mp e r a t u r e s b e co m e m a r k e d
, ,

t he s oo n e r t h e g r e a t e r th e f r e qu e n cy o f th e a t o m s .

§ 3 M e t h od s
. of D e te rmi ni n g the F re qu e ncy

Th i s f r e qu e n c y v— t h ely u n k n ow n m a gn itud e i n E i n stei n s ’

on

f o r mul a ( 3 4) — m a y b e d e t e r m i n e d b y se v e r a l i n d e p e n d e n t a n d
v er y n o t e wort hy m e t h o d s O n e w a y t h a t i s a lw a ys p o ssib l e.

i s o f c o u r s e the fo ll o w i n g : F o r a gi v e n s ub s t a n c e w e c h oo se
a n e x p e r i m e n t a lly w e ll k n o w n v a lu e o f t h e a t o m i c h e a t 0
-

3 ,

*
whi ch c or r e s p o n ds t o a d e fin ite t e mp e r a t u r e T F r om ( 3 4) .

2
0
it foll ow s t h e n t h a t I 2 ’ an e qu a ti o n fr o m wh i ch
3R

x
9
12 ; can be d e ter m i n e d ,
a nd t he n ce v . F r o m t he v t hus

f o u n d the c ou r s e o f th e wh ol e 0 c ur v e c a n b e c a l c ul a t e d for ,

a l l t e mp e r a t u r e s a n d c o mp a r e d w it h e x p e r i m e n t
,
.

”
B e si d e s t h i s e mp i r i c a l
“
m e th o d o f d e t e r m i n i n g v t h e r e ,
“ ”
a r e a n u m b e r of o t h e r m or e t h eo r e ti c a l m e t h o ds whic h ,

d o n o t r e qu i r e t he u s e o f t he v a lu e s of t he a t om i c h e a t .

E i n stei n 102 a s fa r b a c k a s 1 9 1 1 d i sc o v e r ed a n i mp o r ta n t
, ,

c o n n e c t i o n b e tw e e n th e f r e qu e n c y v a n d t he e l a s t i c p r o p e rt i es

o f t h e bo dy Th a t s u c h a c o n n e x i o n mu st e xi st i s e a s i ly
.

r e c o g n i se d f r o m t he f oll o wi n g c o n s i d e r a t i o n s : i m a gi n e t he
a t o ms o f t h e b o dy a r r a n g e d up on a s p a c e l a t t i c e a s in a -

c r y sta l a n d supp os e a c e r t a i n d e fi n i t e a to m a r b i tr a rily d i s

,

t u r b ed f r o m i t s p o si t i o n o f r e st t h e n t h i s a to m wh e n r e l e a s e d , , ,

wi ll e x e cu t e vib r a t i on s a b o u t i t s p o s itio n o f e qu i l ibri um If .

w e s upp o s e t h e s e vi b r a t i o n s t o b e s i mply p eri o d i c ( m o n o

“

ch r o m a ti c ) — w e S h all h o w e ve r so on r e c ogn i se tha t t hi s

”
, ,
 D ETE R M I NI N G T H E FR E QU E N C Y 33

su p p o s i ti on i s a n i n a dm i s si bl e a pp r ox i m a t io n — w e se e t ha t
t h e fr e qu e n cy v i s t h e gr e a t e r t h e s m a ll e r t he a t o m i c m a s s ,

a n d t h e r e fo r e a l so t h e a t o m i c w e i gh t o f t he bo dy a n d t h e ,

gr e a t e r o n t h e o t h e r h a n d the f or c e wh i c h r e s tor e s t he
a t o m to i t s p o s i t i o n o f e qu i l i b r i um Th i s r e s to ri n g f o r c e i s .
,

h o we ve r for i t s p a r t t he s t ro n g e r t he l e ss e x t e n s ibl e a n d
, ,

t h e r e fo r e c o mp r e s s ib l e t h e b o dy i s H e n c e i mu s t t u r n ou t . f

t h e g r e a t e r t he s m a ll e r t h e a t o m i c w e i ght a n d t he c o m p r e s
,

s i b i l i t y o f t he s ub st a n c e Th e e x a c t w o r k i n g o u t o f t h i s i d e a
.

l ed E i n s tei n t o t h e fo r mul a 03 1

V :

A tpt x i

W h e re A i s t h e a to m i c w e i gh t p t he d e n s it y a n d K the , ,

c o mp r e s s ib i l i t y o f t he b o dy .

A fur t h e r i n t er e st i n g r e l a t i o n wh i c h c o n n e c t s v wi t h t h e r
,

m a l d a t a n a m e ly t h e m e l t i n g p o i n t w a s fo u n d by F A
, ,
-

, . .

L i nd ema nn 104 by w o r k i n g o u t t h e c o n c e p t i o n t h a t t h e ampl i

t ud e o f v i b r a t i o n o f t h e a to m a t t h e m e l t i n g p o i n t i s o f t he -

o r d e r o f m a g n i t ud e o f t he d i st a n c e s b e t wee n t h e a t o m s If .

TS i s t h e a b so lu t e m e l ti n g p o i n t t h e n i t f oll o w s t h a t
-

v 2 8 10 12
.

A n ot h e r for mul a d e duc e d by E . Gr u n ei sen 105 m ay a ls o be

gi ve n h e r e
if 2 91 . 10 11
. A ( 7)
3

H e re 0, i s t he h e a t a t c o n st a n t volum e a n d i s t he
ato mi c ,
a
.

c o e ffic i e n t of t h e r m a l e x p a n s i o n ; t h e i n d ex 0 m e an s t h a t t he

v a lu e o f Cfi a i i a t a b solu t e z e r o i s t o b e u s e d
p
'

F r o m fo r m u l ae ( 3 5 ) a n d ( 3 6 ) w e r e c o g n i s e a t o n c e the
a b n o r m a l be h a v i o u r o f d i a m o n d fo r e x a mpl e i n r e sp e c t to i t s
, ,

a to m i c h e a t .For i t i s k n o w n t h at d i a m o n d h a s a h i gh m e l t
i n g po i n t a n d v e r y l ow c o m p r e s si b il i t y a c c o mp a n i e d b y a l o w
-

a to m i c w e i h t It s v i s t h e r e fo r e c o mp a r a t i v e ly l a r g e ; a n d
g .

i t foll o ws t h e r e f or e a c c o r d i n g t o t h e a b ov e c o n s i d e r a ti o n s
, ,

t h a t i t s a to m i c h e a t fa ll s b e l ow D u long a n d P eti t s va lu e o f
’

3B s at c o mp a r ati v e ly h igh te m p e r a t u r e s In fa c t
(i
.
34 T HE QU ANT U M THE ORY
ca l
the m ic h e a t of d i a m on d is ly
.

2 84 abs
°
a to at on
d eg
.
’
.

413 ab s it i s ven
°
and e 1 169 ch e s o n ly
°
. at ab s . it rea

“3 1
t he valu e 52 4
d eg .

Fi n a lly , p a rti c ul ar i mp o rt a n c e a tta ch e s

fir s t to a l
r e a t io n ,

d i s cov e re d b y E Ma d el u n g 103 a n d W S u ther l a nd 1°7 b e twe e n

. .
,

t h e fr e qu e n c y v o f t h e a t o ms a n d t h e O p ti c a l p r o p e r ti e s
of b o d i e s Th e t w o i n v e s ti g at o r s s t a r t e d i n t h i s c a s e f r o m
.

t he fo ll o w i n g c o n c e p t i o n Cryst a ls o f d i a t o m i c c o mpo u n d s
( a r y sal t s) such a s r o ck s a l t ( N a Cl) s ylv i n ( KCl )
b i n ,
-

, ,

p o t a ss i u m b r o m i d e (KBr ) a n d o th er s a r e k n o wn t o b e , ,

cub i c a l sp a c e l atti c es i n wh i ch t he s i n gl e a to ms c arry e l e ctr ic

-

ch a r ge s a n d th e r efor e a pp e a r a s i on s In fa ct t he p oi n t s of
, .
,

t h e S p a c e l a t ti c e a re o c c up i e d a l t e r n a t e ly by t h e p o s it i ve ly
-

ch ge d N a (or K ) a t o ms a n d th e n e ga tiv e ly c h a r g ed 01
a r
’
r +
,
“

( r Br
) t m If l c t m g t i l i gh t w v f f qu cy
“

o a o s a n .e e r o a n e c a e o r e e n -

v f a ll s up o n t h i s c r y s t a l t h e t w o i o n s a r e t h r o w n i n t o f o r c e d
,

o s c i ll a t io n s r e l a t i v e ly t o on e a n o t h e r a n d fu r t h e r o n a cc o u n t , ,

of r e s on a n c e t h e m or e s t r o n gly th e m o r e e x a ct ly t h e fr s
, ,

q u e n c y v o f t h e i m p i n g i n g w a v e a g r e e s w i t h t h e n a t u r a l fre

q u e nc
y W wh i
,
ch l i e s i n t h e i n f r a r e d o f t h e i o
-
n s t h e m ,
se lv e s .

Si n c e t he i on i c v i b r a t i o n s a r e s e t up a t t h e c o s t o f t h e e n e r gy
o f t he i mp i n gi n g w a v e t h i s e n e r gy w i ll b e w e ak e n e d (a h
,

sorb ed m r e du r i n g i t s p a s s a g e t h r ough t h e b o dy t h e
) t h e o ,

n e ar e r v l i e s to v On t he ot he r h an d t h e v ib r a t in g i o n s
r. ,

r a d i a t e b a c k w a v e s o f f r e qu e n c y v s i n c e t h e y a r e c o mp e ll e d

t o ex e c u t e t h e s e v i b r at i on s wh e n s e t i n t o f o r c e d v i b r a ti o n
, ,

d o i n g s o t he m or e s tr o n gly t he m or e p ro n o unce d t he r e s on
,

ance i s ,
a ga i n t h e r e fo r e t h e n e a r e r v l i e s t o v
, ,
H e n ce a 7 .

r e gi on of m a x i mum a b s orp t i on a n d s t r on g e s t
( m e t a ll i c
) re

flec t i on w i ll l i e i n t he n e i ghb o u r h oo d 108 of I Th e s e f

r e gi o n s of m e t a ll i c r e fl e c t i o n o f a g i v e n su b s t a n c e m a y b e
.

d e t e c t e d by t h e m e th od of Re st s tra hl e n ( r e s i du al r a ys) “

w o r k é d o u t by H Ru ben s a n d E F N i c hol s .
1 °9 . Fo r t h i s. .

pu r pos e w e on ly r e qu ir e t o r e fl e c t r a d ia tion o f a c on s i d e r a bl e
ra ng e o f f r e qu e n c y a bo u t I r e pe a t e dly f r o m t h e s u b sta n c e
f .

In t hi s w a y a ll w a v e s w ill b e gr a du a lly a b so r b e d e x c e p t t h os e
m o s t s tron gly r e fle c te d The s e a r e h o wev e r ju st tho se of
.
, ,
 N E R N ST S H E AT ’
T HE O R EM 5
“
fr e que n cy v 7 Th e y a r e t hu s r e s i du a l
. The ul t r a r e d fr e
.
-

qu e n oy v o f t he i o n s t h e r e fo r e a gr e e s w i t h t he f r e qu e n cy o f
,
]

h
t e e r s i du a l r a y s 11° O n t he o t h e r h a n d t h i s v i br a t io n of t he
.
,

c h a r g e d a t o m s i s d e p e n d e n t o n t h e e l a s t i c p r o p e r t i e s o f t he

s u b s t a n c e a s w e r e c o g n i se d i n c o n s i d e r i n g t h e f or mul a
,

We t hu s c o n clud e t h a t t he e l a s t ic fr e qu e n cy o f the a toms

”

o f bi n a r y s a l t s a g r e e s t o a c l os e a pp r o x i m a t io n w i t h t he

op t i c a l f r e qu e n cy o f t h e i r r e s i du a l ra y s B u t s i n c e t he
“
.

el a s t i c fre qu e n cy of th e a t o m s d e te r m i n e s the b e h a vi o u r
of the ir a tomi c h e a t th e r i n g i s t h e r e b y c l o s e d a n d W
, , .

N er n st 1 1 1 w a s t hu s j u s t i fi e d i n p r o p o u n d i n g t h e fu n d a m e n t a l
l a w tha t i n ca lcu la ti n g t he a tom i c hea t of bi n a r y sa l ts w e
, ,

m a y si mp ly i n ser t for the a tom i c fr equ enci es v the fr equ en cies

of t he r esi d u a l r a y s .

In t h i s w a y a n um b e r o f i n d e p en d e n t w a y s w e r e op e n e d
U fo r d e t e r m i n i n g t he a t o m i c f r e qu e n c i es r e qu i r e d fo r t h e
p
c a lcul a t i o n o f t h e a t o m i c h e a t A c o mp a r i so n of th e v a r i o u s
.

v a lu e s o f v d e t e r m i n e d by th e s e d i ff e r e n t m et h ods sho w s i n
ge n e r a l s a t i s f a c t o r y a g r e e m e n t a t a n y r a t e i n o r d e r o f m a g n i
,

t ud e 112
. On e c o uld h a r dly e x p e c t m o r e a s w e s h a ll s o o n s e e , ,

i n v i e w o f t h e m a n y i d e a l i se d c on d it i o n s t h a t w e r e u s e d i n
t h e t h e or y .

§ 4 N erns t
.
’
s He a t T he ore m

W it h a v i e w t o d i sc ove ri n g e xp e r i m e n t a lly the ge n e r a l l a w

for the d e c r ea s e of the a t o m i c h e a t wh e n a pp r oa c h i n g l o w t e m
u re s W N er n s b e g a n i n 1 9 1 0 i n c o op e r a t i o n w i t h
t 113
p e ra t .
,
-

h i s r e se a r c h s t ud e n t s a s e r i e s o f m a st e r ly a n d wi d e ly pl a n n e d
,

re s e a r ch e s .F o r b y a n e n t i r e ly d i ff er e n t r ou t e f r o m E i ns tei n
,

— n a m e ly b w a y o f t h e r m o dy a m c s
n i — h e a l so ha d b e c o m e
.
, y
co n v i n c e d t h a t t h e a to m i c h e a t o f s o l i d b o d i e s mu s t b e c o m e

v a n i s hi n gly sm all on a pp r o a ch i n g a b s ol u t e z e ro In hi s .

O p i n i o n t h i s r e sul t w a s o n ly o n e o f s e v e ra l c o n se qu e n c e s o f a

g e n e r a l p ri n c i pl e n a m e ly a w w o h
,
n e l a ,
f e a t 1 14 Th i s H ea t .

h
T eo re m o f N ns
er t— O ft e n c a ll e d t h e Th i r d La w o f Th e r mo

dy n a m i c s—s ta te s i n its or i gi n a l f o r m the foll o wi n g fa c t : If

, ,

w e r e ga r d a sy s te m o f c o n d e n s e d ( i e l i qu i d o r s o l i d ) bo d i e s
. .
,

whi c h p a ss e s a t te mp e r a t u re T by m e a n s o f a n i soth e r m a l
r ea c t i o n f r o m o n e s t a t e t o a n o t h e r a n d if A i s t h e m a x i mum
,

work whi ch c a n b e ga in e d f rom th i s r ea c t io n th e n ,

 36 T H E Q U ANT U M TH E O R Y
dA
0 fo r th e l i m i t T 0
dT

tha t i s to sa y , i n the i mm ed i a te n e i ghbou r hood o

f a bsolu te z er o ,

the m a x i m u m w or k w hi c h be ga i ned i s
ca n i nd ep en d en t of the
temp er a tu r ’
. B u t i t f o ll o w s i mm e d i a t e ly
fro m t h i s if w e ,

a pply th e t w o l a w s o f t h er m o dy n a m i c s
115 t h a t fo r a n
y ,

r e a c t i o n wh i c h ch a n g e s t he s ys t e m f r o m t he i n i t i a l c o n d i t i on

wi th e n e r gy UI t o the fi n a l c on dition w i t h e n er gy U2 t he ,

r e l a t i o n h olds t h a t

d U1 d U2
for t he l Im It T 0
7T dT

l—I
lT
gr a m me
N ow , S i n c e
I i f w e ta k e a a to m of t he s u b st a n c e
-

” ,

g i v e s th e a t o m i c h e a t , w e a r e l e d t o e n u n c i a t e t h e f o ll o wi n g

r ul e : i n the i m m edi a te n ei ghbou r hood of a bsol u te z er o , the

a tom i c hea t of cond en sed sy s tem s r em a i ns u n c ha nged d u r i n g

a ny for m a tion
tr a n s .

P l a n ck 116 h a s gi ve n N er n s t s Th eo r e m a st ill m or e ge n e ra l
’

for m : N ot on ly the d if er ence of the a tom ic hea ts ( befor e a n d

after t he r ea c ti on) i s to a ssu m e t he v a l u e 0 a t a bsol u te z er o bu t ,

a l so ea ch a tom i c hea t i tself i s to do t he sa m e Thu s i t f o ll o w s .

fr o m t h e e x t e n d e d N er n st Th e or e m i n a gr e e m e n t wi th the
°
,

d e m a n d s o f th e qu a n t um t h e or y t h a t t he a t o m i c h e a t s o f
,

s ol i d b o d i e s d i s a pp e a r a t a b s o lu t e z e r o .

m m E ins te i n T h e ory A t omi c Hea ts

’
T h I e nt on s of
5. e p r o v e

T he ex p e r i m e n t s o f N er n st a n d hi s c o ll a bor a to r s p r o v e d
qu i t e c o n v i n c i n gly th a t t he a to m i c h e a t o f a l l sol i d b o d i e s
t e n d s t o w a r d s a z e r o v a lu e a s t h e t e m p e r a t u r e f a ll s In .

t h e m a i n th e c o u r s e s of t h e se d e c r e a s i n g v a lu e s sh o w e d a
,

n o t a b l e a g r e e m e n t w i t h E i n stei n s f o r mul a
’
A t l ow
t e mp e r a t u r e s h o w e v e r s y s t e m a t i c d i s c r e p a n c i e s w e r e fo u n d
, ,

i n a l l c a s e s i n t h e se n s e t h a t t h e ob s e r v e d a t o m i c h e a t s f e ll
,

o ff mu c h m or e s l o wly t h a n E i ns tei n s f o r mul a d e m a n d e d 1 1 7

’

1V N er n s
7 .
t a n d F A L i.nd em a.nn 1 1 8 t r i e d t o t a k e t h e se d i s
c r e p a n c i e s i n t o a cc ou n t b y c o n s t r u c t in g a n e mp i r i c a l f o r mul a ,

a n d t h i s a c t u a lly e x p r e s s e d t he O b s e r v a t i o n s mu c h m or e
a ccu r a t e ly t h a n d i d t he E i n stei n f or mul a Th i s N er n s t .
 I M PRO VEM E N T O N E I N S TE I N S T HE O RY
’
37

Li n d em a n n fo r mul a wh i ch ,
is n ow o n ly of h i s tor i c a l i n t e r e st ,
is as fo ll o w s

z“
3R x c

m 4 wh e re x
(

It rec e i v e s a m e a n i n g if w e supp os e t h a t o n e h a lf o f a ll the

a t o m s v ib r a t e w i t h t h e f r e qu e n cy v t he o t h e r h a lf w i t h ,
th e
,

f r e qu e n cy 5 Wh i l e t h i s s upp o s itio n is u n te n a bl e i n th i s

raw f or m i t c o n t a i n s a k e r n e l o f t r u th n a m e ly r e c o g n i t i o n
, , ,
”
o f the f a c t t h a t t h e m o n oc hr o m a t i c t h e o r y of a to m i c
“

h e a t s wh i ch a s s u m e s o n ly a si n gl e fix e d f r e qu e n c y v fo r a l l
,

a t o m s g o e s t oo fa r b e i n g a n i d e a l i s a t i o n o f t h e r e a l s t a t e o f
, ,

a ffa i r s . E i n stei n w ho a t fi r s t fo r t h e s a k e o f s i mpl i c i t y

, , ,

r e ck on e d wi t h o n ly o n e f r e qu e n c y ha d h im s e lf a l r e a dy ,

r e c o g n i se d h o w m a t t e r s s t o o d a n d d ra w n a t t e n t i on t o t h e
,

n e e d fo r a m e n d i n g h i s t h e o r y 1 19 N o wa d a y s i n fa ct w e t h i n k
.
, ,

o f a s ol i d b o dy s a y a c r y s t a l a s bu i l t up o f a t o m s r e gul a r ly
, ,

a r r a n g e d up o n a s p a c e l a tt i c e a c c o r d i n g t o B r a va i s c o n c e p
’
-

t io n a n d t h i s hyp o t h e s i s h a s b e e n v e r i fi e d a s a c e r t a i n t y

t h r o ugh L a u e s d i sc o v e r y o f t he i n t e r f e r e n c e o f Ro n t g e n ra y s
’
.

In s uch a c o mpl i c a t e d m e c h a n i c a l s y s t e m h o we v e r t he , ,

S i n gl e a t o m s d o n o t v i b r a t e i n de p e n d e n t ly o f o n e a n o t h e r

w it h a s i n gl e f r e qu e n c y v B u t t h e p os iti o n of e qu il ib r i um
.

o f e a c h a t o m a n d t h e r e b y t h e t yp e o f i t s o s c i ll a t i o n s a b o u t
,

t h a t p o s i ti o n i s d e t e r m i n e d r a t h e r by t he f o r c e s wh i c h a l l t h e
,

o th er a t o m s o f t h e b o dy e xe r t up o n t h e a t o m i n qu e s t i o n .

W e ar e c on fr o n t e d w i t h a str uct u r e wh i c h i s c o mp a ra bl e to
t h e o n e d i m e n s i o n a l c a s e o f a v ib r a t i n g s tr i n g a n d wh i c h
-

t hu s p osses se s a wh o l e s p e c t r um o f n a t u r a l f r e qu e n c i e s ,

c o r r e sp o n d i n g t o th e o v e r t o n e s o f t h e s t r i n g If t he b ody .

c on s i s t s o f N a t o m s i t p o s s e ss e s i n g e n e r a l 3 N n a t u r a l
,

fr e qu e n c i e s 120 of w h i ch the s l ow e st a r e s ou n d w a ve s wh il e
t he qu i c k e s t f a ll In t he i n fr a r e d Th e m o s t ge n e r a l p o s s ibl e
.

m o ve m e n t o f e a c h a t o m t h e n c o n s i st s i n a s up e r p o s it io n
o f a l l t h e se n a tu r a l f r e qu e n c i e s N o w si n c e e a c h n a t u r a l
.
,

f r e que nc y r e p r e se n t s a l i n e a r i e S i mpl e p e r i o d ic m oti o n

,
. .
, ,

e x a c tly l i k e t he m o ti o n of a P la n ck os c i ll a t o r th e Id e a ,
38 T HE Q U A N T U M T H E O RY
n at u ra lly s ugge st e d i t s e lf , i n l ul a t i n g t he e n e r gy co n te n t
ca c -

of t he b ody t o a ll ot
,
to e a c h n a t u r a l f r e qu e n c y of p e r i o d i th e f

hv
t h e o r e ti c a l qu a n t um a m ou n t h, a s If t he n at u ra l p e r i o d
AT
6 1
w e r e i d e n ti c a l wi t h a l i n e a r o s cill at o r . The to t a l m ea n
e n e r gy o f t h e b o dy t h e n b e c o m e s

3N

in wh i ch th e s umm a ti on i s c a r r i e d o ve r a l l 3 N n a tu r a l
fr e qu e n c i e s v1 2 v3 ,
11 , v N
3
t h
,
a t i s o v e r t he wh o l e e l a st i c
, ,

s p e c t r um o f t h e s u b s t a n c e B y d i ffe r e n ti a t i o n w i th r e s p e c t
.

t o T w e ob t a i n t h e a t o m i c h e a t

T h e ory A tomi c Hea t s

’
§ 6 D eb y e
. s of

Th e k e r n e l of p r ob l e m t hu s c o n si st s i n c a lcul a ti n g the
the
e l a st i c s p e c tr um of a gi v e n b o dy t h a t i s i n d e t e r m i n i n g , ,

fo r a n y b ody th e p o si ti o n of i t s n a t u r a l p e r i o d s In t h i s s e n se .
,

th e t h eor y ha s b e e n w o r k e d ou t f r o m t w o d i ffe r e n t s i d e s ; o n
t h e o n e h a n d by P D ebye ”1 w h o t oo k a n e l a sti c c o n t i n uum
.
,

a s a n a pp r o x i m a t i on t o t he a c tu a l a t o m i c a lly c o n s t r u c t e d
b ody a n d o n the o th e r b y M B or n a n d v Har m an ; 22 w ho
,
. .

r e pl a c e d t he c r ys t a l o f l i m i t e d s i z e b o n f i fi i t e di
y e o n n

m e n s io n s . Th e d i ffe r e n c e b e tw e e n t h e s e t w o m e th od s o f
a pp r o x i m a t i o n c a u se s the m a i n p r ob l e m n a m ely th e w or k i n g , ,

o u t o f t he e l a s t i c S p e c t r um t o b e s olv e d u i t e d iff r e n t ly i n
q , e

t he t w o c a se s . The D ebye t h e or y wh i c h f r o m t he o u t s e t ,

l ea v e s o u t o f c o n s i d e r a t i o n t he c r y sta ll i n e a n d e v e n the ,

a to m i c s tr u c t u r e o f t h e b ody r e s t s U p o n t he c l a s s i c a l t h e o r y
, ,

o f e l a s t i c i t y wh i ch o f c o u r s e t r e a t s b o d i e s a s s t r u c tu r e l e s s
, , ,

c on t i n u a . F r o m i t f oll o w s t h e i m p ort a n t l a w : t he n umb e r

Z (v) dv o f a l l t h o s e n a t u r a l p e r i o d s t he f r e qu e n cy o f wh i ch ,

fall s w ith i n the i n te r v a l v d a m o u n t s t o 12 3

v, v,
 D E BY E TH E OR Y AT O M I C HEAT S 39
’
S OF

2
Z (y) d y 4 71
'

4 - —
3
0

H e r e V i s the volum e of the b ody or a n d c, a re t he v el o c i ti e s

,

w i t h wh i ch l o n g i t udi n a l a n d t r a n s ve r s e w a ve s re sp e c t i v e ly , ,

a r e p r op a g a t e d w i t hi n t he b o dy In t h i s c a s e h o w e v e r th e
.
, ,

f oll o w i n g d iffi c ul t y o c c u r s i n r e pl a c in g the b ody wh i ch i n ,

r ea l it y c o n s i s t s o f N a t o m s b y a c o nt i n uum n a m e ly t he
, , ,

e l a st i c s p e c t r um e x t e n ds t o i n fi n i t y t ha t i s the n umb e r o f
, ,

n a t u ra l f r e qu e n c i e s b e c o m e s i n fi n i t e ly g r e a t F or e x a mpl e .
,

the n umbe r o f n a t u r a l fr e qu e n c i e s ( fu n d a m e n t a l to n e a n d
o v e r to n e s ) of a l i n e a r s tri n g o f l e n gt h L a r e
-

i i
Vi :

2L fl
r es
p e c t1 ve l
y ( i 1, 2,

a cc or d i n g a s to wh e t her w e a r e c on si d er i n g tr a n sve rs e o r
l o n g i t udi n a l f r e qu e n ci e s The s e ri e s of o ve r to n e s t he r e fo r e
.

e x te n d s wi t h o u t l i m i t t o i n fi n i t y In r ea l i t y h o we v e r a s t he
.
, ,

b ody c on s i s t s o f N a to ms ( m a s s p oi n t s) i t m a y n ot p o s se ss
-

m or e t h a n 3 N n a t ura l fr e qu e n c i e s In o r d er t o a tta in t his.

,

D ebye he lp s h i ms e lf o u t by m e a n s o f t he fo ll o wi n g b old
s upp os it i o n In ste a d of ca l c u l a t i n g s tr i c tly the e l a sti c S p e c
.

t rum of t he r e a l b o dy c o n si s ti n g o f N a t o ms h e r e pl a ce s i t b y ,

t ha t o f t h e c o n t i n uum as a n a pp r ox i m a t i o n bu t br ea ks i t 01? ,

a r bi tr a r i l y a t t he 3 N th n a tu r a l p er i od D e by e t hus g e t s t he.

r e a t e s t f r e qu e n cy v m whi ch o ccu r s t h a t i s t h e U p e r l i m i t
g p , ,

o f t he e l a s t i c s p e c t r um f r o m t h e co n d it i o n
,

47 V 1 2
at ) v3
m
= 3N

t h e r e fo re
9N
it

The a to m ic h e a t of the body wh ic h fo ll o ws fr o m

,
is

Cr k Z ( ) d
2
v v
40 T HE QU ANT U M T H E O R Y
ul t wh i c h c an
a res e a si ly be b r ough t i n t o th e foll ow i n g m o r e
s mpl e f o m :
i r 124

wh e r e xm

Th e a to mic he at i s t h e r e fo r e on ly a fu n c t io n of the m a gn i tud e

6) G) t n
xm, that Is , It dep en ds on ly on t he w h o h e re
T
’

T kT °

Th i s ul t m ay be press e d t e r ms t hu s
’
res ex i n D ebye s : r ec kon

i ng the temp er a tu r e T as a m u l tip l e o f a temp er a tu r e O w hi c h

is c ha r a c ter i s ti c o h i u l a r bod , then t he a tom i c hea t i s
f t e
p a r t c y
re
p r ese n ted
f or a l l m on a tom i c bod i es by the sa m e cu r ve H en c e .

we mus t be ab e l cu rv e s O f a l l m on a t o m i c
t o b r i n g t h e 0,
b o di e s i n t o c o i n c id e n c e i f o n ly t h e s c a l e of t e mp e r a tu r e b e
,

su ita b ly c hos e n fo r e a ch s ub sta n c e 125 F or h i g h t e mp e r a .

t u r e s t h e D ebye f o r mul a p a s se s o v e r a s i t mu st d o i n t o t h e
, , ,

c l as s i c a l v a lu e o f D u lon a n d P e ti t U 3 R 126 j u s t a s d o
g , , ,

t h e E i n stei n a n d N er n st L i n d em a n n f o r mul ae
-
On t h e o t h e r .

h a n d i t d i ffe r s f ro m t h e s e l a t t e r i n fall i n g much m or e s l owly

,

a t l o w t e mp e r a t u r e s F o r wh i l e t he a t o m i c h e a t s a cc o r d i n g
.
,

t o b ot h E i n stei n a n d N er n st L i nd ema n n f a ll e x p o n e n t i a lly

-

( £
c on s t
wi th 72 e
”

T at l o w t e mp e r a tu re s , D eby e
’
s fo r mul a l e a d s
t o t he fu n d a m e n t a l l a w , ”7 tha t the a tom i c hea ts f bodoi eall
s a t
l ow tem p er a tu r es a re r o or tion a l
p p to the thi r d p ow er of the
a bsol u te temp er a tu r e .

It i s fu rt h er r e m a r ka b l e t h a t w e m a y w r i te fo r mul a ( 4 4 )
,

fo r t he m ax i mum n a t u ra l f r e qu e n cy i n a f o r m s u c h t h a t o n ly
m e a su r a b l e m a gn i tude s o c c u r i n i t F o r i f w e e x p r e s s t he t w o
.

v e l oc i t i es o f s ou n d 6 , a n d Cl i n t e r m s o f t he e l a st i c c o n st a n t s o f
t he b o dy a n d r e pl a c e th e v o lum e V o f t he g r a mm e a t o m b y
,
-

t he q u o t 1 e n t
d e n s i t y ( p)
5 28
-

1 07 t a)
A tp t x t

wh e r e
 D E BY E S TH EO R Y OF AT O MI C HEAT S 41
’

In i t x ga i n the c o mp r e s sib i l i t y o f t he b o dy a t he
is a ,

P oi sson r a ti o t h a t i s t he ra ti o o f t h e t r a n s v e r s e c o n t r a c t i o n
, ,

to t h e e x t e n s i o n The s i m i l a r i t y o f t h i s f o r mul a w i t h t h e
.

E i ns tei n r e l a t io n ( 35 ) s t r ik e s o n e i m m e d i a t e ly B u t i n t h is .

ca se the s e c o n d e l a st i c c o n s ta n t o f t he i s o tr Op i c b o dy a , ,

e n t e r s i n t o t h e e qu a t i o n a s w e ll A l t o g e th e r t he U pp e r l i m i t
.
,

vm o f t h e e l a s ti c s p e c t r um a t wh i ch a s o n e c a n S h o w 129 t h e
, , ,

n a t u ra l f re qu e n c i e s a lw a y s c r o wd t o g e t h e r cl o s e ly pl a y s i n ,

the s tr i c te r t h e o r y a n a n a l o g o u s r Ol e to t h a t pl a y e d by t he
”
s i n gl e n a t u r a l f r e qu e n c y v i n t h e m o n ochr o m a t i c th e o r y “
.

Co mp a r i s on w i t h e x p e r i m e n t s h ow s 130 t h a t t he D e bye
f o r mul a a t a n y r a t e fo r the m on a to m i c e l e m e n t s s u c h a s
,

a lum i n i um c o pp e r , s ilv e r l e a d m e r cu r y z i n c d i a m o n d d e
, ,
, , , ,

s c r i b e s t h e c o u r se o f v a lu e s o f t h e m e a s u r e d a t o m i c h e a t s

v e r y a c c u r a te ly P a r ti c ul a r ly a t l ow t e m p e r a t u r es t he p r o
.
,

p o r t i on a li t
y b e t w e e n t h e a t o m i c h e a t a n d t h e t h i r d p o w e r o f
t he a b s olu te t e mpe r a t u r e r e c e i v e s f a ir c o n fir m a t i o n ”1 In .

V i e w o f t h e f a c t t h a t t h e i d ea l i s e d V i e w r e pl a c e m e n t o f t h e
(
a c t u a ll y a t o m i c b o dy by a c o n t i n uu m c a r r i e d v e r y fa r w e
) i s ,

mu s t n ot r e ga r d t he a gr e e m e n t b e t w e e n t h e or y a n d e x p e r i
m e n t a s s e lf e v i d e n t A t l o w t e mp er a tu r e s D ebye s id e a l i s
-
.
,
’

hv
a tio n wi ll ju s ti fy i t se lf F o r t h en la r ge an d hen c e t he
.

1s
kT
.
,

h”
a m ount of e n er gy h v
is s m a ll ,
exce p ti n g wh e n v i t s e lf as

efi 1
’

s um e s s m a ll va lu e s . A t l ow temp er a tu r es ther ef or e , , on l y lon g

w a ves w i l l con tr ibu te sen sibl y f to the ener gy o a bod y , a nd hen ce
to i ts a tom i c hea t F o r l o n g w a v e s h o w e v e r t h a t i s fo r
.
, , ,

w a ve s t he l e n gt h of wh i ch i s g r e a t c o mp a r e d w i t h t he d i s
,

t a n c e b e t w e e n t h e a t o m s th e s p e c i fi c a t o m i s t i c c o n s t r u c t i o n o f
,

t he b o dy pl a y s n o p a r t ; fo r t h e m t h e s u b s t a n c e i s a lm o s t a
c o n t i n uum The p o s i t i o n i s qu i t e d i ffe r e n t a t h i gh t e mp e r a
.

t u r e s a t wh i c h t h e l o n ger f r e qu e n c i e s up t o the m a x i mum vm

,

( t h a t i s t h
, e s h o r t e r w a v e s d o w n t o t h e s m a ll e s t ) fu r n i s h c o n

t r i b u ti o n s o f e n e r gy F o r t he w a v e s wh i c h c o r r e sp o n d t o t h e
.

i
h gh e s t fr e qu e n c ie s p o s se ss l e n g th s a s c a n e a s i ly be S how n 1 32
, ,

wh i ch a re c o mp a r a bl e w it h the d i sta nc e s b e t we e n t he a t o m s ,

a n d fo r t h e se s h o rt e r w a v e s t h e m e d i um c a n n o t f a i l t o b e t r a y

i t s a t o m i c s t ru ct u r e H e r e t h e r e fo re ; i t s r e pl a c e m e n t b y a
.
,
42 T HE Q U AN T U M THE O RY
c o n ti n uum b ec o m e s qu e s tio n a bl e Si n ce t he a pp r ox i m a tion is
o n ly v e r y r o ugh .

§ 7 T he L a tt ice T he ory of A tomi c He a ts a cc or d ing t o B or n a nd

.

Kar man T he E l a s ti c S pect ru m of th e m ost ge n e ral Cry s ta l

.

A t t hi s p oi n t b o ve m e n t ion e d i n ve s ti gatio n s of Bor n

t he a -

a n d Kd r m d n i n t e r v e n e wh i ch go i n g b e y o n d D ebye t ak e
, , ,

a c c o u n t o f t he r e a l c r y s t a ll i n e s tr uc tu r e o f t he b o dy t h at i s ,

t o s a y t he S p a c e l a ttic e a rra n g e m e n t of th e a to m s
,
-
In o r de r .

to o v e r c o m e t he gr e a t m a th e m a t i ca l d i fficul ti e s i n vo lv e d t h e y ,

i m a g i n e d a s h a s a l r e a dy b e e n s a i d t h e a c t u a l l i m it e d c r y sta l
, ,

r e pl a c e d by o n e e x t e n d e d i n d e fi n i t ely Thus the d i st u r b i n g .

e ffe c t o f the s u r f a c e o n t h e i n t e r i o r c ould b e e l i m i n a t e d s o ,

t h a t n ow a l l a t o m s w e r e e x p o s e d t o t h e s a m e c o n d i t i o n s .

H e r e a l s o t he m a i n p r obl e m i s a ga i n t o d e t e r m i n e th e e l a s ti c
s p e ct r um o r — i f w e d i sp e n s e w i t h t he e x a c t c a lcul a t i o n o f
,

t he p r o p e r fr e qu e n c i e s — a t l e a s t t o d i sc o v e r t h e l a w a cc or d ,

i n g t o whi ch t h e p r o p e r ( o r n at u r a l ) f r e qu e n c i e s a r e d i s t r i bu te d
a m o n g t h e d i fie r e n t r e g i o n s o f f r e qu e n cy Th i s p r obl e m w a s .

fi r st s olv e d b y B or n a n d Kctr m d n fo r r e gul ar c r yst al s The .

l a w s t hus ob ta i n e d w e r e t h e n ex t e n d e d to t he c ase of s i mpl e

p o i n t l a t ti c e s of a rb i tr a ry symm e try a n d fi n a lly B or n d e
-

, ,
”
d u ce d t h e m i n hi s , D y n a m i c s o f t he Cr ys t a l La t ti c e
“
for ,

t he m os t g e n e ra l f or m of s p a c e
Th e s e m os t g e n e r a l S p a c e l a tti c es a r i s e f r o m t he p e r i o d i c
-

r e p e t i t i o n i n S p a c e of a d e fi n i t e g r o up o f a t o m s a n d e l ectr o n s

( b a s i c g r o up ) wh i c h o n t h e wh o l e i s e l e c t r i c a lly n e u t ra l a n d ,

i s e n c l ose d i n a p a r a ll e l o p i p e d o f s p a c e the “
e l e m e n t ar y ,

p a ra ll el op ip e d In F i g 4 s u c h a l a tt i c e i n t h i s c a s e ho w
. .
, ,

e v e r pl a n e i s i llu s tr a t e d i n wh i ch t he b a s i c g r o up c o n s i s t s
, , ,

of t h r e e p a r t i cl e s o x ) A ll p a rti cl e s f o r m toge th e r a
.

s i mpl e l a tt i c e a s d o t he o a n d x p a r t i cl e s
, W e ha ve i n t h i s .

w a y t h r e e i n t e r l oc k e d s i mpl e l a t t i c e s .

Thu s fo r e xa mpl e t he h a l o ge n c o m p o u n d s o f t he a l ka l i e s
, ,

( N a C l L
,
i Cl K C l ,
K B r K I R, bC l ,
R b B r R ,
b I a n d , so f o r t h), ,

f o r m c u b i c sp a c e l a t ti c e s i n wh i c h t he l a tti c e p o i n t s a r e
-

a l te r n a t e l O ccup i e d b t h e p o s i t i v e a l k a l i i o n a n d t h e n e g a t i v e
y y
h al o ge n io n ( s e e Fi g If w e r e g a r d the wh ol e cub e h er e
.

”
p ic tu r e d a s th e e l e m e n ta r y cub e t h e n t he b a s i c gr o up w o uld
“
,
 LATTI C E TH E O RY OF AT O MI C H EAT S 43

gh t p a r ti cl e s n a m e ly fou r i on s of e a ch so rt (t h e y a r e
c o n ta i n e i , ,

n um b e r e d h e r e ) .We h a v e t hu s e ight i n ter pe n e tr a t in g si mpl e

l a tt i c e s E ve r y fo u r of t h e m would h o w ev e r c o n s i s t o f the
.
, ,

s a m e k i n d o f p a r t i cl e H e n c e i t i s a dv i s a b l e to se l e c t i n th i s
.

c a se i n pl a c e of t he cub e the r h o mb o h e d r on (do ubl e l in e d i n -

as th el m e n ta r y p a ra ll e l o p i p e d Th e n the b a s i c
e e .

gr o up co n sist s o n ly o f t he t w o d i ffe r e n t p a r t i c l e s 1 a nd 8 o f ,

wh i c h the o n e l ie s i n a c o r n e r the o th e r i n t he middl e of t he

,

p a r a ll e l o p ipe d In fa c t w e ca n ge t the wh ol e l a tti c e by d iSp l a c

.

i n g t he b a s i c gr o up i n t he d i r e c t i o n o f t he t h r e e r ho m b o h e dr a l
e dge s a d i st a n c e e qu a l to a wh ol e mul t i pl e o f the l e n g th of
,
44 T HE QU ANT U M THE O RY
t he e dge . l a t ti c e c o n s i s t s t h e r e f o r e a c c o r d i n g t o t h i s
The ,

vi e w o f t w o i n t e r l a ce d si mpl e c ub i ca l a t o m i c l a tti c e s F u r ther

,
.

m o r e th ey a r e s u r f a c e c en t r e d l a t ti c e s t h a t i s t o s a y s u c h
,
-

, ,

t h a t n o t o n ly th e c or n e r s o f t he c u b e s b u t a l so the m i ddl e
,

p o i n t s o f t h e c ub e su r fa c e s a r e o c c upi e d If i n t he m ost
-

,
.

ge n e r a l c a s e t he b a s i c gr o up c o n t a i n s 3 d i ffe r e n t p a rti cl e s the ,

l a ttic e c on s i st s o f s i n t e r l a c e d s i mpl e l a t ti c e s .

F IG . 5 .

In or de r n ow to ge t a g e n e r a l v i e w o f th e l a w s wh i c h
gov e r n t he e l a s t i c S p e c t r um o f s u c h a m o s t g e n e r a l c ry s t a l ,

w e p r o c e e d a c c or d i n g t o B or n a n d Kd r m d n a s fo ll o w s : W e
i m a gi n e a n e l a st i c w a v e o f d e fin i t e w a v e l e n gt h a n d d e fi n i t e
‘

d ir e c ti o n (the n o r m a l to t h e w a v e f r on t ) p a s s i n g t h r ough the

c ry s t a l . Fo r e a ch w a v e t hu s d e fin e d t h e r e a r e 3 3 n a t u ra l
 LATT I CE THE O RY OF AT O MI C HEATS 45

f r e qu e n c i e s wit h p e r i o d ic it i e s v1 v 2 v3 3
T h e fi r st t h r e e v 3 .

f re qu e n c i e s VI in) v3 c o r r e s p o n d t o t h o se n a tu r a l f r e qu e n c ie s
, ,

of t h e c r y s t a l by whi c h t he s i n gl e i n t e r p e n e tr a ti n g s i mpl e
‘

l a t t i c e s a r e s i m i l a r ly d i stor t e d t o a fi r s t a pp r o x i m a t i o n w i t h
ou t b e i n g co mp e ll e d t o m o v e r e l a t i v e ly t o o n e a n o t h e r .

Th e se a r e t h e t h r e e or d i n a r y a co u s t i c n a tu r a l p e r i o d s ( o n e
l o n gi tud i n a l t w o t r a n sv e r s e )
,
T he r e m a i n i n g 3 (s . 1)
f r e qu e n c i e s o n t h e o t h er h a n d c o r r e sp o n d t o a n oth e r typ e
, ,

o f m o t i o n o f t h e cr y s t a l n a m e ly t o t h o s e n a t u r a l f r e qu e n c i e s
, ,

w i t h whi c h th e s i n gl e s i mpl e l a tti c e s o s c ill a te wi t h r e sp e c t t o

o n e a n ot h e r w i th o u t di s t or t io n If t he b a s i c gr o up c o n t a i n s
.

o n ly o n e p a r t i cl e ( s i e if t h e c ry st a l c o n si st s o f o n ly a
. .

s i mpl e l a tt i c e t h i s s e c o n d t yp e of m o t i o n di s a pp e a r s a l to
,

ge th e r a n d w e a r e l e ft w i th o n ly t h e t h r e e a c ou sti c n a t ur a l
,

f r e qu e n c ie s v1 v2 1 3 If o n the ot h er h a n d w e a r e d e a l i n g
, ,
1 .
, ,

wi t h a c r y sta l s a y o f t h e h a l o ge n c o mp ou n d s of a n a l k a l i
, ,

fo r e x a mpl e r o c k sa l t ( N a Cl) 3
,
-
2 t h e r e e x i st a s w e h a ve
, , ,

se e n ,
be s i d e s t h e t h r e e a c o u s t i c o sc ill a ti o n s t h r e e fu r th e r ,

n a t u r a l f r e qu e n c i e s o f t h e s e c o n d t yp e In c on se qu e n c e .

o f t h e r e gul a r c r y s t a l ch a r a c t e r o f t h e a l k a l i n e h a l i d e s t h e s e ,

t h r e e n a t u ra l fr e qu e n c i e s e x a c t ly c o i n c i d e a t a n y ra t e fo r ,

l o n g w a v e s a n d gi ve r i s e t o t h a t m ot io n i n wh i ch the s od i u m
,

l a tt i c e v i b r a te s a ppr o x i m a te ly a s a r i gi d s tr u c tu r e a ga i n st t he
l i k e wi s e r i gi d c hl or i n e l a tt i c e We se e a t on c e t h a t i t i s
.

ju s t the n a tu r a l f r e qu e n c y l a s t c on s i d e r e d t h a t w i ll pl a y t he
c hief p a r t i n t h e O p t i c s o f t h es e c r y st a ls F o r wh e n a n .

e l e c tr o m a g n e t i c w a v e m e e t s t h e c r yst al t he so di um i o n s ,

a r e dr ive n b t h e e l e c t r i c f o r c e of t h e wa v e to t h e on e S i d e
y ,

a n d t h e o pp o s i t e ly c h a r g e d chl o r i n e a t o m s a r e d r a w n t o t h e
-

o pp os i t e s i d e . It i s t hu s ju st t h e t yp e o f v ib ra t i o n d es c r ib e d
a b ov e t h a t i s b r o ugh t a b ou t If t h e fr e qu e n c y of th e .

ex t e r n a l w a v e a pp r o a ch e s cl o s e ly t o t h a t o f t h e n a t u ra l
p e ri od r e son a n c e o cc u r s Th e s e i n f r a r e d v ib r a t ion s t h e r e
, .
-

f or e a r e wh a t d et e r m i n e the c o u r s e of the r e f r a c t i v e i n d ex
, ,

e s p e c i a lly i n t h e i n fr a r e d Th e y a r e t h e s o c a ll e d i n fr a “
- -

r e d di s p e r si o n f r e qu e n c i e s It i s a l so i n t h e i r n e i ghb o u r hoo d
.

t h a t t he pl a c e s o f m e t a ll i c r e fl e c ti o n l i e whi ch a r e d e t e c te d
b y t h e m e th o d o f r e s i d u a l ra y s -
.

W hat ha s jus t b e e n st a t e d fo r t he s pe c i a l c a s e 3 2
( al k a l i n e h a l id e s m a
) y o f c o u r s e b e i mm e d i a t e ly g e n e r a l i s e d
, , .
46 T H E Q UANT U M TH E O RY
For if th e b a s i c gro up s c o n si st s o f 3 d iffe r e n t p art i cl e s , i t
i s ju st t he 3(s 1 ) n a t u r a l fre qu e n c i e s t h at d e t e r m i n e t he
d i sp e r si on of t h e c r y st al A m o n g t h e m a r e t h ose i n th e
.
,

n e i ghb o u r h oo d o f wh i c h t h e r e g i o n s o f m e t a ll i c r e fl e c t i o n

r e s i du a l r a y s li If h e b as i c gr o up c o n t a i n s p p o s i t i v e
( ) e t .

a t o m i c r e s i du e s a n d s e l e c t r o n s t h e f r e qu e n c i e s v
p 4
v ,
3 ,

fa ll c o r r e s p o n d i n gly i n to t w o cl a sse s : th e fir st c l a s s c o n si s t s
of 3(p 1 ) i n f r a re d fr e qu e n c i e s wh i c h a r i s e f r o m t he
-

a t o m i c r e s i du e s ; t h e s e c o n d c on s i s t s of 3 s
( p) U l t ra V i o l e t -

f r e qu e n c i e s wh i ch a r e t o b e a s c r ib e d t o th e i n flu e n c e of t he
,

e l e c tr o n s . The i nf r a r e d n a t u ra l f r e qu e n c i e s d e c id e th e
-

c ou r se of t h e r e fr a c t i v e i n d e x i n t he i n fr a r e d t h e p os i t i o n -

o f t h e r e si du a l r a y s a n d a s w e s h a ll s e e , t h e a t o m i c h e a t s ;
, ,

t h e ul tr a v i o l et na tu r a l f r e qu e n c i e s , o n th e o t h e r h a n d , d e t e r
-

m i n e chi e fly t h e r e f ra c t i v e i n d i c e s i n the vi s ibl e a n d ul t r a

vi ol e t . I ci d e t a lly , t e gen e r a l l at t i c e th e o y o
n n h r f B o n
r 1 34 -

c o n fi r ms t h e l a w p r e v i o usly e n u n c i a t e d b
y H a b er 1 35 t h a t t he

f r e qu e n cie s o f the fir st cl a ss ( i n fr a r e d ) b e a r t h e s a m e r a ti o t o -

t h e se c on d ( ul t ra v i o l e t ) c l a ss a s r e g a r d s o r d e r o f m a gn it ud e
-

, ,

a s t h e s qu a r e r o o t of t h e m a ss o f t h e e l e c tr o n b e a r s t o t h e

s qu a r e r oo t o f th e m a ss o f t h e a t o m .

A f te r t h i s d i g r e ss io n l e t U S n ow r e t u r n t o ou r star t i n g p o i n t -
.

U p t o t he p r e sen t w e h a v e a lwa ys c on s i d er e d a w a v e o f
d e fin i t e l e n gt h A a n d w i th a d e fi n it e n o r m a l d i r e cti on n a n d ,

w e h a ve s e e n t h a t c or r e sp on d i n g t o i t t h e r e a r e i n t he m o st ,

ge n e r a l c a s e 3s n a tu r a l fre qu e n c i e s v 1
, 1
3
L et U S n ow 1
3.

a ll ow the w a v e l e n gt h A t o v a r y c on t i n u o u sly
-
k e e p i n g t he ,

w a ve dir e c ti o n c on s t a n t by goi n g fr o m i n fi n i t e ly l o n g wa ve s
-

t o th e sm a ll e st Th e n e a ch of t he 3 3 n a t u ra l f r e qu e n c i e s wi ll
.

a ls o v a r y c o n t i n u o u s ly a n d w i ll p a ss t h r o ugh a c o n t i n u o u s
,

r a n g e o f v a lu e s In o th er w or d s t h e 3 3 n a t u r a l f r e qu e n c i e s
.
,

a r e c e r t a i n fu n c t i o n s o f t h e w a v e l e n gt h A -

f »
o)
r

F r o m t h i s, h ow e ve r w e l e a r n t he fu n d a m e n t a l fa c t t h a t a ll
,

t h e s e r a n g e s of v a lu e s o f th e s i n gl e n a t u r a l f r e qu e n c i e s a r e
on l y fi n i te i n ex ten t a n d t ha t t her efor e ea c h of the 33 con ti n u a , ,

of fr equ enci es a u tom a ti ca l l y br ea ks Oj f a t a hi ghes t l i m i ti n g

fr equ en cy .
,
”
A u t o m a t i c a lly i e wi t h o u t o u r a r b i t ra r y a s s i s t
. .

a n c e ( a s i n D ebye s c a s e ) s ol e ly o n a cc ou nt o f th e a n a lyt i c a l
’

,
 LA TT I C E T HE O RY OF A T O MI C HEAT S 47

for m of the fu n ction f Th i s i s e x pl a i n e d by t h e f a c t t h a t

,

the w a v e l e n gt h A of p oss ibl e w a v e s i n the c ry s ta l h a s a

-

l owe r l i mit se t t o i t w a v e s o f l e n gth b e l o w a c e r t a i n l ow e st

valu e c a n n ot e x i s t Thi s i s m ost s i mply r e c og n i s e d fr o m the
.

foll o wi n g i n stru c t ive e x a mpl e If w e c on s i d er a s i mpl e .

cub i c a l l a tt i c e h a v i n g t he a tom i c d i st a n c e a a n d e x a m i n e , ,

fo r ex a mpl e l o n gi t ud in a l w a v e s wh i ch a r e b e i n g p r o p a g a t e d
, ,

l
a o n g a n e dg e o f t h e cub e — s o t h a t a l l a to ms o n a n e dg e a t

ri ght a n gl e s t o t h i s s i d e o sc i ll a t e i n the s a m e ph a s e i n t h e

r f h —
di e c tio n o t e e dg e th e n w e s ee at o n c e th a t t he s m a ll e s t
w a v e t h a t i s p o s s i bl e h e r e h a s the l e n g t h Ami 2a F or n .

th i s w a v e n a m e ly s ucc e s si ve pl a n e s of t h e cu b e s w i n g
, ,

i n o pp os i t e ph a se t h a t i s a ga i n st
,
o n e a n ot h e r Th e
,
“
.

fu n c t i on a l r e l a ti on b e tw ee n v a n d A a s sume s the sp e c i a l
f or m 135
V Vm 8 111

F o r i n fi n it e ly l on g w a v e s (A co v 0; if w e p a s s o n
t o s h o r t e r w a ve s v i n c r e a s e s c o n t i n u ously u n t i l fo r A
,
2a , , ,

i t r e a ch e s i t s m ax i mum va lu e vm A t t h i s l i m i t i n g f r e qu e n cy .

vm the r a n ge o f p o s s i bl e v S b r e a k s o ff a u t o m a t i c a lly
’

U p t o t he p r e se n t w e h a v e giv e n t he w a v e d ir e c t i o n ( n t he -

d i r ec tion o f t he n or m al ) a c e r t a i n fi xe d v a lu e a n d h a ve ,

a ll o w e d t h e w a v e l e n gt h A t o v a r y
-
We n ow gi ve the w a ve .

di r e ct i on by de gr e e s ot h e r v a lu e s a n d a t e a c h st e p w e a ll o w ,

t he w a v e l e n gt h t o v a r y f ro m t he v a lu e co t o t he l e a s t
-

p os s ib l e v a lue The n th e n a tu r e o f the fu n c t ion a l d e pe n d e n c e

.

o f t he m a gn i t ud e v ; o r A a n d t h e p o s i t io n o f t h e l i m i t i n g
. ,

fr e qu e nc i e s a l s o c h a n ge c o n ti n u ou sly wi t h t he w a v e d i re c tio n -

s o t ha t w e m a y sa y : t he 3 3 n a t u r a l f r e qu e n c i es a r e i n ,

ge n e r al c on t i n u ou s fu n ct ion s o f the wa ve l e n gt h A a n d of
,
-

t he w a v e d i r e c t i o n n
-

v, n ) , ( i 1, 2, 3, 3 3)

In i t , h o f t he fu n ct ion s f b r ea k s o ff a u t o m a ti c a lly fo r a
ea c ,

m i ni mum v a lu e of the w a v e l e n gt h a t a n upp e r l i m it -

(o
r m an wh
, i ch i t s e lf s t ill d e p e n ds o n t he w a v e d i r e c ti o n -
.

Th e se e qu a t ion s e x p re s s t he l a w of d i sp er si on o f wa ve s i n
c rysta l s for th e y d et e r m i n e for e a ch wa v e the 33 f re qu e n c ie s
,
48 T HE Q U ANT U M THE O RY
vi h e n c e a l s o t ell u s ho w t h e r a t e s o f p r o p a ga ti o n
a nd

q ; v, A d e p e n d o n t h e w a v e l e n gt h a n d t h e w a v e d i r e c ti o n
- -
.

Th e d i s p e r s i o n l a w b e c o m e s p a r t i cul a r ly S i mpl e i n t h e r e g i o n
o f l o n g w a v e s : fo r t h e t h r e e a c o u st i c v i b r a t i o n s t h e r e

l a t i o n s 1 37

91 W) ( )
4 9
A

h old . In t h e m t h e t h r e e
m a gn i tud e s q1 (n ) q2 ( n ) a n d q3 (n ) , ,

are thr e e i n g e n e r a l d i ffe r e n t

,
fu n c t i o n s o f t h e w a v e ,

d i r e ct i o n A n d fu rt h e r t h e s e a r e t he t h r e e v e l o c iti e s o f
.
,

p r o p a ga t i on o f t h e t h r e e a c o u sti c v i br a t i o n s In the r e gi o n .

o f l o n g w a v e s t h e r e f o r e t h e t h r e e v e l o c i t i e s o f p r o p a g a t i on
, ,

o f t h e t h r e e s l o w a co u st i c v i b r a t i o n s a r e i n d e p e n d e n t o f t h e

w a v e l e n gth t o a fi r st a pp r o x i m a t i on
-
.

The di s p e r s i o n l a w ( fo r l o n g w a v e s ) a s sum e s a v e r y
di ffe r e n t a pp e a r a n ce for t h e 3 (s 1 ) r a p i d v ib r a t i o n s
v v V It a s s um e s t h e f o r m
3.
4 , 5 3

g
Pi ”)
p
g 4, 5 , ( )
5 0

h e r e th e di s c on sta n t s t h e
a re a r e a ga i n c e r t a i n
,

fu n c ti on s o f t h e w a v e d i r e c ti o n The v e l o c i ti e s o f p r o p a ga
-
.

t io n h e r e a s sum e t h e v a lu e s

Qt WA Pd”)
and w ould t hu s b e fu l i n e ar n c t i on s of the w v l e n gth
a e -
.

W e m a y s umm a r i s e t hu s : the el a s ti c s ec tr u m of t he m os t
p
gen er a l cr y s ta l , t he ba si c gr ou p o f w hi c h con ta i n s 3 p a r ti c l es ,

con si s ts o f 33 sep a r a te p a r ts E a ch p a r t con s i s ts

of fi n i t
ael y ex ten d ed con ti n u u m of fr equ en ci e s . The thr ee fir s t
a cou s ti c n a tu r a l
p a r ts con ta i n the to ta l i ty o f a ll s l ow , f re

som e ti m es ca l l ed cha r a c ter i sti c The r em a i n i n

qu enc i es ( g
3 (s 1 ) p a r ts i n cl u d e the ra
p d
v i ol e t
i ) ( f
i n r a -
r ed a nd u l tr a -

n a tu r a l f
r e u en ci es, w hi c h p l a y t he chi e p a r t i n d eter m i n i n g
q f
the op ti c a l d i sp er si on a n d t he p osi ti on s of m eta ll i c r e l ec ti on f .

§ 8 Co ntinu a ti o n
. . T he La w O f D i s tri b u ti o n of the N a tu ra l
F re q u e nc ie s

W h i l e t h i s k n o wl e dg e o f the g e n e r a l c ha ra c t e r of t he e l a st i c
S p e c t r um i s a s w e sh a ll s oon see o f g r e a t v a lu e i t i s n o n e
, , ,
 LAT T I C E THE O R Y OF A T O MI C H EAT S 49

the l e s s i ns u ffic ie n t for t he qu e sti on of t he e n e r gy c on t e n t a n d -

m o l e c ul a r h ea t o f t he c r y s ta l i n a smu c h a s e ve n fo r t he
, ,

S i mpl e s t c r y s t a l a s tr i c t c a l c ul a t i o n o f t he e l a s t i c sp e c t r um
,

i s n o t p o ssib l e a t t he p r e s e n t t i m e We k n o w h o w e v e r o n
.
, ,

t he o t h e r h a n d t h a t w e n e e d n o t k n o w t he wh o l e d e t a i l s o f
,

t he e l a s ti c s p e c tr um t o c a l c ul a t e th e e n e r gy c o n t e n t a n d t h e-

m o l e c ul a r h e a t bu t t ha t i t su ffi c e s to kn o w t he l a w a c c or d i n g
,

to w h i c h t he n a t u ra l f r e qu e n c i e s a r e d i st ri bu te d o v e r t he
e l a s t i c s pe c trum ( o r i t s i n d i v i du a l Th i s i s
the m o r e t r u e t h e c l o s e r t oge t h e r t h e n a t u r a l fr e qu e n c i e s
,

li e. N o w i n r e al i t y t he fi n i te c r y st a l p o s s e s se s if i t c o n
, ,

s i s t s o f t h e b a s i c g r o up (o f 3 p a r t i cl e s ) N t i m e s r e p ea t e d ,

3N s n a t u ra l f r e qu e n c i e s w hi c h a r e d i s tr i bu ted so t ha t N f r e
,

u en ci es fa l l to ea ch of t he 3 3 br a n ches of t he s ectr u m If N
q p .

b e c o m e s i n fi n i t e t h e N i n divi du a l n a t u r a l fr e qu e n ci e s o f e a c h
,

br a n c h m er ge i n t o o n e a n ot h e r t o fo r m a c o nt i n uum a n d w e ,

t e a c tly t he e l a s t i c S p e c tr um t h a t w e h a v e jus t b e e n co n
g e x

s id e r i n g . W e s e e f r o m t hi s t h a t th e m o r e w e a r e j u stifie d
,

i n r e pl a c i n g th e fi n i t e c r y s ta l b y o n e of i n fi n i te e x t e n t th e
be tt e r ou r re sul t s i f w e k n o w on ly th e d i s t r i b u t i o n l a w o f the
n a t ur a l f r e qu e n c i e s ( w i t h ou t k n o w i n g t h e i r p o s it i o n e x a c t ly
) .

The l a w of d i s tr i bu t i o n o f t h e n a tu r a l f r e qu e n c i e s wh i ch ,

w a s d i s co v e r e d b y B or n a n d Kctr m d n a n d e xte n de d b y B or n
i n hi s D y n a m i c s o f t he Cr y st a l La t t i c e t o t he m o st ge n e r a l
t yp e o f c r ys ta l m a y b e f o r mul a t e d t hu s : S el ect fr om the
,

tota l i ty of a ll el a s ti c w a ves t he sm a l l gr ou p w ho se l en gths l i e ,

betw ee n A and A d A, a nd w hose n or m a l d i r ection l ies i n the

el em en ta r y sol i d a n gl e 1 38 dQ . E a ch f
o the 3 3 br a nc hes o f the

sp ec tr u m then con tr i bu te Y4
d AdQ n a tu r a l fr equ enci es to thi s
A
gr oup . H e r e V d e n ote s t he volum e of the fi n i t e c r ysta l .

§ 9 Co ntinu a ti on
. . T he A tomic Hea t s a t L ow , v ery Low , a nd

Hi gh T em pe ra ture s

The k nowl e dg e of th i s l a w d istr ibu ti on a ll o ws U S to

of

w ri te d ow n a t on ce the t h er m a l c a p a c i t y o f t he c ry sta l c on
s i s t i n g o f N 3 p a rt ic l e s . F r o m ( 4 2) i t i s
50 T HE Q U A N T U M T H E O RY

(i3- 7
r, k
i
E - l
”

T a
H Y

2 —
a le T
35 4 1r

i :
1 0
(
6
1d

T hi s f or mul a i s to b e i n t e r p r e te d
foll o w s : the n a tu r a l i r e
as

q u e n c i e s v a r e by
, ,
t o b e e x p r e s s e d as fu n c t i o n s o f th e

w a v e l e n gt h A a n d t he wa v e di r e c ti on n : t h e n the i n te gr a
- -

t i o n i s t o b e p e r f o r m e d w i th r e s p e c t t o A fr o m the s m a ll e s t
wa v e l e n gt h AAn ) wh i ch i t se lf d e p e n d s up o n t h e w a v e
-

d i r e ct i on n up t o the m a x i mum A so
,
Th e r e s ul t of t h i s
i n t e g r a ti o n s t i ll d e p e n d s o n t h e wa v e di r e c tio n a n d th e i n d ex -

i. F i n a lly i n t e g r a t i on i s t o b e p e r for m e d o v e r a l l d i r e c t i on s
,

( t h a t i s o v e r a l l e l e m e n t a r y s ol i d a n gl e s b e t w e e n 0 a n d fi n
, )
a n d s umm a t i o n o v e r a ll 3 3 b r a n ch es of t h e S p e c tr um Bu t .

w e h a v e s e e n t h a t t h e 3 3 b r a n ch e s o f t he S p e c tr um f a ll i n to
t w o gro ups The fi r st 3 b r a n ch e s ( i
. 1 2 3 ) c o n t a i n t he , ,

t ot a l i t y o f s l o w a c ou st i c n a t u r a l fr e qu e n c i e s ; for t h ese
b r a n ch e s w e h a v e th e di sp e r s i on l a w ( 4 9 ) wh i ch i s v a l id fo r
l o n g wav e s The r e m a i n in g 3 (s 1 ) b ra n c h e s c on ta in the
.

t ota l i ty of t h e qu i ck ( i n fr a r e d a n d ul tr a vio l e t ) n a tu r a l fr s
- -

q u en c i e s ,
w i t h t h e e n t i r e ly d iffe r e n t typ e o f d i sp e r s i o n l a w

wh i ch a ls o holds for l on g wa v es H e n ce t he s u g .

33

g e s t i on n at u ra lly o ccu r s of d i v i di n g t he su m of ( ) i n to
5 2

tw o p a r t s c or r e sp o n d i n g
,
t o th e t w o diffe r e nt gr oup s of fr e
u e n c i e s a n d o f wr i t in g
q
“
‘
I, I ?
wh e r e

R? ) W

Th e s e s t ill ve r y c o mpl i c a te d f or mul a m a y a c c o r d i n g t o ,

B or n , b e b rought i nto a v er y si mpl e a n d co mp r e h e n s iv e for m

 LA TT I C E T H E O RY OF A T O M I C H E A T S 51

by l i m iti n g co n s i d e r a ti o n s to l o w te mp e ra tu r e s a n d i n
ou r

tr o d u c i n g c e rt a i n a pp r ox i m a ti o n s A s w e h a v e a l r e a dy re .

c o gn i se d a t l o w t e mp e r a t u r e s o n ly t h e l o n g w a v e s c o n t r i bu t e
,

to th e e n e r gy c o n t e n t-
H e n c e w e s h a ll a pply i n fo r mul a ( 53 )
.

a l l t h os e a pp r o x i m a t i o n s wh i ch a r e i n t r o duc e d b y c o n fi n i n g
)
o u r s e lv e s t o l o n g w a v es L e t u s c o n s i d e r fi r st E3
. H e re w e .

s e t i n pl a c e o f t h e W s o f ( 50) t he con s ta n t v a lu e s v wh ich

’

2 ,

a r e i n d e p e n d e n t o f t he w a v e l e n g t h A a n d o f t he wa v e
-

dir e c t ion If w e d o t h i s w e c a n pl a c e the c o n sta n t fa c tor s

,

in f ro n t of b oth i n t e gr a t i o n si gn s ,
and w ri t e

wh er e x ,
2
11

The fa c tor i n s qu a r e b r a ck e ts ha s ho w ev e r a s i mpl e m e a n in g ,

'

, .

Fr o m th e l a w o f d i s t r i bu t i o n o f t h e n a t u r a l p e r i o ds w e s e e ,

n a m e ly , t h a t t h i s fa c t o r gi v e s t h e su m to t a l o f a ll n a t u ra l -

fr e qu e n c i e s t h a t o ccu r i n o n e of the 3 3 b r a n ch e s of t he
s p e c t r um ; i t t h e r e f o r e h a s t h e v a lu e N whi c h a s ha s a l r e a dy ,

b ee n s a i d i s t h e n um b e r o f b a si c g r o up s wh i ch go to m a k e
,

up t he cr ysta l If w e ch oos e t he p i e c e of crys ta l u n d er c o n

.

s i d e r a tio n s u c h t h a t i t s s i z e i s s o t h a t N i s e qu a l t o t h e

A voga d r o n umb e r t h e n i f w e r e m e mb e r t h a t N k
,
R for
Pg ” t he e x p r e s s i o n
,

I ( 2)
‘
R wh e re x,
v

fo ll ows If w e comp a r e t hi s r e sul t wi th ( 3 4 ) w e s e e th a t F?)

.

(
— e xce p ti n g for t h e m i ss i n g f a c to r 3— c o n s i s ts o f 3 s 1 )
E i n stei n fun c ti o n s W e wr i t e the e x p r e s s i on i n the for m
.

33

wh ere xi

in whi ch th e a bb r e vi a ti o n is o bv ious . The f a c t th a t , in u si n g

52 T HE Q U AN T U M T HE O RY
t h e se a pp roxi m a t i o n s w e c o m e a c r o s s E i n stei n f a c t or s i e
, ,
. .

t hat w e e n c ou nte r t h e m o n o c h r o m a ti c t he o r y m i gh t h a v e ,

b e e n a n ti c i p a t e d F o r s in c e w e t r e a t e d the v s h e r e a s con
.
,
’

s ta n ts t h a t a r e qu i t e i n d e p e n d e n t o f w a v e l e n g t h a n d w a v e
-

d ir e c ti o n th e s e vib r a t io n s r e p r e s e n t p r o c e s s e s wh i c h h a v e
,

n o t h i n g t o d o w i t h t h e p r o p a g a ti o n o f e l a s ti c w a ve s i n t h e

c r y s t a l a s a wh o l e : a n d t h i s m e a n s t h a t t h e i n d i v i du a l
p a rti cl e s u n c o upl e d a s i t w e r e p e r f o r m 3 ( s
, ,
1) mon o
ch r o m a t i c v i b r a tion s .

Th e a pp r o x i m a t e e v a lu a t i o n o f t h e fi rs t p a r t I ) i s qu i t e
g
‘

d i ffe r e n t .Fo r h e r e w e h a v e t o u s e fo r t he fr e qu e n ci e s
v
1,
v
2
,
v
3
t
,
h e r e l a t i on s w h i c h c on n e c t t h e t h r e e a c o u sti c

n a t u r a l f r e qu e n c i e s w i t h w a v e l e n g t h a n d w a v e d i r e c t i o n
- -
.

H e r e w e h a v e t h e r e for e to d e a l w i t h t h r e e r e a l e l a st i c o s c i ll a
t i o n s wh i ch a r e p r o p ag a t e d i n t h e c r y s t a l w i t h t h e t h r e e
,

d i ffe r e n t a c o u s t i c v e l o c i t i e s q1 ( n ) q2 (n) q3 (n ) e a c h o f wh i c h
, , ,

d e p e n d s o n t h e d i r e c ti on ( n ) . Th e c r y s t a l a c t s h e r e a s a
dyn a m i c wh ol e e x a c tly a s i n D ebye s p oi n t o f V i e w H e n c e
,
’
.

w e m a y c o n j ec t u r e t h a t all ow s i t s elf t o b e b r o ugh t ,

i n t o th e f o r m of t h r e e D ebye fu n c t i o n s Th e m o r e
e x a c t ca l c ul a t o
i n n r s t i
c o fi m h upp o si ti o n a n d giv e s u s
s s ,
1 4 0

1 x c
4 f
-

dx
__

E ( r — 1V
i =1 0

wh ic h t a k i n g D ebye s f o r mul a ( 4 5 ) i n to c o n s i d e r a t io n
,
’
,
we

m a y w r i t e i n t he foll o w i n g i mm e d i a t e ly i n t e ll i g ibl e fo r m

The t h re e m a gn itud e s x , h e r e pl a y t h e par t of thre e upp e r

l i m i ts o f f r e qu e n c y Th e ir v a lu e s a r e
.

w h e r e t h e t h r e e m a g n i tud e s qi r e p r e se n t c e r ta i n m e a n d i r e c
t i o n s o f t h e a c o u s t i c v e l oc i t i e s , wh ich t h e r e f or e n o l on g e r
 LATT I C E THE O RY OF AT O M I C HEAT S 53

d e p e n d o n t he w a v e d ir e c ti o n F r o m ( 55 ) a n d ( 5 7 ) w e ge t for
-

t he t h e r m a l c a p a c i ty of t h e p i e c e o f c r y s t a l c o n si d e r e d

D ( )
xi
5 13 6130

N ow , c e N p a rt i cl e s o f e a c h o f t h e 3 d i ffe r e n t k i n d s o f
sin

p a rt ic l es a r e p r e s e n t t h a t is o n e gr a mm e a to m o f e ac h k in d
,
-

of p a rt i cl e e a ct
x ly — fo r N i s t h e A v og d o
a r n um b e r — t he p i e c e
o f c r y st a l c o n t a i n s 3 gr a mm e a t o m s of d i ffe r e n t s o rt s o f -

p a r t i cl e s . If t h e r e fo r e w e c u t the c ry s t a l i n to s e qu a l
, ,

N
p ie c e s in s uch a m a n n e r t ha t , eac h piece co mp ri s e s on ly __ e

ba s i c gr o up s ,
th e n ea ch o f t h e se pie ce s c o n ta i n s a SO ca -
ll e d
H e n ce
'

m ea n o n 1y a
'

i a mm e a to m 1f we n ow c o n s 1d e r
g
-
.

si n gle o n e o f t h e se p ie ce s ,
i ts th e r m a l c a p a c i ty is we c a ll
i t t he “
m ea n a to m ic h eat Cu , an d w e may wr i t e

Em
m +
§ m) E

He re the ha ve th e me me an i ng F o r t he
’
xi s sa as in

p ie c e of c r y s ta l n ow u n de r c o n si d e r a t i o n c on s i s t s of
I
Eb a s i c
8

gr oup s ,
and ha s t h e r e f o r e t he volum e Z . F o r mul a
3

ho w e ve r , o bv i ou s ly re m a i n s u n c h a n g e d wh e n we re pl a c e in
I
K
it N and V by
; a nd
3
. The qu a n t ity
5 , th e v olum e of a

m e a n g r a mm e a to m i s a lso c a ll e d the m ea n a tom ic v olu m e

-

,
.

In the ca s e o f c h e m i c a l c o mp o u n d s i n wh i ch s e v e r a l s o r t s ,

o f a t o m s o cc u r i n t h e b a s i c g r o up a n d a l s o i n t h e ca s e o f ,

poly a to m ic e l e m e n ts i n wh ic h the b a sic gr o up c o n ta i n s s e v e ra l

,

pa r tic l e s o f a l ik e so rt w e fr e qu e n tly S pe a k of t he m ol ecu la r

,

hea t . In d o i n g so w e f oll o w t he u s u a l ch e m i c a l c on ce p t i on
, ,

i n a s mu c h a s w e i m a g i n e t h e 3 p a rt i c l e s o f t he b a s i c gr o up
d i vi d e d i n to on e o r se v e r a l s u b gro up s a n d re ga r d e a c h s u b -

gr o up ta ke n al o n e a s a m ol e cul e If th e n t he m ol e cul e
, , .
 54 THE Q U ANT U M THE O RY
c on t ai n s q ato ms t h e n q C, i s t h e m ea n m ol ecu la r hea t ; fo r
,

exa mpl e th e ,
b a s i c g r o up o f r o ck s a l t ( N a Cl ) c o n t a i n s o n e-

so d i um i o n a n d on e c hl o r i n e i on . The wh ol e p i e c e of cr y st a l ,

N N
wh i ch by d e fi n i ti o n c o n t a i n s b a si c group s c o mp r i s e s
5
, , ,
3

t h e r e fo r e s o d 1u m i on s and th e sa me n um b er of c hl o rin e
l
io n s , tha t i s t o sa y
g N a Cl -
m ol e cul e s .
q i s i n th i s S pe cia l
c ase e
q u al to 2 . He n ce 2 C ,
re p r e se n t s th e t h e r m a l c a pa c i ty
”
of N N a Cl -
m ol e cul e s ,
tha t i s the m ea n m ol e c ul a r h e a t o f
,

r o ck -
lt
sa .

If a m on g th e 3 p a r t i c l e s of the b a s i c gr oup t h e r e a r e p
a t o m i c r e s i du e s a n d s e l e c t r on s t h e n um b e r o f E i n s tei n
p ,

f a c t or s i n (5 9 ) r e du c e s t o 3 ( p s i n c e the 3 s
( p) ul t ra

v i ol e t f r e qu e n c i e s a r i si n g f r o m th e s p e l e c tr o ns c on tr ib u t e
o n ly i n a v a n i s h i n gly s m a ll d e gr ee t o t he a t o m i c h e a t a s c o m

p a r e d w i th t he i n f r a r e d W e thu s a r r i v e a t t h e l aw : the
-
.

m ea n m olecu l a r hea t of a cr y sta l w hose ba si c gr ou p i nc lu d es p

m r or d i er en t) a tom i c r esi d u es m
( s i i l a
fi i s a d e u
p a t a s u
f , ,

en tl y low tem er a tu r e o thr ee D e b y e ter ms w i th i n en er a l

fi c i p f , ( g , ,

thr ee d ijfer en t up p er l i m i ts of fr equ en cy) a n d 3 (p 1 ) E i n st e in

ter m s (i n w hic h the 3 (p 1 ) i nfr a r ed n a tu r a l fr equ en ci es f or -

l ong w a ves app ea r a s fr equ en cy n u m ber s) .

W h e n w e d es c e nd t o t he l ow est t e mp e r a t u re s t h e E i n stei n ,

t e r m s d i s a pp e a r e x p o n e n ti a lly a n d o n ly t h e t h r e e D ebye t e r m s
,

r e m a i n fo r t h e se a s w e k n o w
, ,
d e c r e a s e mu c h m or e sl o wly , .

In t h e m w e c a n fu r t h e r r e pl a c e a l l t h e upp e r l i m i t s o f t h e
t h r e e i n t e g ra l s (s e e b y oo so t h a t t he i n t e g r a l s t h e r e b y
,

b e c o m e n um e r i c a l c on st a n t s R e m e mb e r i n g ( 58 ) w e ge t t h e
.

fu n d a m e n t a l l a w th a t the m olecu l a r hea t of ever y cr ys ta l a t

,

the l ow es t temp er a tu r es i s p r op or tion a l to the thi r d p ow er of

the a bsol u te temp er a tu r e S o t h e g e n e r a l l a tt i c e t h e o r y c o n
.

fi r m s D ebye s r e s ul t The f o r mul a o b t a i n e d h a s t h e f o ll ow i n g

’
.

s i m pl e of r m 14 1

5
1 6 77 10 VA
- 4

5h 3

wh e r e VA i s t he m ea n a to m i c v olum e
m e a n a t o m i c w e i gh t
m ea n d e n s i t y
 TE S T S O F T H E BOR N KA R M A N T H E O R Y -
55

an d q p re
r e s e n t s a qu a n t i t y wh i ch i f s u i t a bly d e fi n e d m a b
y e , ,

c all ed the m e a n a c ous ti c v e l oc i t y i n tr oduce d i n pl a c e of the ,

th r e e d iff e r e n t a c o us ti c v e l o c i t i e s ql q2 q3 , , .

Al so i n t he o t h e r e xt r e m e c a s e for h i gh t e mp e r at u r e s a , ,

v e r y u s eful fo r mul a ca n b e o b ta i n e d a s H Thi r r i n g 142 , .

S h o we d H e s t a r t e d f r o m ( 5 2 ) a n d d e v e l op e d t h e e x p o n e n t i a l
.

fu n cti on s i n se r i e s The f oll owi n g va lu e i s t h e n ob ta i n e d fo r

.

t he m e a n a t o m i c h eat :

>
J, h 2
J, h 4
J, h 6
C = 3R l +
tr
-

v
t oeo

wh e re t he co efli c i e n t s J1 J2 J3 , , ,
d e p e n d i n a c o mpl ic a t e d
m a n n e r on the e l a s t i c c o n st a n ts o f t h e c r y st a l s t h e a t o m i c ,

m a s se s a n d t he a t om i c d i sta n c es
,
.

the B or n Kar ma n T h e ory

’ ’

§ Io
. T e s ts of -

H o w d o m a tt e r s s ta n d w i t h r e g a r d to the t e s ti n g o f t h e
B or n Kd r m d n Th eo r y ? We s e e a t o n c e t h a t i t i s i n co m
-

p a r abl
y m o r e d i fficul t t h a n i n t h e c a s e o f D eb e s T h e o r y : fo r
y
’

e v e n i n s i m pl e c a s e s t h e c a l c ul a t i on o f t h e m e a n a t o m i c
,

h e a t o f a c r y st a l i s v e r y c ompl i c at e d a n d r e qu i r e s a b ov e a l l ,

a m o r e e x a c t k n o wl e dg e o f i t s e l a s t i c b e h a v i ou r t h a n w e a t

p r e s e n t p o ss e s s O n ly b y r e st r i c t i n g o u r a tt e n t i o n t o l ow
.

a n d v e r y l o w t e mp e r a t u r e s o n t h e o n e h an d wh er e t he ,

for mul ae (6 0) a n d ( 6 1 ) m a y b e a ppl i e d a n d o n the ot h e r , , ,

t o t h e r e g i o n o f h i gh t e mpe r a t u r e s w it h i n t h e l i m i t s of ,

a ppl i c a b i l i t y o f Thi r r i n f r mul a a r e w e e n a bl e d t o

’

g s o

c a rr y o u r c a l c ul a t i o n s fo r a n um b e r of s i mpl e s u b s t a n c e s t o

t he p o i n t o f c o mp a r i s o n w i t h e x p e r i m e n t a l r e s ul t s B or n .

a n d Kar m d n t h e m se lv e s i n o n e o f t h e i r fi r s t publ i c a t i o n s 14 3
,

t est e d t he f or mul a v a l i d fo r t h e l o w e st t e m p era tu re s

( D e by e s
’
T 3
l a w )-
by c o mp, a r i n g i t s r e s ul t s w i t h t h o s e o f
ex p e r ime nt Th e y l i m i t e d t h e m s e lv e s i n t h i s c a s e t o m e t a ls
.

( A l ,
C u A g
,
P b ),
wh i c h h o w e v e r — at a n
, y r a t e i n t h e u s u a l
f m a r e n ot p r op e r c r y s ta l s b u t i rr e g u l a r c r ys t a ll i n e
o r —
,

a ggr e g a t e s . F o r t h i s r e a s o n t h e y p r o c e e d e d a s i f t he m e t a l
,

w e r e a n i sotr op ic b ody a n d ob t a i n e d t h e m e a n a c o u s ti c
,

ve l o c it y— t he on ly qu a n ti t y i n ( 6 1 ) wh i ch i n ge n e r a l re qu ir e s
56 THE Q U A NT U M TH E O RY
e x te n s i v e lcul a t i o n — fro m t he foll ow i n g
ca l
re at on i wh ic h
h o ld s fo r i so t r O p i c b od i e s : 144

3
"
s?
3
‘

2 rt
H e r e q, and q, are v t he
e l o c i t i e s o f p r o p a ga ti o n o f t h e

l o n gi t udi n a l a n d t r a n s v e r s e e l a s t i c wa v e s m a g n it ude s t h e r e , ,

for e wh i c h m a y b e s i mply c a l c ul a te d f r o m t h e t w o e l a s t i c
,

n t
c o s a ts o n f h
t e i s o t r O p i c b o dy a n d i t s d e n s i t y 1 4 5 T h e .

a g r ee m e n t o f t h e v a lu e s o f C” t hu s f ou n d w i t h t h e e x p e r i

m e n t a l d a t a i s e s p e c i a ll y i n th e c a s e o f Al a n d Cu (a n d a lso P b)
, ,

qu t e goo d
i .A E c u . k e n 1 46 h a s h ow e v e r p o i n t e d o u t r i gh t ly
, , ,

t h a t n o w e i gh t s h o uld b e a t t a ch e d t o t h i s a g r e e m e n t For .

t h e v a lu e s o f t he e l a s t i c c on s t a n t s wh i ch B or n a n d Kci r m d n
u se d fo r c al c ul at i n g qZ a n d q, a r e t h ose whi ch a r e c or r e c t a t
t he o r d i n a r y r oo m t e mp e r a t u r e If w e t ak e t h e i r d e p e n d e n c e
.

o n t e mp e r a t u r e i n t o a c c o u n t th e g oo d a g r e e m e n t b e t we e n
,

t h eo r y a n d e x p e r i m e n t d i s a pp e a r s Me t a ls a r e i n d e e d n o t
.
, ,

i so t r o p i c b o d i e s a n d h e n c e i t i s n o t p e r m i s s i b l e t o u s e t h e
,

o bs e r v a bl e e l a s t i c c o n s t a n t s wh i ch d e p e n d up o n t e mp e r a t u r e
, ,

i n c al c ul a ti n g g .

Ma tt e r s a r e mu c h m or e f a v o u r a b l e i n t he c a s e o f r e a l
c r y s t a l s i n wh i c h a s e x p e r i m e n t s by E
, ,
Ma d e l u n g 1 4 7 S h o w
.
,

t he e l a st i c c o n s ta n t s v a r y v e r y l it tl e w it h t e mp e r a t u r e Bu t .

h e r e the c a l c ul a t i o n of t he m e a n a c oust i c v e l o c i ty 5 gi v e s r i s e
i n g e n era l t o n ot a b l e di ffic u l t i e s 148 wh i ch m a y h ow e v e r , , ,

b e c l e a r e d a w a y i n s i mpl e c a s e s b y a v e r y p r a c t i ca l m e t h o d
d u e t o L Hopf a n d G L echn er “9 H op f a n d L echn er we r e
. . .

t hu s e n a b l e d s u c c e s s fully t o c ar r y o u t t h e c a l c ul a t i o n s fo r
s ylv i n
( K C l ) r ock s a l t
,
-

( N a Cl
) fl u or s p a r
( C aF
2)
-
a n d py r i t e s

( F eS
2) . T h e y p r o c e e d e d t o c a l c ul a t e t h e qu a n t i t y
g f r o m t he

o b s e r v e d v a lu e s o f G a s sum i n g t h e c o r r e c t n e s s o f f o r mul a
e,

a n d t h e y t h e n c o mp a r e d t h e s e w i t h t h e v a lu e o f
q
c a l c ul a t e d f r o m e l a st i c d a t a Th e r e sul t s h o we d v e r y s a t i s fa c
.

t o ry a g r e e m e n t 150 .

It i s o f p art i c ul a r i n t e r e st t o t e st th e v e r y c l e a r fo r mul a
( )
6 0 wh i ch g i v e s t h e m e a n a t o m i c h e a t a s a su m o f t h re e

D e bye fu n c t i o n s a n d 3 (s 1 ) E i n stei n fu n c t i o n s H e r e t he .

t h r e e i n fr a r e d n a t u ra l f r e qu e n c i e s v v v c o i n c i d e a n d the
2 2 2
-

, , ,
 T E S T S O F T H E B O R N KA R M A N T H E O RY -
57

t h r e e E i n ste i nfu n c t io n s b e co m e e qu a l to o n e a n o t h e r If w e .

i n t r o du ce t he fu rt h e r a pp r o x i m a t i o n o f r e pl a c i n g t he t h r e e
d iffe re n t qu a n t i ti e s mg i n th e D eby e fo r mul a b y a m e a n va lu e
at i t fo ll o w s t h a t
,

on WM ) ? E ( w) } ( )
6 4

In t h i s w e u se d e du c e d f r o m f o r m ul a ( 58 )
t he v a lu e o f a;

b y m e r e ly r e pl a c i n g q, i n i t b y a m e a n v a lu e 9 wh i c h c a n b e ,

c a l c ul a t e d by t he m e t h o d o f H opf a n d L echn er ju st m e n t io n e d .

0
h
x , on th e ot he r ha n d ,
a cc or d i n g t o i wh e r e v
0
i s t he
kT
i n f ra -
re d u ra l f r e qu e n c y o f t he c ry s t a l ( fo r l on g wa v e s)
n at ,

wh i c h m a y b e d e t e r m i n e d f r o m the di s p er s i o n i n the i n f ra
r e d or b
y t h e m e t h o d o f r e s i du a l r a y s .

F o r mul a ( 6 4 ) h a d a l r e a dy b e e n g i v e n p r e v i o u s ly t o B or n , ,

by W N er n st 15 1 w ho h o w e v e r b a s e d hi s a r gum e n t o n a
.
, , ,

s upp o s i t io n wh i c h i s n o l o n g e r t e n a b l e N er n st s ta r t e d .

f r o m t he c on c e p t i o n t ha t fo r e xa mpl e i n the c a s e of r oc k , ,

s a l t t h e N a Cl m o l e cul e s a r e l o c a t e d up o n t h e p o i n t s o f t h e
,
-

spa c e l a t t i c e
-
a n d t h a t t h e m o s t g e n e r a l s t a t e o f o sc i ll a t i o n
,

of t he l a tt i c e a r i s e s f r o m t he s up e r p o s i t i o n o f t w o m od e s o f

m ot i o n firs t ly t he o s c ill a t i o n o f t he wh ol e m ol e c ul e s i n the

,

l a tt i c e str u c tu r e wh i c h gi v e a D ebye t e r m a n d s ec o n dly t he

-

, ,

i n t r a m o l e c ul a r o s c i ll a t i o n s o f t he t w o a t o m s wh i c h b e i n g
-

, ,

a lm o s t m o n o c h r o m a t i c l e a d t o a n E i ns tei n t e r m
,
Th e .

a g r e e m e n t o f t he B or n N er n s t f o r mul a w i h h
( )
6 4 -
t t e ex

e r i m e n t a l d a t a i s n o t v e r y sa t i s f a c to r y i n t h e c a s e o f N a Cl
p
a n d KC] b u t mu c h b e t t e r i n t h e c a s e o f A Cl wh i c h b e l o n g s
, g ,

t o t h e s a m e c r y s t a l t yp e ”2 The r e a so n fo r th i s i s b e l ie v e d
.

b y E Schr od i n ger 153 t o li e i n t he e x ce ss i v e ly r o ugh a p

.

p r o x i m a t i o n i n he r e n t i n for mul a
F i n a lly Thi r r i ng s fo r mul a ( 6 2) ha s a l s o b e e n t este d b y
’
'
, ,

Thi r r i ng h i m s e lf 154 fo r N a Cl KCl a n d b y n e gl e c t i n g c e r t a i n

'
, , , ,

fa c t o r s fo r Ca F2 a n d Fe sQ Ta k i n g i n t o a c c o u n t t h e va r i a tio n
, .

o f t he e l a s ti c c o n s t a n t s w i t h t e mp e r a t u r e wh i c h ho w e ve r i s
( , ,

to be r e ga r d e d a s u n c e rt a i n a n d p r o vi s i o n a l s i n ce t he v a lu e s
a r e o n ly o b ta i n e d b i p l h f u nd o o d a gr e e m e n t
y n t e r o a t i o n
) e o g
b e t wee n t h eo ry a n d ex p e ri m e n t In c o n n e c ti o n w i t h t h e .

M i n i n g fo r mul a B or n 155 ha s a l so c a lcul a t e d t he ato m i c

,
'

h e a t of d ia m on d a n d co mp a r e d it wi th e x p e r i m e n t S i n c e in .
58 THE Q U AN T U M T H E ORY
thi s s h w v
ca e, ol cc e w
er , u
the wn B orn
e a st i on s t a nt s er e nk n o ,
'

p r oc e e d e d t o e v a lu at e the cu r v es of a to m i c h e a t fo r v a r i ou s
p os s ib l e v a lu e s a n d t o se l e c t fr om t h e m t h a t c u r v e whi ch
,

c o n f o r m e d m ost c l o se ly t o t h e r e s ul t s o f o bs e r v a ti o n s Thu s .
,

fo r ex a mpl e ,
the va lu e x s ob t a i n e d fo r

t he c o mp r e ssib i l it y ; th i s i s i n s a ti sfa c tory a gr e e m en t w it h th e

v a lu e p r ob a bly t oo s m a ll m e a su r e d by W Richa r d s vi z
, , .
, .

12
06 10
“

Fr o m a ll this w e p oss ib il i ti e s of t e sti n g t he

se e t h a t th e
B or n Kci r m ci n Th e o r y of A t o m i c H e a t s p a r t ly o n a c c o u n t o f
-

the g r e a t d i ffi cul ti e s o f c a l c ul a ti o n p a r tly o n a c c o u n t o f o u r ,

i n s u ffi c i e n t k n o wl e dg e of t h e e l a s t i c b e h a vi ou r of c r y st a l s a r e ,

e x c e e d i n gly s p a r se s o t h a t fo r t he p r e s e n t D eb e s mu c h m or e
’

, y
t r a c t a b l e f or mul a ( i f n e c e s sa r y w i t h t he a dd i t io n of E i n stei n ,

t e r m s) a pp e a r s m o r e u s e ful If in S p i t e o f t h i s fa ct s o much
.
, ,

s p a c e h a s b e e n d e v ot e d h e r e t o t h e B or n Kd r m d n Th e o r y t h e -

r e a so n i s t o b e s o ug h t i n t h e c o n v i c t i o n t h a t t h i s t h eo r y h a s

go n e mu c h fu r th e r t h a n t h a t o f D ebye i n to t he k e r n e l of t he
m a tt e r Fo r w i thou t a m or e ex a ct t r e a t m e n t of t h e s t r u c tu r e
.
,

o f t h e s p a c e l a t ti c e a n d i t s dy n a m i c s o u r k n o wl e dg e o f t h e
-

n a t u r e o f t h e s o l i d s t a t e mu st w it h o u t d o ub t r e m a i n f a ul t y .

§ II . T he E qu a ti on of S ta t e of a S o li d B od y
Li n k i n g up wi th t h i s n e w d e vel op m e n t of t h e t h e o ry
of a to m i c h e at s a n umb e r o f i n v e st i ga t or s c h ie fly E
, , .

Gr i i n ei sen 1 5 6 S R a tn ow ski
,
1 57 a d P D bye
n . e 1 53 h a ve w ork e d
,
.
,

o u t a t h e o r y o f t h e s o l i d st a t e w i t h t h e o b j e c t o f c r e a t i n g a s

a c o u n t e r p a r t to t h e Ki n e t i c T h e o r y o f G a se s a Ki n e t i c

Th e or y o f S ol i d s O n e of t he m a i n p r obl e m s i n t h i s c o n
.

”
n e x i o n i s t o f o r mul a t e a n E qu a ti o n of St a t e t hat i s a
“
, ,

r el a tio n b e t we e n p r e s sur e v olum e ( V) a n d t e mp e r a t u r e

(p ) , ,

T a p r o b l e m wh i c h a c c o r d i n g t o t he d o c tr i n e o f t h e r m o
( ) , , ,

dy n a m i c s i s t o b e r e ga r de d a s s olve d a s s o o n a s t h e f r e e
,
“

e n e r gy E of t h e b o dy i s k n o wn a s a fu n c tio n o f the t e mp e r a
u
t r e a n d th e o v lum e 1 5 9 Th e n t he p r e s s u r e for e x a mpl e w i ll
.
, ,

fo ll ow f ro m t h e s i mpl e e qu a t i o n
 E Q U A T I O N OF ST A T E O F A S O LI D B O D Y 59

wh ic h ,
l b e t we e n p V a n d T g i v e s the e qu a t io n
a s a r e a tio n , , ,

o f s ta te a t o n c e If th i s i s k n ow n w e h a ve m a ste re d qu a n t i
.
,

t a t i v e l y t h e b e h a v i o u r o f t he b ody fo r a l l c h a n g e s o f s t a t e .

F o r e x a mpl e t he c oe ffic ie n t s o f e x p a n s i o n
,
a n d t he c o m (1 ,

r e s si b il i t r e s ul t f ro m t h e w e ll k n o w n f o r mul ae
p y x, -

K :

V
( 0 i s t h e v o lum e a t t h e z e r o p o i n t ) -

P D ebye 1 5° w a s t h e fi r s t t o dr a w a tt e n ti on t o t h e f a ct t h a t
.

t he m o d e l o f th e s ol i d b o dy wh i ch fo r m s t h e b a si s of t h e
a t o m i c h e a t t h eo r i e s o f E i n s tei n D eb e, a n d B or n Kd r m d n ,
y
-

i s n e c e s sa ri ly t o o h i ghly i d e a l i s e d for thi s i d ea lised solid

bod y ha s a s i s e a si ly s e e n a z er o coefiici e n t of exp a n si on
, ,
‘
In .

fa c t i f a s ha s a lwa ys b e e n ass um e d h it h e r to t h e f orc e s

, , ,

whi c h pull t he a to m s b a ck i nto th e i r p osi tio n of e qu i l ibr i um

a r e p r o p o r t i o n a l t o t h e fi r s t p ow er o f t h e i r r e l a t i v e d i s pl a c e

m e nt s ( a s sumpt i o n of qu a s i e l a sti c ity H ooke s La w ) t h e n

-

,
’

th e a t o m s w i ll e x e cu t e symm etr i c a l o s c i ll a t i on s a b ou t t h i s
po sit i o n of r e st If th i s supp o si ti on , vi z H ooka s La w be
. .
’

v a l i d fo r a ll t e mp e r a t u r e s t h e n t he m e a n v o lum e of t he
,

bo dy— th a t i s , the v olum e t h a t i t p osses s e s wh e n a l l a t o m s a r e

e x a c t ly i n t h e i r p o s i t i o n s o f r e st — mu s t b e j us t a s o f t e n o v e r

s h ot a s u n d e r s h ot h o w e v e r g r e a t t h e a mpl i t ud e o f t he h e a t
,

v i b r a ti o n s m a y b e H e n c e if w e wa r m the b ody f r o m z e ro
.
,

u n ti l i t p os s e ss e s t h e v olum e V0 a n d if w e a s s um e th a t a l l ,

a t o m s a r e a t r e s t a t z e r o t h e n i t s m e a n v o lum e a t a n t e m
, y
e r a t u r e w i ll a l s o b e e qu a l t o V0 Th b dy t h r e fo r e d o e s
p e o e .
, ,

n o t c h a n g e i t s m e a n ob se r v a bl e v o lum e w i t h r i s e o f t e mp e r a
,

t u r e i t s c o e ffic i e n t o f e x p a n s i o n i s t h e r e f o r e 0 If w e d es i r e t o .

r e p r e s e n t t he a c t u a l b e h a v i o u r of t h e s o l i d b o dy , n a m e ly i t s ,

ex p a n s io n wh e n h e a t e d ,
as fr o m t h o u s a n dfold e x
k n ow n to us

e r i e n c e w e a r e n e c e ssa r i ly o b l i g e d a c c o r d i n g t o D e b e t o re
p , y , ,

pl a ce B oc ke s L a w o f F o rc e by a n e x p r e s s i on i n v o lvi n g h i gh e r
’

p o w e r s of t h e va r i a t i o n o f a to m i c d i st a n c e T he n t he os c ill a .

t io n s o f t h e a t o m s be c o m e u n s ymm e t r i ca l a n d t h e r e o c c u r s a ,

d i spl a c e m e n t of t h e ir po s it i o n o f r e s t a s the e n e r gy o f v i br a t io n
i n c r ea s e s If w e a rr a n ge t he ge n e r a l i s a t io n o f Hooke s La w
.
’

so t h a t a gr e a t e r fo r ce i s n e c e ssa ry t o b r i n g t h e a t o m s n ea r e r

t o g e th e r t h a n t o se p a r a t e t h e m t h e n t h e c h a n ge i n t he ,
60 T HE Q UA NT U M T H E O RY
p os i t io n of r e s t o c cu r s i n su c h a m a n n e r t h a t fo r i n c r e asi n g
e n e r gy o f v i b r a t i o n t h a t i s fo r r i s e o f t e mp e r a t u r e t he
, , ,

r e l a t i v e d i s t a n c e s o f t h e a t o m s i n c r e a se a n d h e n c e t h e b o dy ,

i n c re a s e s i n v o lum e D eby e h a s e x te n d e d t he t h e o r y i n t h i s
.

s e n se A m o n g ot h er t h i n gs t his gi ve s u s the l a w pr e v i o u sly d e

.

d u c e d b y Gr n ei sen
i t 1 6 1 t h a t a t s uffi c i e n t ly l ow t e mp e r a t u r e s t h e
t h e r m a l c o e ffi c i e n t o f e x p a n s i o n i s p r o p o r ti on a l t o t h e s p e c i fi c
a

he at . Mo r e o ve r t h e v e r y s m a ll c h a n ge i n c o mp r e s s ibil i ty
,

wi t h t e m pe r a t u r e i s we ll a cc o u n t e d for o n D ebye s Th eo ry ’

§ 12 . T he T he rma l Co nd u c ti v ity of S o li d B od i e s a cc o r d in g t o D eb y e

Th e i mp o r ta n c e D ebye Th e o r y i s b y n o m e a n s
c on fin e d
’
of s

t o t h e r m a l e x p a n sio n On . the c on tr a r y , i t b e c a m e
m a n ife s t
t h a t a n ot h e r i mp o r t a n t gr o up o f ph e n o m e n a r e qu i r e t h i s
ge n e ra l i s a t i o n of H ooke s L a w In t h e i d e a l i s e d s ol i d b o dy
’
.
,

i n wh i c h t h e e l a s t i c f o r c e s ob e y H ooke s La w t h e e l a s t i c
’

w a v e s w i ll b e c o m e s up e r p o se d with ou t d i st u rb a n c e a n d w ill ,

p e n e t r a t e t h e wh ol e b o dy w i th o u t b e c o m in g w e a k e n e d If .

w e i m a g i n e t h e i d e a l i s e d b o dy a s a h o r i z o n t a l i n fi n i t e ly ,

e x t e n d e d pl a t e o f fi n i te t h i ck n e s s a nd if w e t ra n sm i t a ,

p o w e r ful m o ti o n ( hi gh t e mp e r a tu r e ) t o th e upp e r l a ye r o f
a to m s wh i l e w e k e e p t he l o w e r l a ye r a t r e s t ( i e a t z e r o
,
. .

t e mp e r a t u r e ) t h e n a n e l a st i c e n e r gy c u r r e n t ( h e a t cu r r e n t )
,

w i ll p a s s c o n t i n u a lly f ro m a b o v e t o be l o w A n e n e r gy .

gr a di e n t (t e mp e r a t u r e g ra d i e n t) d o e s n ot h o w e ve r e x i s t , ,

i n t h e b o dy s i n c e o n a c c ou n t o f t h e u n da mp e d c h a r a c t e r
, ,

o f t h e w a v e t h e m ea n d e n s it y o f e n e r gy i s e v e r ywh e re t h e
,

same Si n c e i n g e n e r a l t h e c o n du c t i v i t y fo r h e a t i s e qu a l
.
, ,

t o t h e flu x o f h e a t d i v i d e d b y t h e g r a d i e n t o f t e m p e r a t u r e ,

i t f oll o w s t h a t t he id ea l i sed sol id bod y p ossesses a n i nfi n i te

ther m a l con d u c ti vi ty The c a s e b e c o m e s d i ffe r e n t ho we v e r
.
, ,

i f w e e x te n d H oc he s L a w i n t he m a n n e r d e sc r i be d a n d t hu s
’

p a s s o ve r t o t h e r e a l s o l i d b o dy The w a v e s i n t h e b o dy
“
.

wi ll t h e n o n a c c ou n t o f t he d e p a rt u r e o f t h e e qu a ti o n s o f
,

m oti o n f r o m l i n e a r i t y n o l o n ge r p a s s o v e r o n e a n o th e r u n
,

d i st u r b ed O n t h e c o n tra r y a n o s c i ll a tion a l r e a dy p r e s e n t
.
,

w i ll i n c o n se qu e n c e o f the flu c tu a t io n s i n d e n s i t y c a u se d by
,

it d i st u rb t he o s c ill a t i o n s s up e r i mp o s e d up o n i t w i t h t he
, ,

e ffe c t t h a t a s c a tt e r i n g a n d t h e r e f o r e a w e a k e n i n g o f t he
,

w a v e s i n the b o dy re s ul t s i n p r e c i se ly the s a m e w ay a s a ,
 T HE E LECT R O N T H EO RY O F M E T A LS 61

c o l udy m e d i um we a k e n s l i gh t p a ss i n g t h r o ugh
sc a t te r s a n d

it. H e n c e i n t h e c a se t a k e n a t e mp e ra t u r e g ra d ie n t i s s e t
, ,

up i n t he pl a te fr o m t he t op t o t he bo t to m In the c a s e o f .

t he r e a l b o dy w e t hu s a r r i v e a t a fi n i t e t h e r m a l c o n du c t i v i t y .

The m a t he m a ti ca l d e v e l o pm e n t o f t h i s c o n c e p t i o n l e d D eby e to
h
t e l a w 16 3 tha t the ther m a l con d u c ti v i ty of cr ysta l s i s i n ver sel y
r o o r ti on a l to the a bsol u te temp er a tu r e ( i f w e c o n fi n e o u r s e lv e s
p p
t o t e mp e r a t u r e s w h i c h a r e s o h i gh t h a t c l a s s i c a l s ta t i st i c s a r e
a ppl i ca b l e ) Th i s d e du c t i o n s e e m s t o b e i n e xc e ll e n t a g r e e
.

m e n t w ith e xp e r i m e t l e sul s ob ta e d y
n a r t i n b A E h
u c en 53 1 . .

§ 13 . T he E l ec tr on T h e ory of M e ta l s a nd i ts M o di fica ti on b y the

Q u a nt u m T he ory
If m a tt ers l dy c o mpl i c a t e d i n t he i n tr i n s i c a lly
a re a rea

cl e a r c a se of c r ys ta l s t he p o s itio n b e c o m e s st i ll m o r e
,

d i ffi c ul t wh e n w e t u r n t o m e ta l s wh ic h i n ge n e r a l c o n , ,

s is t o f a n i r r e gul a r c o n gl o m e ra t e o f c r yst a ll it e s In t h i s .

c a s e t he c o n du c t i v i t i e s n a m e ly of h e a t a n d e l e c tri c i ty a r e
, , ,

p a r t i c ula rly d e c e p t i v e A cc or di n g to t he c l a ss i c a l t h eor i e s o f

.

P D r u de 164 E R i eche 1 55 a n d H A 7 30r en tz 166 t h e se ph e n o

.
,
.
, . .
,

m e n a a r e b r o ught a b out by t he f r e e c on ducti v i ty e l e c tr o n s -

wh i c h l ik e ga s m ol e c ul es fly a b ou t i n th e s p a c e b e t w e e n t he
,
-

fi xe d a t o m i c r e s idu e s e x ch a n ge e n e r gy w it h t h e se up o n
,

c o ll i s i o n a n d s o t a k e p a r t i n t h e e s t a b l i s hm e n t of t h e r m a l
,

e qu i l i b r i um T hus t he c on duc t i o n o f e l e c t ri c i t y i s e x pl a i n e d
.

a s f o ll o w s : i n a p i e c e o f m e t a l o f u n i f o r m t e mp e r a t u r e an ,

e qu a l n umb e r o f e l e c t r o n s fly o n t h e a v e r a g e i n e a c h , ,

d i r e c ti o n t h r ough a n e l e m e n t of s ur fa c e H e n c e o n th e .
,

a v e r a g e th e r e i s n o t r an s p o rt of e l e c t r i c a l ch a r g e s t h r ough
,

t h i s e l e m e n t o f s u r f a c e t h a t i s n o e l e c t r i c cu r r e n t i s fl ow i n g
, ,

i n t he p i e c e o f m e t a l If n o w w e a pply a p ote n t i a l d i ffe r e n c e

.

t o t he e n d s o f t h e m e t a l a n e l e c tr i c fi e ld e x i st s i n t h e m e t a l
, ,

a n d t h i s fi e ld i mp r e s s e s up o n t h e e l e c t r o n s du r i n g t h e i r f re e “

”
pa th s ( i e t h e i r p a t h s b e t w e e n t w o e n c ou n t e r s wit h a t o m s )
. .

a c e r ta i n on e si d ed a dd i t i o n a l
-
v e l o c i ty wh i c h i s s up e r
i mpo se d up on t h e i r r e gul a r h e a t m o t i o n N o w t h e r e fo r e -
.
, ,

m o r e e l e c t r o n s w ill p a ss p e r s eco n d thr o ug h t he e l e m e n t of

s u r f a c e i n o n e d ir e c t i o n t h a n i n t h e o t h e r a n d s i n c e t he ,

e l e c t r o n s c a r r y a n e g a t i v e c h a r g e a n d so m o v e a ga i n s t t he ,

fi e ld i s i n a d i r e c t io n o pp o si t e to the fi e ld w e h a ve n ow a n
, . .
,
62 T HE QU A NTU M T H EO RY

e l ec tr i c cu r r en t m e t a l The m a t h e m a ti c a l c a lcul a tion

i n t he .

o f t h i s si mpl e c o n c e p t i on g iv e s fo r t h e e l e c tr i c a l c o n du c t i v it y

0 of t e m l
"
h e t a 167

N e
i
l

H e r e N i s t he n um b e r of e l e c tr o n s p e r u n i t of v olum e e a n d ,

m ch a r ge a n d m a s s of t he e l e c tr o n s q t h e i r a v e r a g e v e l oc i ty
, ,

an d l t h e ir f r e e p a th . If we w r i te the ex p r e s s i on ( 6 7 ) i n t he
f or m
N e lg2

c m ( 6 7 a
)
a p
w e m a y , a c c o r d i n g to t h e a s s ump ti o n s o f the c l a s s i c a l t h e o ry ,
r e pl a c e t he m e a n k i n e t i c e n e r gy é m o f t h e e l e c t r o n s b y % hT
2
g .

F or si n c e , as we a ss um e d ,
t he l
e e c t r on s ta k e par t in
e sta bl i s hin g he a t e qu il ib r u i m the l aw of e qu ip a rti tio n o f
-

k i n e t i c e n e r gy a ppl i e s t o t h e i r m o t i o n a n d t h e r e i s t hu s ,

al l o c a t e d t o e a c h o f t h e t h r e e d e g r e e s o f f r e e d o m o f t he

e l e c tr o n s t he e n e r gy QhT In t h i s w a y w e a rr i ve a t the
.

f o r mul a
N e lqz

Gk T ( 6 7 b)
A n al O SOU S IY W 8 ge t f r o m D r u d e Th eo r y the
’

,
s c oe ffic i e n t of

t h e r m a l c o n duc t i vi t y 168

r tNq
so t ha t a m bi n a tion
co of t he tw o fo r mul a
e l e ads to t he
fu n d a m e n ta l r el a t ion

wh i ch i s the l aw of Wi ed ema n n F r a n z a n d of L or ene 169 It -

.

s t a t e s t h a t the r a ti o of the ther m a l to the e l ec tr i ca l con d u c ti v i t y

ha s the sam e va lu e for a l l p u r e me ta l s a n d i s p r op or ti on a l to

the bsol u te temp er a tu r e
a .

Thus a ll a pp e a r e d i n the b e st of or de r The c l a s s i c a l .

t h e o r y a pp e are d h e r e a ls o t o h a v e w ork e d su c c e s sfully a n d

t h e l a w of e qu i p a rt i t i o n c e l e b ra t e d a t r i umph B u t up on .

cl os er i n spe c tio n g a ps a pp ea r e d i n t he a pp a r e n tly sol i d

,

t h eo re ti c a l s tr uc t u r e a n d s e ri o us d oub t s a r os e
, For i f the .
 T HE E LECT RO N T HEORY OF M E T A LS 63
fr e e le e c tr o n s r e a lly t o o k p a r t i n t he t h e r m a l e qu ili b r i um ,

a n d h e n ce cl a i m e d t h e i r full s h a r e gN hT (p e r u n it o f ,
—

volum e ) i n t he e qu a l d i v i s ion of ki n e ti c e n e r gy t h e n t hi s
, ,

sh a r e o f e n e r gy s h o uld b e pl a i n ly n ot i c e a bl e i n the a to m ic
* *
h e a t o f t he b ody n a m ely t o the e x t e n t of % N h wh e r e N
, , ,

d e not e s t he n umb e r o f e l e c tro n s i n a gr a mm e a to m Such -

.

a n i n c r e a s e i n t h e a t o m i c h e a t of t he m e t a l s a s c o mp a r e d

w i t h t he n on m e tals ( wh i ch c on t a i n n o o r va n i s h i n gly fe w
-

, ,

f r e e e l e c tron s) ha s n e v er b e e n o b s er ve d Th i s di fficul ty c ould .

b e a voi d e d b y as sum i n g t h a t t he n umb e r o f e l e c t r o n s i s s m a ll

c o mp a r e d w i th t he n umb e r of a to m s p e r u n it v olum e a n d ,

t h e n t h e i r co n t r i b u t i o n t o t he a t o m i c h ea t w ould b e r e l a t i ve l y
s m a ll . B u t t h e n w e sh ould e x p e c t f r o m ( 6 7 6) mu c h s m a ll e r
c o n du c t i v i t i e s t h a n e xp e r i m e n t ha s d i s c l o s e d u n l e s s w e w e r e ,

t o a s sum e h i gh va lu e s t h a t a r e i mp r ob a b l e for t he m e a n f r e e
, ,

p a th 1 70
.

F u r t h e r H A L or en tz 1 7 1 ha s s ho wn a s w e h a v e s e e n
, . .
, ,

t h a t i f t h e l a w o f e qu ip a r titi o n fo r t h e m o t i o n o f t h e e l e c tr o n s
,

i s a ss um e d t he m e t a l s w o uld r a d i a t e i n t he r e g i o n o f l o n g
,

wa ve s a cc or d i n g t o R a y lei gh s L a w wh e r e a s w e h a v e u n
’

qu e s ti on a bly t o e x p e c t e sp e c i a lly a t l ow t e mp er a tu r e s t he
, ,

r a d i a t io n t o t a k e pl a c e a c c o r d i n g t o P l a n c k s L a w
’
.

The c a l c ul a t e d d e p e n d e n c e o f t he co n du c t i v i ty o n t e mp e r a
t u r e c a n o n ly b e m a d e t o a g r e e w i t h e x p er i e n c e b y m a ki n g
p a r t i c ul a r a s sump tion s a t h i gh t e mp e ra t u r e s wh e r e a s n o ,

a s s ump t i o n s s e e m t o b e a bl e t o m a k e c a lcul a t i o n a n d c hee r

va ti o n a gr e e for l o w t e mp era t u r e s A t h i gh t e mp e ra t u r e s
.

the r e s i sta n c e o f the m e t a l s i n cr e a se s p ro p o rt i on a lly t o

1
t he t e mp e r a t u r e , t h a t i s, 0 de cr ea s e s W i th Thi s c an
T
on ly b e cil e d w it h ( 6 7 b) if the p r o duc t q
c
re o n i s i n de
,

pe nd e n t o f t h e t e mp e r a t u r e If w e a s s um e wi t h J J
. . .

Thomson 172 t h a t N i n cr e a se s p r o p or ti o n a te ly to JT t h e n , ,

s in c e
q s l ik e wi s e p r o p o rt i on a l t o JT l mu s t d e c r e a s e w i t h
i ,

é ,
a hypo th e si s wh i ch ,
as we s h a ll se e , ha s l a tt erly be e n

uph e ld by s e ve ra l i n v e st i ga tor s .

N ow al t hough t he a gr ee m e n t be tw e e n t h e o ry a n d e x p e r i
,

m e n t co uld t hu s b e co mp e ll e d by s p ec ia l a ss ump t i on s a t hi gh
te mp e ra t ur e s the r e g i o n o f l o w t e mp e r a t u r e s r e v e a led i t s e lf
,
64 T HE Q U A NT U M T HE O R Y

as th e vul n e r ab l e p o i n t of t h e t h e or y
p e r i m e n t s by . For ex

H Ka me l g O
. r i n h n n e s 1 7
- 3 i n t he l a b o r a to r y for l o w t e mp e ra
t u r e s a t Le yd e n ha d s h o w n t h a t t h e r e s i s t a n c e o f m e t a l s
a t v e r y l o w t e mp e r a t u r e s ( t h e e x p e r i m e n t s e x t e n d e d a s fa r

dow n a s ab s
) f a ll s a w a y t o a qu it e e x t r a o r d i n a r y d e g r e e
.
,

a n d p r a c ti c a lly d i s a pp e a r s b e f o r e t h e z e r o p o i n t i s r e a c h e d -

A t a n y r a t e th e r e s i s ta n c e c a n n o t a s f oll o w s i n vie w o f wh a t
, ,

ha s j u s t b e e n s a i d f r o m f o r mul a ( 6 7 b) s i n k p r o p o r t i o n a t e ly ,

t o o n ly t h e fir s t p o w e r o f t he t e mp e r a t u r e ; o n t h e c on tr a r y
t he f a ll i s w i t h o u t d o u b t p r op o r ti o n a l t o a h i gh e r p o w e r .

Th a t the Wi ed em a n n F r a n z L a w a ls o c e a se s t o b e va l i d i n
-

th i s r e g i o n ha s b e e n p r o v e d b y e x p e r i m e n t s of O H L ees 1 74
, . .

a n d W Mei ssn er 1 7 5
. .

In o r d e r t o e s c a p e f r o m a l l t h e s e d iffic ul tie s t h e qu a n tum

t h eo r y w a s a pp e a l e d t o a n d a tt e mp t s w e r e m a d e i n the m o s t
, ,

v a ri e d w a ys t o m ak e i t h a r m on i se wi t h t he e x i sti n g t h e or y
, .

A fi r s t a t t a c k w a s v e n t u r e d by W N er n s t 1 7 5 a n d Ka m er l i ngh .

0n n es 177 w ho g a v e fo r t he r e s i s t a n c e o f t h e m e t a l s e mp i r i c a l
,

for mul ae wh i ch l i n k e d up d i r e c tly w i t h th e for m o f P l a nck s ’

e n e r gy e qu a t io n a n d wh i ch g a v e t h e ch a n g e i n t h e r e s i s t
( )
9
a n c e w i t h t e mp e r a t u r e s a t i sfa c t o r i ly F A L i n d em a n n 78 1. . .

and W Wi en 1 79 c o n c e i v e d m or e d e t a il e d t h eor i e s L i n de .

m a n n a cc e p t s i n hi s fi r st p a p e r J J Thom son s hyp oth e s i s

’
. .
,

a c c or d i n g t o wh i ch N i s p r o p ort i o n a l t o
J T a n d r e t a i n s t he ,

e qu i p a r t i t i o n l a w for t h e m ot i o n o f t h e e l e c t r o n s s o t h a t
q ,

a l s o b e c o m e s p r o p o r t i o n a l t o JT Then a ccor d i n g to ( 6 7 b)
.
, ,

the v a r i a ti on o f the r esi s ta nce 1 w i th the temp er a tu r e dep end s

a

en ti r el y on the m ea n fr ee p a th l . B u t t h i s i s , a c c or d i n g t o
we ll -
k n ow n d e r a t i on s of t h e
c on si t h eo r y o f g a s e s , the g r e a t e r
t h e s m a ll er t he r a d i us o f a c ti on o f t h e m e t a ll i c a to ms ; fo r

t h e e l e c tr o n s c a n pu r su e g r e a te r p a t h s f re e ly i e w i t h o u t ,
. .

c oll is io n s t he s m a ll e r t he hi n d r a n c e s s e t i n t h e i r p a t h The
,
.

n o v e l p a r t o f L i n dem a n n s T h e o r y i s t h e f a c t t h a t h e b r i n gs
’

t he r a d i us o f a c t i o n o f t h e a to m i n t o r e l a t i o n w i t h i ts a mpl i
t ud e o f sw i n g i n i t s h e a t m o ti on Fo r i t i s a t o n c e obv i o us
-
.

t h a t t he a t o ms i n t h i s h e a t m ot i o n w i ll c o v e r a g r e a t e r sp a c e
-

i n a g i v e n t i m e a n d t h e ir sph e r e of a c t i o n w i ll b e t he gr ea t e r
, ,

t he l a r ge r t h e i r a mpl i t ud e o f o s c ill a t io n i e th e h i gh e r the ,

. .

t e mp era t u r e Thus t he m e a n f r e e p a t h a l so b e c o m e s a
.
 T HE E LEC T RO N T HEORY OF M E TA LS 65
fu n cti on of the t e mp eratur e i n a smuch as i t i s b rough t i n t o
,

r e l a t i on wi t h t he e n e r gy o f vi b ra t i o n o f t he a t o m s B u t for .
,

t h e l a tt e r t e r m Li n dem a n n i n s e r t s t he v a lu e gi v e n by t h e
,

qu a n tum t heor y an d fi n d s for t he r e si sta n c e t he for mul a 130

,

wh e re v de n ot e s th e fr e qu e n cy o f the a t o ms (a g a in t he m o n o
c h r o m a t i c t h e or y) ; A a n d B a r e c o n s ta n t s F o r h i gh t e m .

e r a t u re s W t h e n b e c o m e s p r op or ti on a l t o t he t e mp e r at u r e
p
T ; fo r l o w t e mp er a tu r e s W d e c r e a s e s e x p on e nt i a lly w it h
hv
e 7 7
2 to c o n st a n t va lu e 3
a Wi t h the h e lp of thi s for mul a
2
.
,

Li nd em a n n succ e e d s in r e p re s en ti n g t he ob se rv a t i o n s qu it e
w e ll ( the for mul a c onta i n s t w o c on s ta nt s wh i ch ca n b e m a n i
b u t s i n c e t h e l a w o f e qu i p art i t i o n h as b ee n r e t a i n e d
p u l a t e d ) ,

fo r t h e e l e c tr on s t he d ifli cu l ti e s o f th e e x c e ss i v e a to m i c h e a t
,

a n d o f R a y lei gh s r a d i a t i on f or mul a r e m a i n Mor eov e r t h i s

’
.
,

t h e o ry i s u n abl e t o ex pl a i n the d e p a r t u r e s fr o m t he Wi ede

m a nn F r a n z La w a t l ow t e mp e ra tu r e s ; for th e m e a n fr ee
-

p a t h l — t he only qu an tity d ep e nd e n t on T which o ccu r s in 0

— d i sa pp e a r s e nti re ly f r o m t he fo r mul a

W Wi en a t ta c k e d t he qu e s ti on much m or e ra d i c a lly t h a n
.

Li nd em a nn In o r d e r o n c e a n d for a ll t o get r i d o f the

.

c o ntri bu t ion of t he e l e ctron s to t he a to mi c h e a t t hi s i s the -

we a k p oin t of al l t h eori e s wh i ch m ak e u se of the l a w of

e qu i p a rt i t i on — h e a s sum e d t h a t t h e e l e c tr o n s d o n ot t a k e

p a r t i n the t h e r m a l e qu il i b r i um b u t p oss e ss a v e l oc i t y g
,

wh i c h i s i n d e pe n d e n t of t he te mp e r a tu r e Mor eov e r he
.
,

m ak e s the n umb e r N of the e l e c t ron s p er u n it volum e e qu a l

fo r a ll t e mp e r a t u r e s Th e n a cc o r d i n g to
.
,
t he v a r i a t i o n

of 1 w i th t e m pe r a t u r e is a ga i n d ete r m i n e d on ly b y t he
a

d e p e n d e n c e o f t he m ea n f r ee p a t h l o n the t e mpe ra tu r e .

Wi en i n a m an n e r si m i l a r t o t h a t o f L i n d em a nn c o n n e c ts l
, ,

wi th t he e n e r gy o f v ib r a ti on of the m e t a ll i c a to ms t a ki n g , ,

howe ve r the c o mpl et e e l a sti c sp e c trum i n to a cc ou n t a c c o r d

,

i n g to D ebye He t hus ge t s for the r e si s ta n ce the va lu e

.

5
66 T HE Q U A NT U M T H EO R Y

W con st .
hv

F or h igh t e mp er atu r e s th i s f or mul a g i v e s W c on s t T i e .

,
. .

p r o p ort i on a l it y wit h the t e mp e r a t u r e Fo r l ow t e mp e ra t u r e s .

i t f o ll o ws t h at W == c o n s t T i e a p a ra b ol i c d e c r e a s e
2
.
, . . .

The obs e r v a ti on s a r e v e r y w e ll r e p r e se n t e d by Wi en s f o r mul a

’
.

B u t a b o v e a l l t he u n s a ti sfa ct o r y f a c t r e m a i n s t h at t h i s
, ,

m e t h o d d oe s n ot l e a d us on to a t h e ory of h e a t c on duct i on -

u n l e ss w e m ak e n e w a ssump ti on s n o r to t he Wi edema n n ,

F r a n z La w F or by th e c on ditio n t h a t t h e m ot i on o f th e
.
,

e l e c t r on s t a k e s pl a c e qu it e i n d e p e n d e n t ly o f t he t e mp e ra t u r e ,

Wi en ha s t ak e n a wa y th e p os s ib i l i ty o f a ls o a scr ib i n g the
t r a n s p o rt o f h eat t o t he e l e c tr o n s .

Th i s d i fficul t y a r i se s a g a i n i n a m or e r e ce n t p a p e r of
F A L i n dem a n n 181 i n wh i ch i n con t in u at i o n of t he c o n
. .
,

c ep t i o n s of B or n a n d Kd r mci n t h e s upp o s i t ion i s i n t r o du c e d

,

h
t a t — jus t a s t h e a t o m s i n a c r ys ta l — the el ectr on s i n a m eta l
for m a l a ttice F Ha ber .
1
.
8 1 » h a s a ls o a d opt e d a s i m i l a r hyp o
9

t h e si s The c on du c t ion of e l e c t ri c i t y i s t h e n e x pl a i n e d b y
.

supp os in g t hi s e l e ctr on l at ti c e t o m ov e p ra c ti c a lly a s a ri gi d

s tr uc tur e r e l a t iv e ly t o t he a to m i c l att i c e a n d so t hr ough the
m et a l Th i s m od e l has m a n y a dv a n t a g e s
. Si n c e i n t he .
,

h e at m oti on i n whi ch the e l e c tron l a tti ce n atu ra ll y t ak e s

-

p a rt t he e l e c tr on i c v i b ra t ion s on a cc ou n t of t h e i r m a ss a r e
, , ,

e x t r e m e ly r a p i d ( h i gh fr e qu e n cy) t h e s e vi b r a ti on s o f t he
,

e l e c t r on a cc o r d i n g t o P l a n ck s f o r mul a fo r t h e e n e r gy m a k e
’

, ,

n o a pp r e c i a bl e c o n t r i bu t i o n t o t h e a to m i c h e a t In a dd i t i o n .

t he a b n or m a l c o n duc t i v it y ( sup r a c on du c t i vi t y ) wh i c h h a s -

be e n ob s e r v e d a t v er y l o w t e mp e r a t u re s m a y if w e u se ,

e a r l i e r c on s i d e r a t i o n s by J S ta r k “2 b e e x pl a i n e d w i th ou t
.
,

d ifficul ty by the c on c e p ti on t h a t a t t h e s e v e ry l ow t e mp e r a
t u r e s a t w hi ch t h e a t o m i c sp a c e l a t t i c e i s p ra c t i c a lly a t r e st
-

t h e e l e c t r o n i c l a tti c e gl i d e s a lm o s t u n i mp e d e d t h r ough t he
g a p s o f t h e a t o m i c l a tt i c e .

G Bor el i u s 188 i n a sk e t ch wh i ch w a s r e c e nt ly pu bl i sh e d
.
, ,

u s e s i d e a s s i m i l ar t o t h o s e of L i n d em a n n .

Fi n ally w e m a y re f e r to a p a p e r by K Her zfeld 1“ wh i ch

, .
,
 T HE E LEC T RO N T H EORY OF M E TA LS 67
i n c on tr a s t to t he p r e c ed i n g i n v e s t i ga t io n s , a tta ck s the qu e s
t ion f r o m a m or e ph e n o m en o l og i c a l p oi n t of vi e w wi t ho u t
m a ki n g u se of a p ar t i cul ar m od e l For if, in the for mul ae .

for o a n d y , ( 6 7 ) a n d w e b ri n g i n to e v i d e n c e t he e n er gy
E 1 m l c s by w i g h qu i s hus
3 g? o f t h e e e t r o n r t i n t e e a t on t : 1 85

2
Ne l
a
2 J2 mE
2E d E
Y § N l

1
r i . E 912
2
0
'

36 dT

as t he ss ion whi ch r e p r e s e n t s t he Wi ed ema nn F r a nz

e xp r e -

La w H er zfel d th e n sh o ws t h at if w e c o mp a r e the r e sul t

“

.
, ,

wi th obs e rv a tion t he for mul a ( 7 3 ) c a n b e m a d e to a gr e e w e ll

,

with the a c tu a l m e a su r e m e nt s i f w e se t P l a nck s e x p r e ss i on

’

1 hV
h,
fo r E ( The f a c tor 5 ha s b e e n i n troduc e d b e c a us e
2
.

kT
e -
l
th e e n er gy o f the e l e ctron s i s sol e ly ki n et i c ) The va lu e s for .

v wh i ch h a v e t o b e us e d s t a n d i n n o r e c o g n i s a bl e r el a t i on t o

h
t e a o m c f e qu e n c e s
t i r i A p a p e r by F v H a u e
. r 1 86 work s
. .

a l on g s i m i l a r l i n e s .

If w e su r v e y the whol e fi e ld o f the c on duc ti o n of h e a t a n d

e l e c t r i c i t y i n m e t a ls w e r e c o gn i s e t h a t h e r e the l a s t wo r d

ha s n ot b e e n sp ok e n a n d th a t a gr e a t d e a l o f har d w o r k w i ll
,

b e n e c e ss a r y t o cl e a r up fi n a lly t he e x tr a o r di n a r i ly c om
pl i c a t ed r el a t i o n ships B u t much w ould d oub tl e ss b e ga i n e d
.

for the t h eory i f i n fu t u r e t he o bs e r va t io n s a s fa r a s p o s s i bl e , ,

a re n o l on g e r m a d e o n c r ys t a l a gg r e g a t e s b u t o n m et a l ,

c r y st a l s t h a t a r e pu r e a n d h o m o ge n e o us .
 CH A P TE R V

T he I nt ru s i o n of Q u a nt a i nt o t he T he o ry of G as e s

§ I. T he He a t of R ota t i o n D i a t o mi c G a se s
of acc or d i ng t o th e
Q u a nt u m T he ory
H I LE th e m ol e cul ar t he or y o f th e s o l i d s t a te t hus
ga i n e d n e w n o u r i shm en t f ro m the d o c tr i n e of qu a n t a ,

t h e ki n eti c t heo r y o f g a s e s c ould n o l on ger b e p r e s er ve d fr o m

th e n flu of
i x t h e n e w v w
i e s W N ns
.er t 1 3 7 h a d p oi n t e d o u t
quit e e a r ly t h at qu a n tum e fle c t s a re t o b e e x p e ct e d i n the
-

r ot a t i o n o f d i a n d p o l y a t o m i c a s m ol e cul e s a n d a l so i n t h e
g
-

o sc i ll a t i o n o f a t o m s i n t he

m o l e c ul e Let u s t ak e a s
.

a n e x a mpl e t he d i a to m i c

g as hyd r o g en t h e m,
o l e

c ul e of wh i ch w e m a y
p i c t ur e p r ov i s i o n a lly a s a
r i gi d dumb b ell (Fi g -
.

Th e k n ob s o f t he dum b b e ll -

a r e th e hyd ro g e n at o ms ,

t he g r i p r e p r e s e n t s t h e i r
ch e m i c a l b on d Such a .

m ol e cul e i s k n o w n to
p o s s es s b e s ide s i t s t r a n sl a
,

t or y m ot i on ( t h r e e d e gr e e s
F IG 6. .

of fr e e do m p s b l y
) t h e os
,
i i i t
o f r ot a t i n g a b o ut a n ax i s a t r i ght a n gl e s t o t h e l in e j oin i n g the
a to m s ( t w o d e g r e es o f f r e e d o m c or r e s p o n d i n g t o t he t w o a x e s
,

dott e d i n t he figu r e ) Rotati on a b out t he l i n e j o i n i n g t h e

.

a t o m s d o e s n ot i i w e a c c e p t Bol tzma n n s c o n c e p t i o n o f t he
’
—

a b s olu t e ly ri gi d sm o ot h a t o m — c o m e i n t o pl a y i n t he ex
ch a n ge of e n e r gy by c oll i s i on a n d h e n c e i n t he d is t r i but ion
cf e n e r gy a m on g the s epa r a t e d e gr e e s of f r e e d om : for t h i s
I

68
H E A T O F RO TA T I O N OF D I A T O M I C G A SES 69
r ot a t i o n c a n n ot b e ch a n ge d b y c o ll is i on Co n s i d e r e d f ro m
.

t he n e w p o i n t of v i e w o f qu a n ta wh i ch r e j e c t s r i g i d i ty
“
, and

s m o o t h n e ss a s a n u n ju s t i fi e d i d e a l i s a t i o n t he p o s it i o n i s a s
,

f oll o ws Th e m o m e n t o f i n e r ti a of the m ol e c ul e r e l ati ve ly t o

t he l i n e j o i n i n g t he a t o m s i s e x t r e m e ly s m a ll c o mp a r e d w i t h
t he m om e n t o f i n e r ti a a b o u t e i t h e r o f t he a x e s a t r i gh t a n gl e s
to th i s l i n e B u t i t i s k n o w n t h a t r ot a ti o n s wh i c h t a k e pl a c e
.

a b o u t a x e s w it h s m a ll m o m e n t s o f i n e r t i a o c c u r w i t h much

g r e a te r r a p id i t y t h a n t h o s e a b o u t a x e s w i th l a r g e m o m e n t s o f
i n e r ti a ( t h e s a m e e n e r gy h a vi n g b e e n i mp a rt e d i n e a ch c a s e ) .

If t h e r efor e w e i d e n tify t he r e v olu t i on s p e r s e c o n d w i t h fre

, ,

u e n c i e s a n d u s e t he P l a n ck e n e r gy e x p r e s s i o n fo r t h e e n e r gy
q ,

o f r ot a t io n wh i ch i s n o t s t r i c t ly c or r e c t qu a n t i t a t i v e ly a l ine
( ) ,

o f a r gum e n t wh i ch h a s a l r e a d y b e e n f r e qu e n tly a ppl ie d s h ow s

u s tha t the r o ta ti on a bou t the li n e j oi n i ng the a tom s sesses

p os

on l y a va n i shi n gl y sm a l l sha r e of the en er gy F or t h e s a m e

.

r e a so n
( h i gh f r e qu e n c i e s
) t h e d e g r e e s of fr e e do m wh i ch ,

co rre s p o n d t o t he v i b r a t i o n of t he a t o m s i n t he m o l e cul e ,

b e c o m e of i mp or ta n ce o n ly a t h i gh t e mp era t u r e s A s a r e sul t .

I
of a ll this , cl a s si c a l s ta ti s t i cs giv e s us t he v a lu e 2 f! RT
2
fo r t he m e a n e n e rgy of r ot a t i on o f t he hydr o g e n m ol e c ul e ;
p e r gr a mm e m o l e c ul e i t th e r e fo r e b e c o m e s Nh T R TI
-

H en ce tha t p a r t of the mol ecu l a r hea t w hi ch a r i ses from

r ota ti on i s equ a l to R , tha t i s , a bou t i ll
G
,
a nd i t i s in
deg .

dep en d en t of the temp er a tu r e In c r a ss c on t r a d i c ti o n t o thi s

.
,

A E u c hen 188 f ou n d e x p e r i m e n t a lly t h a t t he r o t a t i o n p a r t o f

.

t h e m ol e c ul a r h e a t o f h yd r o ge n h a s the v a lu e R d e m a n d e d b y
the cl a s s i c a l t h e o r y o n ly a t h i gh t e mp e ra t u re s O n t he o t h e r .

h a nd ,
gr a du a lly d e c r e a s e s a s w e p a s s t o l owe r t e mp e r a t u re s
it ,

a n d a pp r o a c h e s a s ymp to t i c a lly t h e v a lu e z e r o a t t h e a b s o

lu t e z e ro In the i mm edi a te n ei ghbou r hood of a bsolu te z er o

.
,

hyd r ogen beha ves a s a m on a tom i c ga s E u chen s r e s ul t w a s

’
.

c o nfi r m e d b e x p e r i m e n t s c o n duc t e d b K S h l a nd W
y y c e e . .

H eu se 189 w h o h owe v e r m e a s u r e d t h e v a lu e s o f th e m o l e c
, , ,

ul a r he a t o n ly for t h re e t e mp e r a tu r e s a n d 2 89
°

o n th e a bso lu t e s c a l e f ll g r ot a t i o n a l h e a t
) T h i s . a i n o ff o f t h e

i s w it ho u t d oub t a qu a n tum e ffe c t s i m il a r t o t he d e c r e as e i n

-

t h e a t o m i c h e a t o f s o l i d bo d i e s .
70 T HE Q U A NT U M T HE ORY

The fi r s t mp t to c a lcul a t e t h i s phe no m e n on t heore ti c a lly

a tt e
,

i s d u e t o A E i n stein a n d 0 S ter n 19° w ho p r oc e e d e d a s

. .
,

foll ows : If J a n d v a r e the m om e n t of i n e rt i a a n d t h e

n umb e r of r e vo lu t i o n s r s e c on d o f t he m ol e cul e r e s p e c ti ve ly
p e ,

t h e n i t s r ota ti on a l e n e r gy i s

If ,
s i mpl ify m a tter s w e n ow supp o s e t h at a ll m ol e cul e s
to ,

r o ta t e w i t h th e s a m e m ea n n umb e r of r e v olu ti o n s 1
7 pe r se cond ,

t h e n w e ca n i n t ro duc e for the c o r r e sp on d i n g m e a n e n e r gy of

r o tati o n

J
7 z
g ( )
em

the t h e o r et i c al qu a n tum va lu e 1 9 1

h;
i

r di n g t o P l a nc k s fi r s t t h e or y )
( cc ( 7 6)
’
a o

%
3 a nck s
’

( P l s e c on d t h eory) ( 7 7)

Fr o m ( )
7 6 or by co mb i n in g w it h we o b ta i n 7
1 as a
,
dE
fu n c tion of T . If fi n a lly we f or m E
i — ’
an d mul tip ly by t he
dT
(

A voga dr o n umb e r N , t h e n w e ge t the s h a r e o f t h e e n e r gy of

r o t a t i o n i n th e m ol e cul a r h e a t , a n d w e se e how i t d e p e n d s o n

t he t e mp e r a tu r e It t hus a pp ea r e d t h a t o n ly by u s i n g the
.

ex p r e s si on ( 7 7) for E would w e b e e n a bl e d t o ge t a s a t i s
T

f a c t or y c on n e x ion a gr e e in g w it h E u chen s m ea su re m e n t s a ’

f a c t wh i c h E i n s tei n a n d S ter n u se d a t the t i m e a s a n a rgu

m e n t for t he e x i st e n c e of a z er o p o i nt e n e rgy It mu s t ho w
-
.
,

e v e r b e e mph a s i s e d t h a t t h i s t h e o r y c a n o n ly b e r e g a r d e d a s
,

a fi r s t a tt e mp t t o fin d g e n e r a l b e a r i n g s a n d t h a t i t d o e s n o t

fulfil m or e r i gorou s r e qu ir e m e n ts F or t he P l a n ck e n e rgy

.

f or mul a u s ed ( 7 6) or ( 7 7 ) a r e va l id a s i s s h o w n by th e ir
, ,

ge n e s i s o n ly for c on figu r a ti on s whose fr e qu e n c y v i s a c o n

,

s ta n t qu a n tity i n d e p e n d e n t of t he te mp e r a tu re H e r e on .
,
H E A T O F RO T A TI O N O F D I A T O M I C G A SE S 71

th e co ntra r y ,
we ha v e m a d e u se of a m ea n s p e e d of r o t a t i o n

7, dep end en t on the temp er a tu r e

1 .

P E hr enfes t 92 i n 1 9 1 3 bu il t up a t h e ory o f t he h e a t d u e to
.
1

r o ta ti o n o n a s tri c te r b a s i s H e h a d , h o w e v e r , t o c on fi n e
.

h i ms e lf to con figu ra t i on s wi th one d e gr ee of f re ed o m , th a t i s ,

to r o t at ion s of t he m ol e cul e a r o un d a fi x ed a xi s a s a t t ha t ,

t i m e a n ex te n si o n o f t he qu a n t um t h e o r y t o se v era l d e g r e e s
o f f r e e d o m ha d n ot e t b e e n wor k e d o u t Th e e x p r es s i on
y .

t hu s o b tai n e d fo r t h e h e a t o f r o t at i on w as t h e n , i n o r d e r t o
t ak e i n to a cco u n t b o t h d e g r e e s of fr e e d o m s i mply mul t i pl i e d ,

by 2 , a m eth od wh i ch rea d ily s ugge s t s i t se lf bu t i s n ot j usti ,

fia bl e .E hrenfes t s t ar t e d i n hi s c a lcul a t io n , f ro m th e or i gi n a l
,

for m of the qu a n tum hyp ot he si s, a c c or din g to wh i ch the

e n e r gy o f l i n e a r o sc ill a t or s m a o n ly b e wh o l e mul ti pl e s o f h
y r,

a n d a cc or d i n gly m a d e t he c on d i ti o n t h a t t he r ot a t i on a l e n e r gy

o f a c on figu ra t ion wi t h on e d e g r e e of fr ee d o m ( fi x ed a xi s m a y
)
k
on ly c o n s i s t of wh ol e mul t i pl e s o f The fa c tor 1} a pp e ar s ,
g .

b e c a us e the e n e r gy o f r ot a t io n — i n c o n tr a st wi t h t he v ib ra
t ion a l e n e r gy o f t h e o sc i ll a to r — i s s ol e ly k in e t ic by n a t u r e .

f
The E h/ren es t c on d iti o n i s , t h e r e fo r e , a cc or d i n g t o ( 7 4 )

3?
i
( ) g
2
2 m
E. n
( n 0, 1 2 3, , ( )
7 8

h e n ce
u,
$ 3 ( n o, 1 , 2 , 3 ( )
7 9

a nd by s ub sti tu ti o n m ( 7 8 )

i;
t”
g
< >_ 0
( o 1, 2 3 ( )
8
u
E n , ,

He nce the molecu les ca n on l y r ota te w i th qu i te de fin i te ,

di scr ete
sp eed s a n d cor r esp ondi ngl y a cqu i r e on l y a ser i es o f d i scr ete
r ota tio n a l ener i es u i te in a gr eemen t w i th the se n se of
g q
P la nc k s qu a n tu m theor y It i s n ote wo rt hy t h a t t h e se d is
’

c r e t e r ota t i o n a l e n e r gi e s a r e re l a t e d t o o n e a n ot h e r a s t h e

squ a r es o f t he whol e n umb e r s , wh e re a s t he e n e r gi e s of t he

P l a nck c i ll a to r s a r e p r o po rt io n a l
os t o t he wh ol e n umb e rs
th e mse lve s .Wit h the d i s c o ve ry of th e d i s c r e t e valu e s (8 0)
o f t he e n e r gy the d y na mica l p a r t o f
,
t he p r ob l e m w a s so lv ed .
72 T HE Q UA N T U M T H EORY

But we re qui r e t he m ea n
gy E o f a tot a l it y o f N s i m il a r
en er ,

m ol e cul e s It i s h er e t h e n t h a t t he s e c on d sta ti s ti ca l p ar t
.
, , ,

of t h e c a lcul a t i o n b e g i n s If w d e n ot es t he p r ob a bi l ity t h a t
.
n

"
a m ol e cul e
p o s se s se s th e r ota t i on a l e n e r gy E
? a t t he t e mp e ra

t u r e T ( wn i s t h er efor e t he d i str i bu t i o n fu n c tion wh i ch ha s -

b een e x te n d e d in a cc or da n c e w it h the qu a ntum t he ory) t h e n ,

t he m e a n r ot a tio n a l e n e rgy of a m ol e cul e i s k n ow n t o b e e qu a l

co

n
E =o
E?“ wn . Mul t ipl i c ati on by N an d d iffer en ti a t i on w ith

res p e ct to T gi ve us i mm e dia t e ly the h ea t d u e t o r ot a t ion 193 .

E hr enfes t t hu s ob t a i n e d fo r t h e r el a t i o n shi p b e t w e e n th e
r o t a t i o n a l h e a t a n d t he t e mp e r a t u r e a cu r v e w h i ch c o uld i t i s ,

t r u e be m a d e t o a gr e e w e ll w i t h t h e m ea su re m e n t s ob t ai n e d
,

a t l o w t e mp e r a t u r e s b y cho osi n g t he a r b i t r a r y c o n s t a n t J ( t he

m o m e n t of i n e r ti a ) s u it a bly b u t a t h i gh t e mp e r a t ur e s it sh ow e d
, ,

b efor e re a ch i n g the cl a s s i c a l va lu e R a m a x i mum a n d a su b ,

s e qu e n t m i n i mum wh i ch d i d n ot c orr e sp o n d wi t h t he ex i s ti n g
,

o b s e r v a t i on s .

We m a y n ot e h er e a n i mp ort an t c on s e qu e n c e of e qu a tion
s i n c e i t h a s pl a y e d a n ot e w o r t hy r é l e i n t h e f urt he r

d e v e l o pm e n t of the qu a n t um t he or y If n a m e ly w e wr ite .
, ,

d ow h a gul a m o m um (t e m om e n t of m o m e um )
n t e n r e n t h n t 1 94

o f t h e m ol e cul e t h a t i s t he qu a n t i t y p = J x 2 1W t h e n i t
, , ,

f o ll ows fr o m ( 7 9) t h at o n ly t he sp e c ia l qu a ntum v a lu e s
nh

27 1
( n

of th e t u r n i n g m om e n t e xi s t Thi s r e l at i on m a y a ls o b e
-
.

d e duc e d dir e c tly f r o m t he th e or y o f t he qu a n t um of a c ti o n a s

f o r mul at e d i n F or i f w e s e l e c t a s ou r g e n e r a l c c
,

o r d i n a te ,
i n t hi s c a s e q t h e a n gl e o f r ot a t i o n
,
t h e n t he
c o rr e sp o n d i n g m o m e n t um o r i mpul se p i s k n ow n t o b e
n o n e o t h e r t h a n t h e m o m e n t o f m o m e n t um 1 95 It f o ll ows .

fro m t h i s s i n c e p i s i n d e p e n de n t of gt t h at
, ,

d
t d’ 2 m "h

in a gr ee m e n t w it h
H EA T OF RO T A T I O N O F D I A T O M I C G A SE S 73
In t he sa me w ay, on t he b a s i s of fir st th eo ry
P la nc k
’
s ,

n a m e ly ,
t he c o n c e p t i o n t h a t the s p e c i a l qu a n t um ra t e s o f
r o ta t i o n v a r e t h e o n ly p o s s i bl e o n e s a n d u s i n g t h e dumb be ll
n ,
-

m od el he a u h o 96 h a s r e c e n tly c a rr i e d ou t t he str i c t c a l c ul a
,
t t r 1

t ion for s tr uc tu r e s wi t h tw o d e gr e e s o f f r e e d o m ( fr e e a x es o f
r ota ti o n
) m,
a ki n g u s e o f t h e l a t e r i d e a s o f t h e qu a n t um t h e o r y .

Th i s s t r i c t e r m e t h o d l ik e wi s e gi v e s u s cu r v e s for t h e r o t a t i o n a l
h e a t whi c h a re u sel e s s for t h e y a l so h a v e a m a xi mum a n d
,

a s u bs e qu e n t m i n i mum a s i n E hr enfes t s ca s e O n ly b y
’
.
,

m a ki n g s p e c i a l sub si dia r y a s sumpt io n s s uch a s e x cludin g ,

c er t a i n qu a n t um s ta t e s c a n w e ge t cu r v e s wh i c h r i se s te a d ily
,

wi th i n c r e a si n g t e mp e r a tu r e a n d wh i c h a gre e a t l e a s t t o a
, ,

c e rt a i n e x t e n t wi t h ob s e r va ti o n 197
, .

N ot much m ore s a tis fa c tory r e s ul t s w e r e ob t a i n e d i n t h o s e

i n v e s t i g a tion s wh i c h a g a i n w i t h t h e u s e o f t he dumb b e ll
,
-

m od e l w e r e b a s e d o n P l a n ck s s e c on d t h e o ry A cc or d i n g to
,
’
.

t h i s t h e ory t he d i s cr e t e v a lu e s v o f th e r ot a t i o n a l s p e e d s a r e
, n

n o t th e o n ly p o s s i bl e o n e s ; o n t he c o n t r a r y t h e m o l e c ul e c a n
,

r o ta t e wi th a ll r o ta t i o n a l s p e e d s b e t w e e n 0 a n d co a n d he n c e

c a n a ss um e a ll v a lu e s o f r ot a t i o n a l e n e r y b e t w e e n 0 a n d co
g ,

e x a c tl l i k e t h e P la n ck o s c i ll a t ors i n P l a n ck s s e c o n d t h eo r y
’

y .

Th e p e cul i a r i t y of the s p e c i a l qu a n t um v a lu e s ( 8 0) for t h e

e n er gy h e re co n s i s t s i n t h e fo ll o wi n g i m a gi n e t h e e n e r gi e s
E pl o t t e d as a bs ci s s a ( Fi g 7 ) a n d t he cor r e sp o n d i n g p r o b
, .

a b il i t i es w a s o r di n a t e s ; t h e n a s te l a dd e r c u rv e r e s ul t s
p
-

,
74 T HE Q UA N T U M T H EORY

t he st ep s of wh i c h li e e x a c tly a t the v a lu e s E 2 The p rob ) .

a b i l i t y t h a t a g i v e n v a lu e E of t he r ot a t i o n a l e n e r gy w i ll
r

a pp e a r i s t h e r e for e con s ta n t w i thi n the r a n e o en er

g f gy b e tw een

E 9 a nd
9
bu t cha n ges su dd en ly a t the en d s of thi s r a nge .

A cc or d i n g t o P l a n ck s fir st t h e o r y wh i ch a ll o ws o n ly t he
’

qu a n t um v a lu e s t h e e n c i r cl e d p oi n t s a l o n e h a ve a
m e a n i n g O n ly at t h o s e p oi n t s i s t he p r ob a b il i ty o t h e r t h a n
.

z ero w hil e al l i n te r m e d i a te v a lu e s of the e n er gy p o s se ss the

,

p r ob a b i l i ty z e r o t h a t i s d o n ot o ccu r
, , .

In t h i s c a s e t oo the p r obl e m w a s fi r s t s olve d for o n e

, ,

d e g r e e of fr e e do m (fix e d a x i s of r ota tio n ) E Holm 193 a n d . .

J v Weyssenhofi 199 f o u n d i n a g r e e m e n t w it h on e a n o t h e r a
. .
r
, ,

s te a d ily r i si n g cur ve for t he r ot a tio n a l h e a t whi ch fitt e d th e ,

o bs e r va ti on s w ell a t l o w t e mp e r a t u r e s b u t u n d o ub te d ly w e n t
,

t o o h i gh a t h i gh e r t e mp e r a t u r e s ( fro m a b ou t 1 4 0 a b s u p
°
.

w a r d s) .

B u t wh e n t h e m o d er n d e v e l opm e n t o f t he qu a n tum hyp o .

t h e s i s fo r s e ve r a l d e gr e e s of fr e e d o m t o wh i ch w e sh a ll b e
,

i n t r oduc e d l a t e r w a s a v a i l a bl e a s tr i c te r c a lcul a t i o n fo r
, ,

f r e e a x e s of r o ta ti o n i e fo r t w o d e gre e s of f r e e do m c o uld b e
, . .
,

c a r ri e d ou t Th i s p r obl e m w a s a tta ck e d o n t he o n e h a n d b y
.

M P l a nck 200 o n t he o th e r by F r a u S Rotsza y n fi01 b u t w a s

.
,
.

t r ea te d d i ffe r e n tly i n e a ch c a s e P l a n ck s ta r t e d w i t h t h e
.

p r e m i s e th at t h i s p r obl e m b el ongs to the c a te gor y of s o c a ll e d -

d e g e n e r a te p robl e m s Th i s t e r m i s t o c o n ve y the foll ow

.

i n g : t h e m o l e c ul e r o ta t e s wh e n n o e x t e r n a l f or c e s a c t
,

on i t a c c or d i n g t o t he d o c t r i n e s of m e ch a n i c s
,
w i t h c on ,

s t a n t S p ee d i n a s a ti a ll y fix ed pl a n e T h e p o si t io n of
p
-
.

th i s pl a n e i n s p a c e mu s t so P l a nck a r gu e s b e o f n o i m
, ,

p ort a n c e fo r t he sta t isti c a l s ta te of the m ol e cul e H e n c e the .

c o n d it io n o f r o ta t i o n of t h e m o l e cul e in t he s e n s e of t he

qu a n tum t h eo r y i s d e t e r m in e d b y a si ngle qu a n ti ty n a m e ly , ,

t h e r o ta ti on a l e n e r gy In s p i t e o f t he f a ct t h e r e for e t h a t
.
, ,

th e p r o bl e m i s o ri g i n all y a n d n a t u ra lly a p robl e m of t w o

d e gr e e s o f f r e e do m —for t he p o s i tio n of th e m ol e cul e i n s p a c e
i s d e t e r m i n e d by t w o a n gl e s — w e mu s t a c c or d i n g t o P l a nc k , ,

t re a t i t i n the qu a n tum t h e or y a s a p r obl e m o f o n ly o n e

d e gre e of fre edom The t w o de gr e e s of fre e do m c oa l e sc e a s
. ,

it w e r e ; t h e y a r e coher en t .

In c o n t ra s t to th i s F r a u Rotsza y n p r oc e e ds t o tu r n t he
,
H E A T OF RO T A T I O N OF D I A T O M I C G A SE S 75

p r obl e m in to a n o n d e ge n e ra te o n e by t he add i ti on of a n e x
-

t e rn a l fi e ld a n d a ft e r s o lvi n g t hi s p r obl e m r e duc e s the fie ld

, ,

of f or c e t i ll i t v a n i s h e s Th i s m e t h od wh i c h w as a ls o u se d
.

b y t he a u t h or i n th e p a p e r a b ove c i t ed a pp e a r s t o b e p a r ,

t i c u l a r l y a dva n t a g eo us wh e n t he c a lcul a t i o n i s b ase d o n

,

P la nc k s fir st th e ory for p e cul i a r d ifli cu l t i e s a ri s e in d e ge n

’

,
"
erate c a s e s Succ es s h e r e d e c i d e s i n fa vou r of the s e c on d
.

m eth od For whi l e P la n ck fi n ds a cu r v e 303 wh i ch ri s e s a bov e

.

the cl a s s i c a l v a lu e t o a m a x i mum a n d t h e n d escend s a s y m p,

t o t i ca l l y t ow a r d s t h e v a lu e R — a n d i s t h e r e for e o f n o u se
t he c a lcul a t i o n o f F r a u R otse a y n g i ve s a ste a d i ly r i sin g cu r v e ,

wh i ch a gr ee s w ell w it h the m ea s u re m e nt s for l ow e r a n d h i ghe r

te mp e ra t u r e s ; o n ly th e va lu e obs e r ve d a t T 1 9 7 ab s l i e s
°
.

a bo u t 1 0 e r c e n t t oo l ow 203
p .

Wh il e al l the a b o v e m e nt io n ed i n ve s t i ga t i o n s
-
b a se d o n
the dumb b e ll m o d e l wh i ch c a n o n ly be r e ga r d e d a s a p ro
-

v i sio n a l s ch e m a ti c co n s tr uc t i on P S Ep s tei n 204 i n 1 9 16

, ,
. .

c a r r i e d o u t th e c o rr e sp o n d i n g c a lcul a t i o n s fo r a n ot h e r m o l e

c u l a r m od e l p r o p o se d by N B ohr 205 Th i s m o d e l o f t h e
. .

hydroge n m ol e c ul e t o wh i ch w e s ha ll r e t u rn l a t er i s bu i l t up
, ,

o f t w o p o s i t i v e h d r o g e n a to m s e a ch o f wh i ch c a r r y a s i n gl e
y ,

po sitiv e c h a r g e a n d a r ou n d t he c onn e c t in g l i n e of whi ch tw o

,

e l e c t r o n s d i a m e t r i c a lly o pp o s i te r o t a t e i n a fi x e d c ir cl e a t a
, ,

fix ed ra te (s e e Fi g . Si n c e th e e qu il ib r ium i n t h i s pu re ly
e l e c t r i ca l s y s t e m i s d e te r m i n e d b t h e pl a y o f t he Cou lom b
y
a t t ra c t i o n s a n d t he c e n t r if ug a l f o rc e s a n d sin c e t h e r a di us o f
,

t he e l e c tr on i s d e te r m i n e d by a qu a n t um c o n di ti o n t h i s m o d e l ,

p o s se s s e s t he a dva n ta ge th a t al l i ts d i m e n s io n s a re co mpl e t e ly
76 T HE Q U A NTU M T H E ORY

fi xe d so t h a t t h e re i s n o l on g er a n y qu e s t i o n o f the a rb itra r i
,

n e s s o f t h e m o m e n t o f i n e r ti a Th e dumb b e ll kn ob s a r e .
-

r e p re se n t e d h e r e b y t he t w o p o si ti ve ly c h a r ge d hyd r o g e n -

a t o m s ; t h e r ot a t i o n s of t h e m ol e c ul e h i t h e r t o c o n s i de r ed
wo uld th er e fo r e c or r e sp on d t o t h o s e m otio n s i n wh i ch t he
m ol e cul e r ot a t e s wi t h a m o m e n t o f i n e r ti a J a b ou t a n a x i s
a t r i gh t a n gl e s t o t h e l i n e j o i n i n g t h e a t o m s B u t to t his .

t h e r e mu st v e r y pl a i n ly b e a dd e d t he r o t a t i o n o f the s y s t e m
a b o u t t h e a x i s o f s ymm e t r y ( i e t he l in e j o i n i n g t h e a t o m s). .
,

wh i ch r e s ul t s fr o m the e x t r e m e ly r a p i d r ota t i o n o f th e e l e c
t r on s The m o m e n t o f i n e r ti a c or r e sp o n d i n g t o t hi s a x i s i s
.
,

i n c o n s e qu e n c e o f t h e ex t r e m e ly sm a ll m a s s o f t he e l e c t r o n s
.
,

v e r y sm a ll c o mp a re d w i th J Th e wh o l e s y st e m o bv iou sly .

p o s s e s se s i f w e r e ga r d i t a pp r ox i m a t e l y a s r igi d the p r o p e r ti e s
, ,

o f a sy mm etr i ca l to
p It s m o t i o n i s t h e
. r e f or e i n c on s e qu e n c e ,

o f i t s o w n r o t a t i o n a b o u t t h e a x i s o f s ymm e t r y n ot a r o t a t i o n , ,
”
b u t i n st e a d t he w ell k n o wn m ot i o n r e gul a r p r e c e s s i o n
- 205
,
.

Ep stei n t r e a t e d t h e p r o bl e m f r o m t h i s p o i n t o f v i e w b u t co uld
n o t ob t a i n a g r e e m e n t a t l ow t e mp e r a t u r e s w i t h t he m o m e n t

o f i n e r t i a c a lcul a t e d f r o m t he m o d e l i t s e lf 207 n a m e ly J 28 2 , ,

41
x 10 P r e su m a b ly t h i s f a i lu r e d e p e n ds o n th e f a c t t h a t
.
,

t h e m o d e l d o e s n o t c o rr e s p on d w i t h r e a l i ty a n d i n f a c t w e ,

s h a ll se e l a t e r t h a t w e ll f o u n d e d d o ub t s h a v e a r i s e n a s t o t h e
,
-

c orr e c t n e s s o f t he B ohr m o d e l We mu s t t h er e fo re a dm i t .
,

u n for t u n a t e ly a s o n e o f a n umb e r o f i n s ta n c e s i n the qu a n t um

t h e or y t h a t t he i mp o r t a n t p r o bl e m o f t h e r o ta t i o n a l h e a t of
,

hyd r oge n s till a w a it s s olu t i on .

2 . T he Bj e rr um Infr a -
red R ota ti on -
s pe c tru m

N . Bj er r u m pp li e d t he r e l a tio n ( 7 9 ) i n a ve r y
208 ha s a

i n t e r e s t i n g m a n n e r t o t he i n f r a re d a b so r p t i o n o f p o lya t o m i c -

ga s e ous c o mp o u n d s Th e s e ga s e s ( for e x a mpl e H Cl H B r

.
, ,

CO H 2 0 i n t he f or m o f s t e a m bu t o n t he o t h e r h a n d n ot
, ,

t h e e l eme n ta r y g a s e s H 2 02 N 2 01 ) s h o w a c c o r d i n g t o t h e
2 , , , ,

i n v e st i g a t i o n s o f S P L a n gley 209 F P a schen 2 10 H R u ben s 2 11

. .
, .
,
.
,

H R u ben s
. E A schki n a ss, 2 12 H R u ben s a n d G H e ttn er ,2 13
an d . . .

W B u r me i s ter , “ E va v B a hr fi’15 e x te n s iv e a b s or p ti on b a n d s
. .

i n th e s h or t a n d l o n g w a v e i n fr a r e d W h i l e i n the l o n g
- -
.

w a v e i n fra r e d w e a cc ou n t for the a b s or p tio n by t he rota ti n g

-

m ol e cul e , wh i ch ,
co mp o s e d of p o si tiv e ly an d ne g a t i v e ly
 IN FR A R E D -
RO T A T I O N S PE CTR U M 77
c ha r ge d a to ms a c t l ik e e l e c t r i c d o ub l e p o l e s a n d h e n c e i n
,

t u r n i n g e m i t a n d a b s orb r a d i a t i o n Bj er r u m w a s t he fir st to ,

p oin t o u t th a t the m ol e cul a r ro t at i on mu s t a l s o m a ke i t s e lf

n o t i c ea b l e i n t h e sh o rt w a v e i n fr a r e d -
F o r if t h e r e e x i s t s -
.

i n t h i s r e gi o n a l i n e a r v i b r ati o n v0 of t he i o n s i n t he m ol e cul e
r e l a t i v e ly to o n e a n o t h e r — a n d h e n c e a n a b s or p t i o n a t t hi s

p o i n t — a n d if i n a dd it i on t he wh ol e m ol e cul e r ot a t e s a t t he
, ,

sp e e d y t h e n it i s k n own t h a t t h e r e w ill b e p r oduc e d a s a

r,

r e s ul t o f t h e c o mp o s i t i o n o f t h e v i b r a t i o n w it h t h e r o ta t i o n 2 16

t w o n e w v i b r at i o n s ( a n d c o r r e s p o n d i n gly t w o n e w r e gi o n s
, ,

o f a bs or p t i o n h v i n g th e p e r i o ds v0 and t o sym
) a v v r 7 ,

m etr i c ally di sp o s e d o n b ot h s i d e s of the i o n i c v ibr a t i on v0 .

O n the wh ol e t h e n w e h a v e t hr ee p o i n t s of a bs orp t i on
, ,

v7 , v0 V0 v t o wh i ch w e mu s t a d d t he n o n r ot a t i on a l
»
7 ,
-

s t a t e v0 a s a f o u r t h B u t i f n o w a cc or d i n g t o P l a nck s fir s t
’
.
,

t h e or y t h e m ol e cul e ca n o n ly r ot at e w i t h d i s c r e t e S p e e ds o f
,

r o ta t i o n v, [ see w e get symmetr i ca l l y to the or i gi na l

i a bsorp tion d, bo th sid es o f i t, a ser i es

p osi t on o f v v0 a n on

o
f fu r ther d i scr e te equ i d is ta n t p osi tion s o f a bsorp ti on

h
v = vo + vn v0 + n
2
J
‘
h
( 83)
m m
ae
-
r
,

Th e se d i scr e te e qui di s ta n t p o s it i on s of a bsor p t ion h a v e

a c t u a lly b ee n f ou n d b y E va v B a hr i n t he c a s e of w a t e r .

va po u r a n d ga seo u s hyd r o chl or i c a c i d a n d w e r e m e a s u r e d ,

l a ter w i th s t ill grea t e r a c c u r a cy b y H Ru ben s a n d G H ettn er . .

fo r w a t e r v a p ou r In a n e x a m i n a t i o n c a rr i e d o u t o n a n
.

e x te n s iv e sc a l e E S Im es 21 7 h a s o n c e m or e t h o r o ughly
. .

i n ves t i g a t e d t h e hydr o g e n h a l i d e s ( H Cl H B r H F ) a n d c o n , ,

fir m e d th e l a w ( 8 3) for the p o sit io n of t he a bs orp tion l i n e s .

It w a s ther eby fou nd tha t the m idd l e l i n e we w a s a l wa

y s

m i ssi ng Fr o m t he st a n dp oi n t of the t h e or y h e r e d e sc ri b e d
.

th i s wo uld m e a n t h a t th e n o n r ota ti on a l s t a t e d oe s n ot e x i s t ,
-

t ha t i s , tha t the molecu l es a l w a ys r ota te ( z e ro p o i n t ro ta t i o n ) -

.

A E u cken ,21 8 w ho d i sc uss e d t he r e s ul t s of E v B a hr ,

. . .

whi ch we r e a t t ha t t i m e th e o n ly on e s k n o wn , d e duc e d fro m

t h e goo d a gr ee m e n t b e tw e e n o bse rv a t i on a n d ca lcul a tion t h a t
'
P la nck s se co n d th eo r y i s n ot v a l i d , for t he e xp e ri m e n t s
78 T HE Q U A NT U M T H E ORY

s ee m e d so obv i o usly to p rov e t ha t t h e m ol e cul e c a n a ct u a lly

on ly r ot at e w it h t he di sc r e t e sp ee ds v Th i s c on clus i o n
n. ,

,
k
h owe v e r i s n ot i n e vitabl e a s P l a n c 9 S how e d i n a p e n e
,
21

t ra ti n g i n v e sti ga ti o n O n th e c on t r a r y t h e obs e r v a t i o n s
.
,

m ay a f te r a ll b e ex pl a i n e d su r p ri s i n g a s i t m ay s e e m on th e
, ,
”
b a s i s o f h i s s e c on d t h e or y ( c on ti n u o us cl a ss ic a l ab s or p
t i on ; a ll S p e e ds of r ot a t i o n p o s s ibl e ) Thi s cu r io us r e sul t i s
.

e x pl a i n e d a s f oll o ws : L e t b e th e p r ob ab i l i t y t h a t
a m o l e cul e ss e s se s e x a c t ly t he r ot a t i o n a l e n e r gy E ; h e n c e
p o ,

fo r N m ol e cul e s w ill b e t h e n umb er t h a t w i ll

p oss e ss e x a c tly t he r otat ion a l e n er gy E Th e s e m ol e cul e s
, .

( )
r ot at e t h e r e fore — a cc or di n g t o 7 8 — w i t h t h e S p e e d

’
The qu a n tit y i s h e r e a cc or d i n g t o P l a nck s s e c on d
,

t h e or y t he step l a d der cu r ve p i c t u r e d i n Fi g 7 P l a n ck s
’
-

, . .

c a lc ul a ti on t h e n l e a ds t o th e foll o wi n g r e sul t : the a bsorp ti on

of a n ex ter na l r a dia tion o fr e u en c *
i — a s on e shou ld
f q y v s n o t
exp ect— p r op or ti on a l to the n u m ber o m s havi ng a
f o l ec u l e

r o ta tiona l s eed v *
i b
p v tha
, t s,t o the qu a n ti ty ,
w ( )
E u t to ,

i ts d if feren ti a l coefiici en t Th i s d i ffe r e n t i a l c oe fitl c i e n t

i s, h ow e v e r ,
as Fi g 7
sh o ws e verywh e r e e qu a l t o z e ro
.
, ,

e x c epti n g a t t he sp e c i a l qu a n t um e n e r gy va lu e s E f ”
f th at i s
-

, ,

a t the r ota t i on a l sp ee ds v It f o ll o ws fr o m t h i s t h a t h e r e
n. ,

a ls o f r o m t he s t a n dp o i n t of P l a nc k s s e c on d t h eory a bsor tio n

’

, p ,

ta kes p l a ce on ly a t the sp ecia l qu a n tu m r a tes of r ota tion v

'

n.

It thus c o m e s a b o u t t h a t a t p r e s e n t at a n y r a t e t h e i n f r a
, ,

r e d a b s or p t i o n sp e c tr a o f the po ly a t o m i c g a s e s c o n t ra r y t o ,

a l l e x p e c t a t i o n d o n ot d e c i d e o n e of t h e m o s t fu n d a m e n t a l
,

qu e stio n s of t he wh ol e qu an t um t h eory wh eth e r n a m ely , , ,

’
P l a n ck s fi r s t o r s e c on d t h e ory i s c orr e c t A n i mp o r ta nt .

r e m a r k mus t b e a dd e d h e r e The d e du c ti o n s of th e r e l a ti o n
.

wh i ch gi ve s th e p o s ition of t he i n f ra r e d a b so rp t io n b a n d s i s
-

ha lf i n a ccord a n c e wi th t he cl as s i c a l a n d h alf i n a cc ord a n c e

wit h the qu a n t um t h eory For a l th ough the r ot a t ion a l
.

sp ee ds v a r e d et er m i n e d by the qu a n tum t he ory the r e solu

7, ,

t i o n o f the o sc i ll a t i on v0 i n t o t he t w o c o mp on e n t s t o f i t r
. .

a r e d e t e r m i ne d by the cl a ss i c al m e t h od s H ow to a tt ac k th i s
.
 T H E D E G E N ERA T I O N OF G A SES 79

pro bl e m f r o m a p o i n t of v i e w e n t ir e ly c o n s i st e n t w ith th e
qu ant um th eory will b e s ee n l at e r i n Ch a p t er VIII .

3 . T he D e gener a ti on of G a se s

The p h e n om e n a d e sc r i b e d a b ove wh i ch w e re obs e r v e d i n

th e c a s e of p oly at o m i c ga s e s ( fa ll i n g o ff of t h e m ol e cul a r h e a t , -

a n d i n fr a r e d a b s or pt i on ) jus t i fy fully t he a ppl i c a t i o n o f the

-

qu a n t um th e or y t o m ot i o n s of r ot a t ion O n the ot h e r ha n d , .

t he a t te mp t s t o go a s t e p f a r th e r a n d t o a pply i t t o t he
tr a n sla tion a l en er gy of ga ses r e s t up o n a much m o r e i n s e cu r e
b a s i s If t h i s s te p is t a k e n , the h it h e r to e x c e p t ion a l p osi tion
.

o ccup ie d by the m on at om i c g a s e s wh o s e m ol e cul e s c on ta i n ,

o n ly t r a n sl a t i o n a l e n er gy b e co m e s d e s t r o y e d for t h e n t h e y
, , ,

t oo must su c cumb t o t h e qu a n tum l a w

,
Th i s p r obl e m .

h a s b e e n a t t a ck e d f r o m v a r i o us qu a rt e r s [ 0 S a cku r flfio H . .

Tetr od e 22 1 W H Keesom fim2 W L en s a n d A S ommerfel d 228

,
. . . .
,

P S cher r er fi
.
fl l M P l a n
‘
ckfl ]
fifl . Thus for e xa mpl e Tetr od e , , ,

Keesom L en z a n d S ommerfeld i m a gi n e the t h e r m a l m ot ion

,

o f t h e ga s S pl i t up i n t o a sp e c tr um of n a t u r a l f r e qu e n c i e s a n d ,

t h e y t h en d i s t ribu t e t h e e n e r gy i n qu a n t a t h a t i s a cc o rdi n g , ,

t o f or mul a o v e r t he i n d i v i du a l n a t u r a l fr e qu e n c i e s qu i t e ,

a n a l o go u sly t o t h e m a nn er of D ebye a n d B or n Kar man i n -

t he c a s e o f s ol i d b o d i e s S cher r er a n d P l a n ck on t he oth e r
.
,

h a n d a pply t he qu a n t um hyp ot h e s i s di r e c tly to the m ot ion

,

of t h e i n di v i du a l ga s a t o ms b a s in g t he i r a r gum e n t o n the
-

m od e rn for m ul a t ion of t he qu a n tum c on d iti on s for s e v e r a l

d e gr e e s of free d o m H ow such a qu a n t um r e solu tio n of the
.

t r a n sl at or y m o t i o n i s e ffe c te d i s p e r h a ps m o s t e a s i ly s e e n
,

b y the f oll o w i n g S i mpl e e x a mpl e ( Scher r er ) : L e t a ga s a t o m -

of m a ss m fly t o a n d fr o i n a cub e s h a p e d S p a ce o f s i d e a -

wi t h t he S p e e d v p a r all e l t o o n e of t he e dge s It t h e n .

1)
exe cu t e s a s ort of o scill at io n wi t h t he p e r iod V
2a
‘ If w e
i t s ki n e t i c gy E v
Q
cco r d i n g t o P l a n ck fir s t
’
se t e ne r , ,
a s

hi
t h e or y f 0, 1 , 2 , 3 the n i t foll o ws t h a t
§ (
n n

fi
2
f
rnv
80 T HE Q UA NT U M T H EORY

he n c e
and En

He n c e th e v e l o c i t y of the a to m a n d i ts tr a n sl a tor y e n e r gy ‘

c a n a c qu i r e o n ly d i sc r e t e qu a n t um d e t e r m i n e d v a lu e s
,
-
.

Th e c a lcul a t i o n s of th e a b o v e n a m e d i n v e s t i g ator s l e a d t o
-

t w o i mp o r t a n t m a i n r e s ul t s a t l e ast i n qu a l i t a t i v e a gr e e m e n t ;
,

i n t h e fi r st pl a c e t h e r e r e sul t s a n a l t e r a t i o n i n t he ga s l a ws
,
.

a t v e r y l o w t e mp e r a t u r e s The n e c e ss i t y for t h i s d e g e n e ra
.

t i on o f t h e m o n a t o m i c g a s es h a d a l r e a dy b e e n r e co g n i se d by

N er n s t,
w h o d e duc e d i t o n t h e b a s i s o f h i s n e w h e a t t h e o r e m 226 .

F o r i f t h e e qu at i o n of s t at e o f i d e a l g a s es

p p r e s su r e
= R
V v o lum e o f a gr a mm e a t o m -

p V
R a b s o lu t e
ga s c on s t a n t
-

T t e mp e ra t u r e

were e xa c tly t r u e fo r a ll t e mp e r a t ur e s d o w n t o the l o we st ,

the n t h e m ax i mum w o r k A wh i c h c o uld b e g a i n e d fr o m

,

the i s o th e r m a l e x p a n s i o n o f t he ga s f r o m t h e v olum e VI t o
t he v olum e V2 w o uld h a ve a s w e k n o w fo r al l t e mp e ra tu r e s
, , ,

t he v a lu e

R RT l og e

Fo r all t e mp e r a t u r e s dow n to a b s olu t e ze r o

wo uld d ifier fr om z er o i n d ir e ct co n tr a d i c t i on t o t he c o n d ition

'

o f N er n s t s Th e or e m H e n ce i t f o ll o ws tha t i n the r egi on

’

( )
38 .

of the l ow es t temp er a tu res the equ a ti on of sta te ( 8 5) mu s t

,

u nd er go m od ifi c a ti on In
. f a c t e x p e r i m e n t
,
s o f O S a cku r zfl" .

o n hyd r og e n a n d h e l i um a pp e a r t o sp e a k i n f a v ou r of the
”
e x i s t e n c e of t h i s d e ge n era tio n .

§ 4 T he Ch e mi ca l Co nsta nts
, of M ona tomi c G a ses

Th e c
se on d m a i n r e sul t gi v en by the a ppl i c a t io n o f the
qua n tum t he ory to m on a tom i c ga se s i s a n e xtre m e ly in ,

t e r e sti n g r e l ati o n of the P l a nck co n s tan t h to the so c a ll ed -

 CO N S TA N TS OF MO N A T O M I C G A SE S 81

che m i c a l c on st a n t of the ga s a qu a n t it y wh i ch pl a ys ,

a n i m po rt a n t p a rt i n ch a n ges o f t he s t a t e o f a ggre g a t i o n

( v a p o r i sa t i o n s ubl i m a ,
t i o n ) a n d i n c h e m i c a l s t a t e s o f e qu i

l i b ri um B u t i t i s h e r e S p e c i a lly e mph a s i se d t h a t t he r e
.

l a tion sh ip ju s t m e n t io n e d i s n ot bo u n d t o t he u n d e n i a bly
hyp ot h eti c a l r e s olut ion of the t r a n sl a tor y e n e r gy in to qu a n t a .

O n th e c on tra ry O S ter n 228 ha s succ e e d e d i n d e duc i n g i t u n

,
.

o bj e c t i o n a b ly w i thou t app l yi ng the qu a n tu m theor y to the ga s

‘

.
,

The o r i gi n a l m e thod wh i ch S ter n a dop t s m a y b e S h or tly

, ,

s k e t ch e d h e r e C o n s i d e r t h e p r o c e s s o f s u b l i m a t i o n i e t he
.
, . .

p a ssa ge fr o m t he sol i d i n to the v a p o u r s ta t e L e t t he .

v a p ou r ob e y the ga s l a w s a n d l et it s de n sit y b e n e gl i gibl e

,

c o mp a re d w i t h t h a t of the co n d e n s e d s o l i d Th e n cl a s s i c a l .

t h e r m o dyn a m i c s gi ve s for the p r e ssu r e p o f the s atu r a t e d

va p our a s a fu n c ti o n of t he te mp e r a t u re t he foll ow i n g
e qu a t i o n

\o
’

RT
-
l
- 5
f
l og T T + O ( )
86

H e r e t o i s t he va p or i s a tio n ( p e r g ra mm e a t o m ) a t
hea t of -

)
a bs olu te z e r o E ? i s t h e e n e r gy o f t he co n d e n se d s o l i d
, (p e r

gra mm e a to m) a t t he t e m p e ra t u r e T ; t he c on st a n t C wh i ch
-

i s t he ch e mi c a l c on s ta nt of th e v a p ou r i s in g subs ta n c e ,

rema i n s u nd e ter mi n ed , a ccor d i n g to the r m od yn a mi cs . On

t he ot h er h a n d ,
t he gh t ha n d s i de o f
i n t e gr a l on t he ri -

e qu a t i o n wh i ch c o n t ai n s t he e n e r gy of the s ol i d
m at e r i a l m a y b e c o mpl e te ly c alcul a te d up on t he b a s is of
,

o u r a s s u r e d k n owl e dg e of t h e e n e r gy c on t e n t o f t h e s o l i ds -
.

We o n ly r e qu i r e t o a ss um e the s ol i d to b e a B or n Har man -

c r y st a l a nd he n c e to u se the qu a n t um t h eo re t i ca l v a lu e (4 1)
,
-

l )
fo r E f If w e n ow r e stri c t our s e lve s to h i gh t e mp e ra t u r e s ‘

.
,

to a r e gi o n t h e r e for e i n whi ch t he cl a ss i c a l t heo r y i s v a l i d

, , ,

( 8 6 ) a s sum e s th e for m

l og p n —
}
1 l og T + 3 l + 0 ( )
8 7
82 T HE Q UA N TU M T H EORY

T SN qu a n ti ti e s vi h e r e f or m the e l a st i c sp e c tr um of t he
( h e

s ol i d b o dy ; 17 i s t h ei r g e o m etri c m e a n ) The f or mul a t i on o f

.

t h i s e qu a t i o n co n st i t u t e s t he fi r s t s t e p o f S ter n s d e du c t i o n
’
.

It gi v e s t he r e sul t of t h e r m o dyn a m i cs , e xt e n d e d b y t h e
a ppl i c a ti on of t h e qu a n t um t h eo r y t o t he c on d e n s e d s u b

s t a n c e The s e c on d s t e p i s t he fo r mul a t i on , i n a c c or d a n c e
.

wi t h m ol e cul a r t h e ory , of a va p o u r pr e s s ur e for mul a for h i gh

-

t e mp e r a t u r e s , i n t h e r e g i on t h e r e for e of cl a s s i c a l s t at i s ti cs .

H e r e , a ls o the B or n Har m an s ol i d m od e l i s us e d for t he c on

,
-

d e n s e d s ub s ta n c e , a n d , o n t he b a s i s o f k n o wn l a w s of
p rob ab i l it y, t he n umb er of the a to ms i s c a lcul a t e d whi ch a r e
i n s ta ti sti c a l e qu i l i b ri um i n t h e v a p ou r ph a s e In t hi s w a y .

the d e n s it y o f th e v a p o u r , a n d h e n c e , a s a r e sul t of t he gas

l aws , i ts pr e ssur e , a re gi ve n So S ter n fin d s
.

i l og T +

H er e m d en ote s t he m a ss o f a n a tom a n d NO i s the wo rk ,

whi c h i s n e ce ss ar y t o b ri n g N a t o m s (N i s t he A voga dr o
n um b e r) fr o m c o mpl e t e re s t t o t he a seo u s s t a t e A n un
g .

d e te r m i n e d c on st a n t n a tu r a lly d oe s n ot a pp e a r i n t hi s for mul a

d e duc e d fr o m pu re m ol e c ul a r t h eor y Fo r t h e m ol e cul a r
.

m o d el i s c o mpl e t el y d et e r m i n ate a n d h e n c e gi v e s t he a bs o lut e

,

v a lu e of t h e va p ou r p r e ssu r e n ot o n ly i t s t e mpe ra t u r e co
,

e ffic i e n t a s i n t h e c a se of t h e r m o dy n a m i c s
, A c o mp a r i s o n .

( )
of 8 7 w i t h ( )
8 8 s h o ws fi r s
,
t ly t h a t ,

3N

a nd s ec on dly th at ,
th e ch e mica l con s t a n t C ha s th e v a lu e

0 l og

Re l a t i on ( )
89 m a y b e i n t e r p r e t e d b y m a k i n g t he supp os i t io n

t h a t t he s ol i d b o dy a l r e a dy p o s s e s s e s a n e n e r gy a m o u n t i n g t o
3 1V

2 1
at th e a bs olute z er o ,
tha t i s , a z e ro
-
p o in t en er gy , to

whi c h the l a t e nt hea t of va p o r i s a t i o n A, mus t be a dd e d ,

in
 CO N S TA NT S OF M O NA T O M I C G A SES 83

or de r to s e t t he a to m s c o mpl e t e ly f r e e f r o m t h e i r u n ion i n the

c rys tal E qu a t i on ( 9 0) gi ve s u s t he s olu t i on o f the p robl e m
.

b e fo r e us . It gi ves the chem i ca l con sta n t of the m on a tomi c

a ses a s a fu n c tion of the a tom i c m a ss a n d the u n iver sa l
g
con s ta n ts h a nd k N owh e r e h o w e v e r i n the wh o l e
.
, ,

d e duc tio n t h i s sh ould b e e mph a s i s e d o c e m ore ha s the

— n —

qu a n t um hyp oth e si s b e e n a ppl i e d to t h e ga s i t s e lf .

In or d e r t o m a k e f o r mul a ( 9 0) av a il a b l e fo r c o mp a r i so n
wi th e xp e r i m e n t 229 w e m ay ex p e d ie n tly i n tr o duc e t he m ol e c
R
ul a r w e i gh t M mN , an d se t k —
: th en
N

7t
C 00 l M wh e re 00 log
(2 2 3
a og ,
1
If we fi n a lly u s e t he b a se 1 0 i n s t e a d of t he n a t u ra l b a se e for
o u r l o g a r i t hms a n d m e a s u r e th e v a p o u r p r e s s u r e n o t i n
,

a b so lu t e m e a su r e b u t i n a t m o sph e r e s w e ge t t he c h e m i c a l,
’
co n s ta n t C u s e d b y N erns t whi ch i s r e l at e d t o S ter n s v a lu e
,
’

fo r 0 t hu s :
0
2 3 02 6

F or i t w e fin a lly ge t t he si mpl e
pr e ss io n ex

M ( )
' '
0 9
’
GO l
g g1 0
o .
wh e re G
O ,
1
Th i s f or mul a ha s b e e n b r i ll i a n t ly v e r i fi e d by exp er i m e n t The .

h i th e r t o m ost t r u st wor thy m easu r e m e n t s of va po u r p r e s s u r e

a n d ch e m i c a l s t a te s o f e qu i l i b r i um g i v e i n t h e c a s e o f hyd r o

ge n a r go n a n d m e r cu r y t h e va lu e s
, ,

i i t
z
We a r e t h e r e for e jus ti fi e d i n s a yi n g wi t h S ter n t h a t the
e x p r ess i on 0 r t he ch e m i c a l c o n s t a n t o f t h e m o n a to m i c
( )
9 fo

ga s e s i s t h eore ti c a lly a n d ex p e r i m e n t a lly o n e of the b e st

fou nde d r e sul t s of the Qu a n tum Th eo r y .
 CH AP TE R VI

T he Q u a nt u m T he o ry of t h e O p t i c a l S e ri e s T he .

D e v e l o p m e nt o f t he Q u a n t u m T h e o ry f o r s e v e ra l
D e g re e s o f F r e e d o m 2 3°

§I . T h e T h oms on a nd th e Ru th erford A t omic M o d e ls

HE gr ea t e s t a dva n c e s in c e M v L a u e s d i sc ove r y o f t h e
. .
’

m et ho d of ROn tge n s p e c trosc opy for d e t er m in i n g c r ys ta l

-

s tr uc t u re w a s m a d e i n t he r e a lm o f a to m i c t h e or y i n 1 9 1 3 ,

wh e n th e Ha n i s h phys i c i st N iel s B ohr pl a c ed t he a to m i c

m od els i n t he s e r vi c e of the qu a n t um t h eory B ohr s l a b ou r s .
’

h a ve i n t h e i r t u rn r e a c te d on t he qu a n t um t h e or y a n d f e rt i l
i s e d i t a n d t hu s a m a r v e ll o us a bu n d a n c e of n ota b l e succ e s s e s
,

h ave b e e n a ch i ev e d in r e c e n t y e a r s t h r ough t he i n tera c tion b e

t w e e n th e dy n a m i c s o f t h e a t o m a n d t h e qu a n t um hyp ot h e s i s .

A m o n g se r v i c e a bl e a t o m i c m o d e l s t h e o n e p r op o s e d by
,

J J Thomson l on g oc c up i e d a much f a v o u re d p o s i ti on a cc or d
. .

i n g t o i t t h e e l e c tr o p o sit i v e p a r t of a n a t o m wh i ch c on s t i t u te s
, ,

th e m o s t i mpo r ta n t p a r t o f i t s m as s i s supp o s e d t o b e a ,

sph e re o f a to m i c d i m e n sion s ( r a d i us a b o ut 1 0 cms ) 8

.

fill e d wit h a p o s it i ve S p a c e ch a r g e in the i nte r i or of wh i ch the

n e g a t i v e p a r t s th e e l e c tr o n s r e st i n a s ta bl e p o s i tio n of e qu i

l i bri um Thi s m
, ,

. o d e l h a s t h e gr e a t a dv a n t a g e of e x pl a i n i n g

o n pu r e ly e l e c t r i c a l g r ou n ds th e p o ss i b i l i ty o f qu a si el a s ti c -

”
a lly b o u n d e l e c t r on s i s such e l e c t ron s a s b e i n g d i spl a c e d
, . .
,

fr o m t heir p o s i t ion o f r e s t a r e d ra wn b a ck i nto it by a for ce

,

w hich i s p r op or ti on a l to the d i sp l a cemen t 331 A n d i t w a s ju s t

w i th the h e lp o f su c h e l e c tr on s t h at a s i s well k n own P , ,
.

D r u de 232 W Voi gt 233 M P l a nck 234 a n d H A L or en tz 235

, .
,
.
, . .

s u c c e e d e d i n b u i ld i n g up l a r g e r e gi o n s o f t h e or e ti c a l O p t i cs ,

n a m e ly ,t he t h eory o f d i sp er s i on a n d a bs or p t i o n a n d t he ,

m a g n e t o o p ti c a l e ff e ct s ( m ag n e to r ota ti on a n d Z cema n e ffe c t)

- -
.

84
 T H O M SO N A N D R U T H ER FORD M O D E LS 85

Mor eo ve r ,
the Thomson m i c m o d e l w a s a bl e b y fo ll ow i n g
ato ,

th e c l a s s i c a l d o c tri n e of t he t h eo ry o f e l e c t r o n s t o d o wh a t ,

mu st be d e m a n de d of e v ery se rv ic e a bl e a tom i c m ode l v i z t o ,

.

e x pl a i n t h e e m i ss i on a s a r e s ul t o f t he o s c i ll a t i o n o f i t s
,
“
e l e c t r o n s o f sh a r p i e e s s e n t i a lly m on o chr om a t i c
, ,
. . S p e ctra l
”
l i n e s the p osi ti on of wh i ch on a c co u n t o f t he qu a s i e l a s ti c
, ,
-

re t os r i n g f o r c e 236 w a s i n d e p e n d e n t o f t h e i n t e n s i t y of t h e
,

e x c it a t i o n t h a t i s o f t he e n e r gy o f t h e o s c i ll a t i o n s
, ,
.

In t h r e e i mp or ta n t p oi n t s o n th e o t h e r h a n d t he m od e l , ,

f a il e d c o mpl e t e ly In the fir s t pl a c e n o succ e s s a t a l l u n l e s s

.
,

wi t h c o mpl ic a t e d a n d a r ti fic i a l hyp ot h e s e s i n ve nt e d a d hoc ,

a t t e n d e d e ffo rt s t o d e duc e f r o m Thom son s m o d e l t h e for mul a

’

fo r t h e O p t i c a l s e r i es fo r e x a mpl e th e s i mpl e f o r mul a fo r t h e

, ,

B a l m er s e r i e s o f hyd o g e r n 23 7 S e c o n dly t he m o d e l c o uld n o t

.
,

a c c o u n t fo r the d i v i s i o n o f t h e s p e c t ra l l i n e s i n a n e l e c t r i c

fi e ld a s o bs e r ve d a n d cl ose ly s tud i e d by J S ta r k 238 (S ta r k .

e ffe c t ) ,
i n s p i t e o f t he f a c t t h a t i t h a d b e e n f o u n d m o s t
v a lu a b l e i n the h a n d s of H A L or en tz for e x pl a i n i n g a n d
, . .
,

ca lcul at i n g t h e Z eem a n e ffe c t 239 Th i r dly it w a s n o t i n a

.
,

p osit i on t o e x pl a in the l a r ge i n d i vi du a l d e fl e ct io n s s o m e t i m e s ,

e x c ee d i n g wh i ch a cc o r di n g t o H Gei ger a n d Ma r sd en “
, .
,

a p a rt i cl e s
-
u nder go i n p a s s i n g t h r o ugh t hi n m e ta ll i c foi ls .

F or o n t h e ir w ay t h r o ugh t he m e t a ll i c f oi l t h e a p a r tic l e s ,
-

whi ch a r e k n o wn t o b e d oubly ch ar ge d h e l i um a to ms c o m e ,

i n t o t he n e i ghb ou r h ood o f t h e m e t a ll i c a t o ms a n d a r e m or e
o r l e ss d e fl e c t e d f r o m t h e ir s t ra i gh t p a t hs by t he e l e c t r i c fi e lds

of t he a t o ms If n ow t he m et a ll i c a t o m s w e r e Thom son
.
, ,

a to m s ,
t he e l e ctri c fi e ld of t h e se a t o ms w o uld a tt a i n i t s
gre a te s t valu e a t t he s u r fa c e o f th e p osit i v e S ph e r e a t a ,

d i s t a n c e t h e r e f or e o f a b o u t c m s f ro m t he c e n tr e o f th e .

a to m . F o r f r o m t he su r f a c e o u twa r ds t h e fi eld d e c rea s e s ,

a cco rdin g t o wi th 125 whi l e i t grows fr o m the

Cou lom b s La w ,
’

,
7

ce n t r e t o t he su rf a ce p r op ort i on ate ly to r Thos e a p a rt i cl es .

-

t h e r e fore wh i ch p a s s cl o s e to t he su rf a ce of th e po s i t i ve
,

s ph e r e mu st u n de r go t he gr e a te s t de fle ct ion A n e a s y a p
, .

p rox im a te c a l c ul ation s h o ws h o we ve r t h a t the fie ld a t t h i s

, ,

di s t a n c e f ro m the c e n t r e i s fa r f ro m be i n g str on g e nough t o

e x pl a i n t he g re a t d e fl e c t i o n s wh i ch Gei er a n d Ma r sd e n h a v e
g
o bse rv e d Thi s w e i gh t y r e a s o n led E Ru therfor d 24 1 t o se t up
.
.
,
86 T HE Q U A NTU M T H EORY

i n ste a d of t h e Thom son m od e l , a n e w o n e , wh i c h w a s a bl e to

e x pl a i n t h e l a r g e d e fl e c t i o n s o f t h e a ra ys A c c or d i n g t o t h e -
.

f
Ru ther or d a t o m i c p i c t u r e , t h e e l e ct r o p o s it i ve p a r t of the
a t o m i s c o mp re ss e d i n t o a e x t e m e ly sm a ll sp a c e
n r 24 2 t h e so
c a ll e d n u cleu s It s ch a r g e E c on si st s i n ge n e r a l of z p o sit i ve
.

e l e m e n t a r y ch a r g e s e s o t h a t E ze ,
H e r e z i s a cc or d i n g t o .
,

a hyp o t h e s i s o f va n d en B r oek
24 3 t h e a tom i c n u m ber o f t h e
,

e l e m e nt i e t h e n umb e r wh i c h g i v e s t h e p o si t i on o f t h e
,
. .

e l e m e n t i n t h e s e r i e s o f th e p e r i o d i c t a bl e Thu s fo r ex a mpl e .
, ,

z 1 fo r hyd r o g e n 2 for h e l i um 3 for l i th i um a n d s o o n

, , , .

A b o u t t h i s n u c l e u s t he e l e c tr o n s d e s cr i b e pl a n e t a r y p a t h s ,

t h a t i s c i r c l e s o r Kep l er e ll i p s e s w it h t he n u c l e u s a s f oc u s
, ,

s i n c e the e l e ctr on s a re a tt r a ct e d by i t i n a c c o r d a n c e wi t h
Cou l om b s La w ( in v e r s e ly p r op o rt io n a l t o t h e s qu a r e o f t he
’

d i s t an c e ) .

In t he e l e c t r i c a lly n e u t r a l a to m h a v i n g t he a t o m i c n um b er
z z e l e c tr o n s c ir c l e r o u n d the n u c l e u s
,
F o r e x a mpl e t he .
,

n e u t r a l hyd r o g e n a t o m c o n s i s t s o f a s i n gly c h a r g e d n u c l e u s

( E 2 ) a r o u n d wh i c h o n e e l e c t r o n r e v o lv e s i n a c i r c ul a r o r

e ll i p ti c p a t h .

Th a t t h i s R u therfor d m o d e l i s a c t u a lly a bl e t o e x pl a i n t he
c a us e o f l a r ge d e fl e c ti o n s o f t h e a p a r t i cl e s i s s e e n a t o n c e ; -

fo r t he fiel d s t r e n g t h o f t he n ucl e us i n c o n t r a st to Thomson s

’
-

m o d e l i n c r e a se s str on gly up t o t he i mm e d i at e n e i ghb our h oo d

,

o f t h e n ucl e u s i n a c c o r d an c e w i t h Cou l om b s La w ; h e n c e
’

, ,

if t h e p o si t i vely ch ar g e d a p a r t i c l e s c o m e v e r y c l o se t o t h e -

n u c l e u s — t h a t i s mu c h n e a r e r t h a n 1 0 8 e m s — t he n t h e y a r e
“

e x p o s e d to t he e x t r e m e ly p o w e r ful r e pul s i o n o f t h e n uc l e u s .

O n cl o se r e x a m i n a t i on t he R u therfor d a t o m i c m od e l d i s ,

a pp o i n t s u s se ri ously : fo r t he r e v o lu t i o n s p e r s e c o n d v of , ,

t h e e l e c t r o n s d e p e n d o n t h e e n e r gy o f t h e sy st e m 244
i
If .
,

t h er e f or e w e s upp o se a c c o r d i n g t o t h e c l a s si c a l e l e c t r o n
, ,

t h eo r y t h a t a n e l e c t r o n r e v olv i n g a t v r e v olu ti o n s s en d s o u t
,

a n e l e c t r o m a g n e t i c r a d i a t i o n o f f r e qu e n c y v t h e n s i n c e the , ,

s ys t e m l os e s e n e r gy b t hi s r a d i a tio n v mus t d i m i n i s h c o r
y ,

r e s on d i n l y B u t t h i s m e a n s tha t the a tom i s u n a bl e to emi t

p g .

a sha rp ,
homogen eou s sp ec tr a l l i n e .

§2 . B oh r
’
s M od el of the A t om
It t hu s pp e ar s t h a t
a we a re obl i g e d t o r ej e ct th i s m o de l a t
th e v e r y ou t s et Bu t . t he h isto r y of phy si c s ha s d e c i d e d
 BO H R S M O D E L OF T HE A T O M
’
87

o t h e r wi s e W i th d ee p si ghte d i nt u i ti on N iel s Bohr saw the

.
-

po ss ib i l itie s of Ru therfor d s m o d e l a n d b r ought i t u n de r the ’

qu a n t um th eor y by m a ki n g t h r e e b old hyp ot h e se s m In t he .

fi r s t pl a c e hg w m t me mm trc m@r el e c tr onsLQ anno t

,

— m e xa ct a gr e e m e n t w i t h th e qu a n tum c on d iti on ( 8 1) or
27T
7

8
( ) 2 f o r t h e r ot a t i n g m o l e cul e .

Th i s gi v e s , i n t h e si mpl e s t
c a s e for the qu a n t um p a ths o f
t h e e l e ct r o n s a d is c r ete f a m ily
,

of c once n tri c c ir cl e s a r o u n d
t h e n u c l e us w i t h r a d n wh i ch
, ,

a r e r e l a t e d t o o n e a n ot h e r a s

th e squ a r e s of the wh o l e
n um b e r s ( 1 4 9 16
Se e F i g 9 . .

Se c on dly , t h e se
“
a ll ow
”
a bl
~ ~~e
e
v
-
or
~ m
w
b its a re s t a ti on ar
~yi
/
” F IG . 9 .

t he y c e rt a m s en s e
are in a

e st i m a t es ? a t trag s
"

hi s s t a b i l i t y i s g ai n e d by m a k i n g
_

t he r a d i c a l c o n d i t i o n t h a t t he e l e c t r o n — i n s tri ki n g c on t ra st
wit h e ve r yt h i n g t ha t t he cl a s s i c a l t h eo ry ha s t a ught u s
sh a ll n ot r a di at e wh e n i n the statio n ary p aths S in c e by m A —
w Afi
- —
qr m w m
.

e n e r gy i s a b o l i s h e d the e l e c t r o n ,
”
ca n c on t i n u a lly r e v o l v e i n s uch a qu a n t um p a th Th a t “
.

t h e r e a r e s uch “
n on r a di a t i n g p a th s i n t he a t o m i s b e
-

y on d do ub t A m on g ot h e r th i n gs the c o n st a n cy i n t i m e
.
, , ,

of t he p a ra a nd f e rro m a gnet i sm of bodi e s whi ch i s -

ge n e r a t e d by r e volv i n g e l e c tr o n s sp e a k s i n fa v o u r of t hi s ,

v i e w B u t h o w e l e c tr o dy n a m i c s mu st b e a l t e r e d i n o r d e r t o
.

gu a r a n t ee t he n on ra di a t io n of t he qu a n t um p a t h s a n d o n ly
-

o f t h es e i s a q u e st i on wh i ch a s y e t r e m a i n s u n a n s w e r e d
,
As .

”
w e h av e n ow ab oli sh e d t he cl a ss i c a l r a d ia ti on of the “
 88 T HE QU A NTU M T H EORY

a to m ,
c tu a lly obs erv e d e m i ss ion must b e a cc o u nte d for
th e a

by a n ew hypoth e s i s H e r e a g a i n i n dir e c t c on n ex i on
.
,

w i th P la nck s or i gi n a l qu a nt um r ul e Boh/r s t hi rd c o n di t i on
’

,
’

t a k e s e fle c t : wh e n th e e l e c tr on p asse sj rom m n e a flowa bl e

’
.

at . A “ ; c “ ‘

qu a n t um or b it i n wh i ch th e ener gy fi s a no th er

m
x

, - ” l
‘ l " _
fl “ ‘ l a
o

u a n tu m a t h o f ene rgy
a p _
.

d iat e d i n the for m of an ener gy qu an tu m h u of

w
—
2 1 1s ra
-
s
“

W m o n oc hr o m at i e r a di ati on
‘
T h e f r e qu e n cy o f .

t he r a d i at i on e m i tt e d i s d e te r m i n e d by B ohr s Fr e qu e n cy “ ’

C o n d it i o n
V :

W e c an foll ow E i n stei n 246 i n i m a gi n i n g the p a ssa ge fr o m

t he s tat e of h i gh e r e n e rgy t o t he s t at e of l ow er e n er gy a s a
s ort of ra di o a c ti v e di si n t e gra tion the o ccu rr e n ce of whi ch i n
-

t i m e i s d e t e r m i n e d by ch a n c e The d e t a i ls o f t h i s p a ss a g e a n d .

the r e l e a s e of e n e r gy a cc o mp a n y i n g i t a r e h ow e v e r e n t ir e ly , ,

ob scu r e up t o t he p r e s e n t .

T he Hy d ro gen T ype of t o B ohr A t om ic

’
§3 . S eries a ccord i ng s
Mod e l

H ow e v e r b old u n or th od ox B ohr s t h r e e hyp oth e se s

and
’

m ay h a ve a pp ea r e d t h e i r succ e ss w a s su rp r i s i n g
,
If w e a pply .

th e m to a
“
hydr og e n t yp e of Ru therfor d a to m i n wh i ch -

a si n l e e l e ct r on r e v o lv e s a r o u n d a p o s i t i v e n ucl e us w i t h a
g
z f o l d c h a r ge w e t 24 7 for t h e f r e qu e n c i e s o f t h e S p e c t r a l
g e
-

l i n e s wh ic h t he e l e c tr on e m it s i n p a s si n g fr o m the n th to the
,

sth qu a n t um p a t h t he f o ll owi n g v a lu e s,

21r 2 4
mz 2
1 1
( )
e
v
T
I

2 2
e, ha r ge a n d m a s s
m c
3 n
o f e l e c t r on s

s n wh ol e n umb e r s
,

If we h er e se t z 1 ( hyd r og e n
) ,
s 2 , n 3, 4 , 5 we
ge t in ex a ctl y the me for m the emp i r i ca l
sa ex
p r essi on
f or the
B alm e r ser i es o f gl ow i n h
g ydr ogen fi18
‘

y = N
 TH E H Y D RO GE N T Y PE OF SER I E S 89

Fo r the co n sta nt N whi ch a pp e a r s i n t he mp i ri ca l form ul a

e ,

so c a ll e d Ryd ber g n um b e r B ohr Th e o r y t h e r e fo r e g i v e s

’
the -

,
s

t he e x p re ss ion

If we u se h er e the w e ll k no wn v a lu e s
-

x 10 10
‘

( Mi ll i ka n ) h x 10
“
27
( P la nc k)
7
10

t h e n it foll ows fr o m ( 9 5) t h a t
N 10 15

wh i l e t he e m p i ri c a l R ydber g n um b e r ha s t he v a lu e 10 15
.

Th i s s t r ik i n g a g r e e m e n t a n d t he r e s olu t ion o f t h e R yd ber g

n umb e r i n t o u n i v e r s a l c o n s t a n t s i s o n e o f t he m a i n a ch i e v e

m en t s of Bohr s Th eory ’
24 9 a n d f o r m s a s tr on g a r gum e n t for
,

i t s i n n a t e p ow e r W e m a y sa y t h a t a cco r d in g to B ohr s
.
,
’

o r i gi n a l t h eo r y t h e i n d i vi du a l l i n e s o f t h e B a lm er s e r i e s (H
, a ,

H3 H 7, ,
a r e e m i t t e d wh e n t he e l e c t r o n jump s f r o m t h e

3 r d 4 t h 5 th
, ,
o rb i t i n t o t h e 2 n d .

Wit h th i s s ta t e m e n t how e v er the a ch ie ve m e n t s o f for mul a

, ,

9 3 a r e n ot e x h a us t e d F r i t i n clud e s a s w e e a s i ly see
( ) o .
, ,

fu rth er sp e ct ral s eri e s o f hydr o g e n N a m e ly if w e se t s 1 .

, ,

n 2 3 4 , ,
w e ge t t he ul tr a vi ol e t se r i e s t h at w a s fo u n d
-

a n d m e a s u r e d by If on t he o th er h a n d w e s e t
3 3 n ,
4 5 6 , , w e ge t th e i n fr a r ed B er gma n n s e ri e s -

th e fi rs t t w o l in e s of wh i ch w e r e m e a su re d by F P aschen fii5 1 .

The e l e m e n t wh i ch f oll ows hydr og e n i n t he P e ri od i c Sys t e m

i s h e l i um ( a t o m i c n umb er z Whil e h o we v e r t he co n , ,

sti t u t i o n of t h e n eu tr a l h e l i um a t o m w i t h i t s t w o e l e c t r o n s

i s a l r ea dy m or e c o mpl i c a t e d — a cc or di n g t o t he l at e s t i n ve s t i
ti o n s t he tw o e l ec t r o n s c i r cl e a r ou n d t h e n ucl e us i n t w o
g a
'
,

di fle r e n t or b i ts — th e s i mply i o n i s e d h el i um a t o m wh i ch ha s ,

t h er e for e a s i n gl e p o s i ti v e ch a r g e i s e nt ir e ly ,
of t h e hyd r o ge n

t yp e ; fo r it c on sis t s o f a do ubly ch a r ge d p o s i t i v e n ucl e us

-

a ro u n d wh i ch a n e l e c tr o n r o t a te s Th e s ol e d i ffe r e n c e a s
.
,

c o mp a re d wi t h t he hyd r o ge n a to m t hus c o n s i s t s i n t he ,

d ou b l in ggof the nu c l ea i flch a rge z 2 The s e ri e s e m itt e d

, .
90 T HE Q U A NT U M T H E ORY

f rom th e p o s i ti v e h el i um a t o m m ay t h e r e fo r e ,
c din g
a c or to
be c omp r i s e d i n the f or mul a

v = 4N

wh e re N i s a ga i n the R yd ber g n umb e r a s d e fin ed i n If

w e h e r e s et s 3 n 4 5 6 , ,w e ge t t he s o c a ll e d
,
-

”
“
p r i n c ip a l s e r i e s o f hyd ro ge n wh i ch w a s ob s er v e d by
F owler 252 a n d v e r y r e c e n t ly m e a su r e d wi t h gr ea t c ar e by F .

P a schen 253 Fo r 3
. 4 n 5 6 7 ,
w e ge t t he s o c a ll e d
, ,
-

s e c on d s ub si d i ar y s er i e s of hydr o ge n wh ich w a s ob s e rv e d ,

b y P i cker i n g 254 a n d E va n s 255 B o t h s e r i e s w e r e b e fo r e the

.
,

a dv e n t o f B ohr s Th e o ry f a l se ly a s c r i b e d t o hyd r o g e n
’
.
,

A n e w a n d e x tr e m e ly n o t e w or t hy r e sul t o f B ohr s Th e o ry i s
’

r e v e a l e d i f w e a ll o w fo r t h e m ov e m e n t of t he n ucl e u s i n o u r
,

c a lcul a t i o n s F o r i n r e a l it y the n ucl e u s i s n ot s ta ti on a ry

.
, , ,

b u t n u c l e us a n d e l e ct r o n r e v o lv e a b o u t t h e i r c omm on c e n tr e
o f gr a vi t y B y t a ki n g t h i s f a c t i n t o a cc ou n t w e a r e l ed to
.

a s l i gh t ly a l t e r e d e x p r e s si o n fo r the R yd ber g c on s ta n t In .

pl a ce of ( 9 5) w e get t he f or mul a

in wh i ch M d e n ot e s t he m a ss of the n u c l e us It foll ows .

f r o m t h i s t h a t for di ffe re nt e l e m e n t s for i n st a n c e hydr o ge n , ,

a n d h e l i um t h e Ryd ber g c o n s t a n t d iffe r s s o m e wh a t a n d i s

,

s m a ll e r fo r hyd r o g e n t h a n for h e l i um
( s i n c e M H < M B ) In e .

ge n e r a l t he va lu e of the R ydber g c on st a n t i n c r e a s e s wi t h
,

i n cr e a s e of a t o m i c w ei gh t t e n d i n g t o wa r d s a l i m i t i n g v a lu e .

A ll t h i s i s i n p e r fe c t a gr e e m e n t w i t h t he r e s ul t s of m a n y
ye a r s of S p e c tr o s c op i c r e s e a r ch .

In t he s a m e w a y a s e m i s s i on a bsorp ti on ha s a qu a n t um ,

l i k e chara c t e r a c c or d i n g t o B ohr s m o d e l If l i gh t s a y o f
,
’
.
,

t h e fir s t B a lmer l i n e fa ll s up on a hydr o gen a t o m a ,

qu a n t um hv o f t h i s e x te rn a l H ra d i a t i o n i s u s e d t o r a i se
,

t h e e l e ct ro n i n to t he t h i r d qu a n t um o r b i t A n a m ou n t of .

e n e r gy t i s t ak e n fr o m t he e x t e r n a l r a di a ti on t ha t i s l i gh t
a , ,

fro m the l i n e H i s a bs or b e d a
. .
 ST R U C T U RE OF T HE P ER I O D I C SY STE M 91

§ 4 T he S tru ct ure
. of the P eri o d i c S y ste m

E v e n i n hi s e a r l i e s t p a p e r s B ohr e n d e a v o u r e d t o c on s t ruct
fo r t he h i ghe r e l e m e n t s a s w e ll ( Li , B e , B , C, i n c on
n e xi o n w i t h t h e P e r i od i c Sys te m , s u i ta bl e a to m i c m o d e l s

w it h s e v e r a l r i n gs o f e l e ctr o n s e a ch o c cup i e d by sev e r a l ,

e l e c t r on s i n wh i ch for ex a mpl e
, ,
t h e w e ll k n o wn o c t a v e s o f
,
-

t he s y st e m a r e r e p r oduc e d b y a re gul a r a r r a n g e m e n t o f t he
e x t e rn a l e l e c t r o n s wh i ch r e cu r s a t e v e r y e i gh t h e l e m e n t ,

wh i l e t h e n umb er o f the e l e c t ron s r e volvin g i n t he o ute r m os t

r i n g i s e qu a l t o t h e v a l e n cy o f t h e e l e m e n t i n qu e s t i o n .

W Ko se. s l m a r r i v e d a t a s i m i l a r s t r uc t u r e o f t h e a t oms a s

a r e s ul t o f a p r o fo u n d i n v e s t i ga ti o n o f t he f o r m a t i o n o f m o l e

cul e s fr o m a to m s Als o L Vega r d .

25
,
7 A S omm erfeld 258 a n d
.
,
.
,

R L a d en bu r g
.
259 h a v e c on s t r uc te d a n a l o go u s at o m i c m od e l s ,

p a r t i cul a r ly t a k in g in t o a c c o u n t the w e ll kn o wn u p a n d d o wn - - -

c u r v e o f a t o m i c v o lum e s a n d us i n g t h e m t o e x pl a i n o t h e r
,

p e r io d i c ally v a r y in g p r o p e r t i e s ( p a r a m a g n e t i sm i on i c c o l ou r) , .

T h e se c o n s i d e ra t i on s a l t h o ugh t he y a r e t en d i n g i n d i spu t a bly

,

a l on g t h e r i gh t l i n e s a s fa r a s t he g e n e r a l p r i n c i pl e s a r e co n

c e r n e d a r e n ot e t fir mly e s t a bl i s h e d i n d e t a i l
, y .

5 T he
.
Q u ant u m Hy p oth e s i s for S e v eral D e gree s of Fre ed om

Wh i l e the qu a n tum hyp ot h e s i s i n i ts m o st p r im iti v e for m

d e m on st ra te d in t hi s w a y it s i n n a t e p o w er by e n te ri n g the
fi e ld of a to m i c dyn a m i cs i t ha d i n d oi n g so gai n e d l ittl e a s
, , ,

far a s i t s o w n d e v e l o pm e n t w a s c o n c e r n e d B u t t he fr u it s o f .

B ohr s Th e o ry r i p e n e d m ore ra p i dly t h a n c o ul d h a v e b e e n

’

d i v i n e d A l r e a dy the y ea r 1 9 15 b r o ugh t a d e ci si ve d e v e l op
.

m e n t : a lm o s t s i mul ta n e ou sly P l a n ck a n d S ommerfeld i n d e ,

p e n den tly f ou n d t h e s olu ti on of a p robl e m t h a t had l o n g b ee n

a b u rn i n g qu es t io n n a mel y ,
the ex ten si on of the qu a n tu m
,

theor y to sev er a l d egr ees of fr eed o m S ommerfeld 26° re t a i n e d a .

c l o s e c o n n e x i o n wi t h B ohr s T h e or y i n a t t a c k i n g t he p r obl e m
’

Th e fir s t m a i n co n di t i on of t h i s t h e or y r e l a te d t o the ch oi c e
of a ll o w a bl e st a t ion a ry o rb it s a m on g a l l th ose m e ch a n i c ally
p oss ib l e A ccord i n g t o t h i s a s w e s a w o n ly t h o s e o rb its
.
, ,

w er e all owe d fo r wh i c h the m o m e nt of m o m e n tum (Imp u ls

momen t) p i s a wh o l e mul t i pl e o f E
l
i Thi s m a y a ls o be .

7?
92 T HE Q U A NT U M T HE ORY

ex pre sse d a c co r d i n g to ( 8 1 ) a n d ( 8 2) t hu s a m on g a l l m e ch a n
i c a l l y po ss ibl e p at hs o nly t h o s e a r e a ll o w abl e a n d s tat i on a r y
,

fo r wh i ch the p ha se i n tegr a l fulfils t he c on d i t i on

-

q u h ( )
9 8

In t h i s qu a n tu m cond i tion w e a r e t o r e pl a c e a cc or d i n g t o
h e g e n e ra l c o or d i n a t e q by th e a n gl e o f r o t a t i o n (t he
( )
8 2 t -

a z i mu t h ) , t h e i mpul s e p b y t he i mpul s e ( o r m o m e n tum )

“
(f
”
c or re sp o n d i n g to ct , n a m e ly , p , (the m om e nt of m o m e n t um ) .

Th e i n te gr a t i on i s t h e r eb y t o b e e xt en d e d o v e r th e wh ol e ra n ge
of v a lue s of th e v ar i abl e q,
t h a t i s ,
i n t he p r e s e n t c a s e fr o m ,

0 to
In t h e c a s e gin a l B ohr Th e ory whi c h c on s id e r s
of th e ori ,

o n ly c i r c ul a r or bit s t h e r e n a t u r a lly e x i st s o n ly a si ngl e

,

qu a n t um c o n d iti o n n a m e ly t h a t for t he c a s e q
, , (f
) sin c e ,

t h e a n gl e o f r ot a ti on qt i s th e o n ly va r i a bl e o f the p a t h .

Ma tte r s a r e o t h e r wi s e wh e n w e r e j e c t th e l i m i ta t i on t o
,

c i r cul ar or b it s a n d h e n c e t a k e Kep l er e ll ip se s i n to a cc ou nt
,
-
.

Th e n e ac h p oi n t of t h e p a t h i s d et e r m i n e d by t w o v ar i a bl e s ,

n a m e ly b y t he d i s ta n c e r of t h e e l e c tr o n fr o m t h e n ucl e u s
, ,

wh i ch i s at the f ocus of th e e ll i ps e a n d by t he a n gl e f) (the ,

c

a z i mu t h whi ch r m a k e s w i th a fix e d d ire c ti on (s a y w it h the

“

s tra i ght l i n e whi ch j oi n s the n ucl e u s to t he p e r i h el i on ) In

, .

t h i s c a s e w e a r e p r e s e n t e d wi t h a p r obl e m of tw o d e gr e e s of
fr e e d o m wi t h t w o ge n e r a l i s e d co ord i n at e s r a n d 98 ( p ol a r
,
-

c o o r d i n at e s e s i m p l e e x t e n s i o n of t h e qu a n t um hyp o
-

) T h .

t h esi s by S ommerfeld n ow c o n s i st s i n s e tt i n g up i n th i s c a s e
two qu a n tum c o n d i t i on s of t h e f or m o n e for t h e c o

o r d in a t e o S wh i ch a g ree s w i t h the s in gl e qu a n t um c on d it io n of
,

B ohr s Th e ory a n d a n e w o n e for t h e c o o r d in a te r s o t h at

’
-

, ,

t he s e l e c t i on of t h e s t a ti on a r y orb i t s i s h e r e d ete r m i n e d by
t he t wo foll ow i n g e qu a t ion s

d
p¢ ¢> 7671

'
u h

’
n an d n h e re wh ol e n umbe rs p ) a n d p ar e the i mpul ses
are , , r

( m o m e n t a
) c orr e s o n d i n
p g t o the co or d i n a t e s ( f a d r
n 361 The -
) .
 T HE Q U A N T U M HY ‘

P O T H ESIS 98
i n te gr a tion i n ( 1 00) i s t o b e t ak e n ov e r the full ra n ge o f
va lu e s of r , t h at is , f ro m the s m a ll e st va lu e r mi n ( p e rih el io n)
to t he gr e a t e st v a lu e r m a x ( a ph e l ion ) a n d b a c k to the s m a ll e s t
rw in ,
c a ll e d t he a z i mu th a l qu a n tum c o nd itio n n b e in g
( )
9 9 i s ,

t h e a z i mu th a l qu a n tum n umb e r ; ( 1 00) i s the ra d i a l qu a n tum

'
c on d ition n t he ra d ia l qu a n tum n umb er
,
.

In a c o rr e sp on d i n g m a n n e r t he e x t e n s ion m a y be c a r rie d
o u t for m o re t h a n t w o d e g ree s of f r e e d o m If t he sy s te m ha s .

f d e g re e s o f f re e d o m a n d i f i t i s t h e r e fo r e ch a ra c te r i s e d by
,

th e f g e n e ra l i se d c o or d i n a te s ql qz q3 -
a n d t he c or re
, ,

s on d in
p g i mpul se s
p l p g p3 t h en , t h e ,
“
a ll o w a bl e

m o ve m e n ts of the s ys te m a re l i m i te d by t he f q u a n tum
c on d ition s :
d
2 q2
u zh, pq f nj h ( 1 01 )
n1 , n2 nf a r e p osi tive wh ol e n umb e r s) .

In .
y o n e of the f ph a s e i n te gra l s the i n tegra tion is to
e ve r -

be p e r for m e d ov er the full r a n g e of v a lu e s of the co or d in a t e -

in qu e st ion .

A d i fficul t y wh i ch a r o se h e r e fr o m t he o u t se t w a s t he
, ,

qu e sti o n a s to w hich co or d i n a t e s ough t to b e ch ose n for the

-

a ppl i c a t i o n o f t h e qu a n t um r ul e o r wh e t h e r t he ch oi c e

i s i mm a t e r i a l In g e n e ra l w e m a y ch a r a c t e r i s e a s y s t e m o f
.
,

se v e r a l d e g r e e s of f r e e d o m by v a r i o u s t yp e s o f c o o r d i n a t e s ; -

fo r i n st a n c e w e m a y d e sc r i b e t h e Kep ler m o v e m e n t of t h e
,

e l e c t r o n e it h e r by p o l a r c o o r d i n a t e s r a n d r by C a r t e s i a n
-

a o ,

c o or d i n a t e s x a n d Th i s qu s t i o n i s t h e m o e u r g e n t
y e r
-
.
,

wh e n o n e c on s i ders t h a t the s e p ar a t e ph a s e -
in do

n ot r ea lly b e co m e con sta n ts fo r e v e r y ch oi c e of c o or d i n a te s -

a s i s r e qu ir e d by t h e qu a n t um r ul e P S Ep stei n 303 . .

a n d K S chwa r z schi l d 264 h a v e s olv e d

. i n d e p e n de n tly of o ne ,

a n o t h e r t h i s p r obl e m o f t he co rr e ct c h oi ce of co ordi n a te s
“ -

to a c e rt ai n e xt e n t In ci d e n ta lly a n i nt er e s ti n g a n d s u r
.
,

p r i s i n g r e l at i on of the qu a n t um r ul e s ( 1 01 ) to a l on g kn ow n -

t h eo r e m of cl a ss i ca l dy n a m i cs w a s r e v e a l e d whi c h h a d be e n ,

p r o p o u n d ed by Ja cobi a n d Ha mi l ton a n d had hi t h e rt o b e e n ,

succ e ssfully a ppl i e d in ce l e s tia l m e ch an i cs Fi n ally qu ite .

,

l a t e ly A E i nstei n fi65 by m o difyi n g the e x p re ss i o n

, . ha s
94 T HE Q U A NT UM T H EORY

p u t f o r w a r d a qu a n t um hyp ot h e s i s wh i c h h a s t he a dvan t a e
g
o f b e i n g i n d e p e n d e n t o f t he c h o i c e o f c o o r d i n a t e s Bu t a -
.

cl o se r d i s cus si on of t h e s e a bs tr a ct i n v e st i gat ion s would l e a d

u s t o o fa r h e r e .

The se c o n d f or m u l a t i o n of th e qu a n tum hypo t h e s i s fo r

s e v e r a l d e g r e e s of f r e e do m i s d u e a s a l r e a dy m e n t ion e d t o , ,

M P l a nc k 266 It i s a s i t w e r e m or e c a u ti o u s i n it s n a tu r e
. .
, ,

t h a n t he m or e r a d i c a l a tt a c k o f S om m erfeld P l a nck c o n .
,

t i n u i n g d i r e c t ly f r o m t h e d i vi s i o n o f t he ph as e pl a ne of l i n e ar -

o s c i ll a to r s a l r e a dy d i scus s e d st a r t s f r o m t h e s o c a ll e d G i bbs
,
-

ph a s e sp a c e to d e a l w i th m ore c o mpl i c a t e d sy s t e m s For a

-
.

syst e m o f f d e gr e e s o f f r e e d o m whi ch i s ch a ra c teri s e d by the ,

co o r d i n a t e s q g2 n d t h i mpuls s
qf a e e
pl p2 pf
-

l , , ,

t h e Gibbs ph a s e S p a c e i s t h a t 2f d i m e n s i on a l s p a c e t h e p o i n t s
-

o f wh i ch p o sse s s th e 2f c o or d i n a t e s q1 E a c h po in t
pf
-
.

o f t h e ph a s e sp a c e ( ph s p i s r e p re s e n t s h r e f o re
-
a e o n t ) -
t e a , ,

d e fi n i t e m o m e n ta ry s t a t e o f t h e s yste m i n qu e s ti o n P l a n ck .

n o w gi v e s t h i s ph a s e s p a c e i n e x a c t a n a l o gy to the ph a se
-

pl a n e a cel l u l a r s tr u c tu r e by b r i n g i n g i nto p r o m i n e n c e
, ,

c e rt a i n sp e c i a lly d i s ti n gu i sh e d b o u n d a r y s urf a c e s A t t he .

s a m e t i m e the s i z e o f t he c ell s i s p r op ort i o n a l t o hf The .

p oi n t s of i n t er s e c tion of t h o s e b o u n d a r y su r fa c e s t h e n r e p r e
s e n t t h e d i st in c t i v e qu a n t um s ta t es o r ph a s e s o f t he s y st e m
( h cc d g fi h y ly p i b l
’
t a t i s,
a o r i n t o P l a n c k s r s t t e or t h e o n o s s e ,

In c o n tr a st w i t h S ommerfel d s
” ’

t he a ll o w a bl e c o n d iti o n s) .

Th eor y i n wh i c h t he m o tio n o f a s ys t e m o f f d e gr e es o f
,

fr ee d o m i s a lwa ys d et e r m i n e d b y f qu a n t um c on d i ti on s i n ,
’
P l a n ck s u n d e r c e r t a i n c i r c um st a n c e s t he c a s e m a y o c c u r
, ,

t ha t f e w e r qu a n t um c o n di t i on s t h a n d e g r e e s o f f r e e d o m e x i s t ,

s o th a t s e ver a l ( c oh er e n t
“
d e g r e e s of fr ee do m a r e l i m i t e d
by a s i n gl e qu a n t um c on d i ti on .

S ommerfe ld T he ory Re la tiv i s ti c F i ne

’
§6 . s of -
s tr u ct u re

Th at t h e s e t h eori e s h a d f o u n d th e k e r n e l o f t h e m a t t e r w a s
s oon to b e sh o wn by a pplyi n g th e m to B ohr s a to m i c m o de l ’
.

A c c or d i n g to t h e m fr o m a m o n g a l l the m e ch a n i c a lly p oss ibl e

p a t hs wh i ch the e l e c t ro n c a n de sc r i b e a b o ut t he z f old
,
-

p o s it i v e ly ch a r g e d n ucl e u s t h e a ll o wa bl e s t a t i o n a r y p a t hs
, ,

mu st b e d e t er m i n e d by the t w o quan tum c on di ti on s ( 9 9 ) a n d

Th i s giv e s i n pl ace of the d i sc r e te qu a nti s e d c ir cl e s
, ,
 RE LA T I VISTIC F I NE -
ST R U C T U RE 95
of Bohr d i scr ete l y qu a n ti sed Kep ler ell ip ses a m on g wh i ch
, ,

a ls o t h e B ohr c i r cl e s a r e in clud e d , a s S p e c i a l c a s e s An d .

f u r t h er th e e ll i p se s a r e qu a n t um d e te r m i n e d , bo t h w ith r e
,
-

fer e n c e to t h e i r s i z e s (i e t o th ei r m a j o r a x e s) , a n d t o t h e ir
. .

for m ( i e th e r el a t ion of the a xe s to o n e a n ot h e r) , so th a t h e r e

. .

e ve r y o r b i t a s c o mp a re d wi t h B ohr , i s ch ara c t e ri s e d by tw o
,
'

q u a n tu m n u m be r s n a n d n 26 7 I n pl a c e of f o r mul a ( 9 3) fo r
.

t he hyd ro g e n t yp e of s e r i e s , w e ge t the g e n e ra l f or mul a 268

N2 ( 02 )
2
v 1

He r e ga in N the Ryd ber g c o n st a n t i s g i v en by

a , ,
or

m o re e x a ctly ( the m otion of t he n ucl e us b e in g tak e n i n to

’
a cc ou n t by s a n d s a r e t h e t w o qu a n t um n umb e r s
)
( a z i mu t h a l a n d r a d i al
) o f t h e fi n a l o r b i t o f t he e l e c t r o n ; n

a r e t he qu an t um n umb e r s o f i t s i n i tia l o r b i t Si n c e
’
and n .

a l so a s a r e s ul t o f t h i s m or e c o mpl e t e v i e w of S ommerfeld
, ,

t he n um b e r of a ll owa bl e o r b it s i s g r e at ly in c r e a s e d a s co m ,

p ar e d wit h t h os e a ri s in g fr o m B ohr s Th e or y (o wi n g t o t he ’

a dd i t io n of t he e ll i p s e s) the e l e c tron s h a v e a g r e a t m a n y
,

m ore p os s ib il itie s i n p a s sin g fro m o n e orb it t o a n ot h e r t h a t is , ,

t he ch a n c e s o f g e n era t in g S p e c tr a l l i n e s a r e mul t i pl i e d Bu t .

w e e a s ily r e c o g n i s e t he foll owi n g fa c t : if w e ch oo se a s th e

fi n al orbit of t he e l e c tron an y on e of t h os e orb i ts for whi ch ,
'
t he su m of t he qu a n t um n umb er s 3 s ha s a d e fi n i t e v a lu e ,
'
say 3 s 2 a n d a s i n i t i a l o rb i t a n y o n e o f t h o s e p a t h s
, , ,
' ’
for wh i ch n n ha s a d e fin it e v a lu e s a y u n 3 then , ,

a l l the d ifier en t tr a nsi ti on s of the electr on s fr om a n y o ne of

’

these i n i ti a l or b i ts to a n y one of these fi n a l or bi ts gen er a te

-

a l w a y s the sa me l i n e in t he c a s e of t he figu r e s a bo v e ch ose n

(
i t wil l b e t he fir st B a l mer l in e) ; fo r a c co r di n g t o ( 1 02 ) the
fr e qu e n cy of the l in e e mi t te d d e p e n d s o nly up on th e s u m
' '
3 s a n d t he su m n
, n a n d o n t h e o t h e r h a n d n ot o n t h e
,
' '
se p a ra t e v a lu e s of s s n n, It wo uld t hus a pp ea r a s if
, , .

n o t h i n g i s ga in e d phys i c a lly b
y S o m m er f e l d s e l a bo ra t i o n o f
’

t h e t h eo r y a s c o mp ar e d wi t h B ohr s o ri g in a l th e o ry H ow
’
.

e ve r ,a s B ohr had a l r e a dy po i n t e d ou t t he c a lcul a t i o n s a re ,

in co mpl e te in o n e i mpo rt a n t re s p e c t wh i c h b e c o m e of fu n da ,

m e nt a l i mpo rta n c e wh en con si ste n tly t ak e n in to a cco u n t ,

an d whi ch re p re se n t s t h e m ai n a ch i e v e m e n t of S omme rfeld s

’
96 T HE Q U A NT U M T H EORY

t h e or y of p e c t ra l l i n e s
s . N a m e ly , th e v el oc iti e s of the
l
e e c t ro n s , wh i ch a pp e a r i n th e se p r obl e ms ca n n ot , be con

sid er ed n egl igi bl y sma l l comp a r ed w i th the veloci ty l i ght

f o .

In t h i s c a s e h ow e ve r w e c a n n ot a s w e k n o w c a lcul at e b y
, , , ,

t he m e t h od s of cl a ss i c a l m e ch a n i cs wh i ch r e g a r ds th e m a s s ,

o f t he e l e c t r on a s c o n st a n t b u t mu st ta ke ou r s ta n d u on the
, p
theor y of r e l a ti vi ty a n d h e n c e t ak e i n to a cc ou n t t h e v a r i a ti on s
,

o f th e m a ss o f t h e e l e c t ron w i t h i t s s p e e d S om merfeld c o m .

p l e t e d t h e c a lcul a t i o n i n t h i s r e sp e c t Th e p a t hs o f t h e .

e l e c t r o n a n d t he n u c l e u s d i ffe r i n t h i s r e fi n e m e n t o f th e ,

t h e o ry f ro m th e o r d i n a ry Kep ler e ll i ps e i n t h a t th e p e r i h e l io n
,

o f t h e o rb i t a dv a n c e s i n t h e c o u r s e of t i m e a n d t h a t t h e p a t h ,

l os e s i ts cl ose d ch a r a ct e r Th i s ha s the e ffe c t t h at th e e n e rg y

.

o f t h e e l e c t r o n i n t h e s t a t io n a r y qu an t um ch os e n o rb it s — wh i ch -

h e r e a l s o a re d e t e r m in e d b y ( 9 9 ) a n d ( 1 00) — a r e n o l on ge r
s ol e l y d e p e n d e n t o n t h e su m of t h e qu a n t um n umb e r s a s i n

t h e c a s e of the n on r e l a t i vi s ti c Kep l er m ot i on b u t t h a t t he
-

,
'
qu a n tum n umb e r s n a n d n al so e n t e r s e p arate ly i nt o the , ,

e x p re s s io n fo r t h e e n e r gy O n ly a s a fi r st a pp ro x i m a t ion
.
,

t h e re for e i s wh e n the r e l a t i v i t y c orr e c t i o n i s n e gl e c t e d

, . .
,

will the f re qu e n cy v of the sp e ct ra l l i n e e m i tte d d e p e n d on

'
t he qu a n t um s um s s n a l on e a s ( 1 02 ) s h o ws
’
s and n , .

If w e t a ke i n to a cc ou n t the r e l a tiv i s t i c ch a n g e of m a ss of the

e l e c t r on on
, t h e o t h e r h a n d i w i ll a ls o d e p e n d o n t h e ,
f

i n d i vi du a l v a lu e s of s s n n 26 9 It fol lows ther efor e tha t

’ '
.
, , , , ,

the va r i ou s p ossibi l i ti es a bove con sid er ed of the gen er a ti on of a

, ,

d efin i te sp ectr a l l i n e tha t i s the p a ssa ge of a n electr on fr om

, ,
'
a n y on e o the i n i ti a l or bi ts s
f s co n s ta n t to a n y on e of the

fina l or bi ts n n
'
lon ger p r od u ce ex a ctl y the
con sta n t, n o

sa me l i ne, bu t gi ve r i se to sl i ghtl y d iffer en t l i n es , wh i c h how ,

e v e r o n a cc ou n t of t h e sm a ll n e ss of t h e r e l a t i v i t y e ffe ct , l i e
,

v e r y cl o se t o ge t h e r Th is i s S ommerfeld s ex pl a n ation of t he
.
’

fin e s t r uc t u r e of th e sp e c t r a l l i n e s i n th e c a s e of t h e hyd ro g e n
-

t yp e of s p e c t ra F or e x a mpl e , a c c or d i n g t o S ommerfeld , t he
.

fi r s t l i n e Of t he B a lmer s e r ie s (the r e d hydrogen l i n e H.) mus t

c on s i s t of fiv e c o mp o n e n t s , wh i ch a r e a rran ge d i n t w o ch ie f
g ro up s (of t w o a n d t h r e e e a ch) The m ean di sta n c e o f t h e se .

t w o g roups f r o m o n e a n o t h e r sh ould a m o u n t , a c cord i n g to the

t h e or y ,270 t o a b o u t O 126 A ; t he b e st m e a su r e m e n t s of t he
°

hyd rogen doub l e t ga v e th e va lu e 01 2 4 A (P a schen , Meissner ) °

.
 H I G H E R E LE M E N T S 97
If t hi s a gree m e n t a l re a dy s p e a k s st ro n gl y i n f a vou r o f S om mer
feld s Th e or y the e xa ct m e a su r e m e n t s by F P a sche n 27 1 of th e
’

, , .
,

fin e st r uct u r e o f t he l i n e s o f p o si t i ve h e l ium ( F ow l er s e r i e s ) h a v e
-

giv e n a s till m o r e c on vi n c i n g p r oof of i t s c o r r e c t n e ss a l mos t

w i thou t an ex cep ti on , a ll the comp on en ts
by the r e qu i r ed

theor y of the fin e s tr u c tu r e a p p ea r ed on the p ho togr ap hi c p l a te,

-

a n d thu s p r oved s tr i ki n gl y the ex i sten ce of the s ta ti on a r

y p hs
a t
of the el ec tr on a n d i ts r el a ti vi s tic cha n ge of m a ss .

T w o i n t e r e s ti n g c o n s e qu e n c es m a y y e t b e m e n t i o n e d h e r e
the y d i r e c tly c o n n e c te d w i th S ommerfel d s Th e o r y a n d
a re
’

P a schen s ob se r va t i o n s F i r s t o f a ll t h e y h a v e r e n d e r e d
’
.

p ossi bl e th e u s e o f the fin e str uc t u r e m ea s u r e m e n t s fo r a-

d i r e c t S p e c tr o sc op ic d e te r m i n a ti o n o f t he t h r e e fu n d a
“

m e n ta l co n st a n t s e m o ( m a ss o f t he e l e c tr o n a t i n fi n i t e ly l o w
,

sp e ed s
) a n d, h 27 2 S e c o.n dly K G l i tscher 273 w a s a b l e t o
,
.

S h o w t h a t w e o n ly fin d t h e s p e c t r os c o p i c o b s e r v a t i o n s fo r ,

e x a mpl e t h e s i z e o f t h e hyd r o g e n d o ubl e t i n a g r e e m e n t w i t h

, ,

t h e t h e o r y wh e n w e u se for t h e v a r i a t i o n i n t h e m a s s o f t he
,

e l e c t r o n t h e fo r mul a g i v e n by t h e t h e or y of r e l a t i v i t y On .

t he oth e r h a n d A br a ha m s Th eo r y o f t h e r i gi d e l e c tr o n l e a d s
’

t o fo r mul a whi ch d o n o t a g r e e w i t h e x p e r i m e n t .

§ 7 Hi gher E l e me nts
.

W e t hus s e e t h a t R u therfor d s a to m i c m o d e l a s fu rt h e r ’

d e ve l o p e d b y Bohr a n d S omm erfiel d fa r e x c e e d e d the e x

e t t i n s wh i c h i t c o uld r e a s o n a bly b e e x p e c t e d t o fulfil A t
p c a o .

an r a t e i t h a s r e v e a l e d t o u s the O p ti c a l s e r i e s o f hyd r o g e n
y ,

a n d h e l i u m w i t h u n d r e a m e d o i p r e c i s i o n a s fa r a s t he fi n est
-

d e ta ils Bu t b e yon d t h e s e p r i m a ry ga in s i t ha s u n de r ta k e n
.
,

a fu rt h e r s e r i e s of succ e s s ful a t t a c k s Thu s L a n d e 274 w a s .

s ucc e s s ful i n c a lcul a t i n g t he t w o se r i e s s y s t e m s o f n e u t r a l -

h e l i um ( h e l i um a n d p a rh e l i u m ) b y t a ki n g i n c o n t ra ,

d i st i n c t ion to B ohr a m o d e l o f t h e n e u t r a l h e l i um a t o m i n
,

whi c h t he t w o e l e c t ron s c i rc l e a r o u n d t he d o ubl e p o si t i v e

n u c l e u s i n t w o d i ffe r e n t o r b i t s e i t h e r co pl a n a r or e l s e
,
-

i n c l i n e d a t a n a n gl e t o o n e a n ot h e r In t h i s c a se t h e n t he .
,

e x t e r n a l e l e c t r o n t he l e a p s o f w h i c h g e n e r a t e t he r a d i a t i o n
, ,

m o v e s i n a fi eld i n wh i c h the s i mpl e Cou l om b La w n o l o n g e r

h old s o n a c co u n t o f the di stu rb i n g i n flu e n c e of t h e in n e r
,

e l e c t r on E xampl es of t hi s typ e wh i ch di ffe r f r o m t h a t o f

.
98 THE Q U A NT U M T H E ORY

hyd ro ge n h a v e b e e n g e n e r a lly i n v e sti ga t e d by S om m erfeld ,

w ho h a s S h o wn 27 5 t h a t b y g i vi n g up t h e Cou l om b fi e ld w e
a rr i v e t o a fi r s t a n d se c o n d a pp r o x i m a t i o n a t t he R y d ber g
, ,

a n d R i tz fo r m s o f t h e s e ri e s l a ws A v e ry p r o m i sin g
.

b e g in n in g i n se tt in g up a qu a n t um t h e o r y o f t he s p e c t r a l
l in e s w a s t hu s m a d e .

§ 8 T he S tark E ff ect the Z eema n E ffec t i n B oh r T h eo ry

’
. a nd s

o f th e A t o m

U n de r t h e c i r cum st a n c e s th e qu e st ion fo r c es i t se lf up on u s ,

wh et h e r t he a t o m i c m od e l i n i t s p r e se n t st at e of d e vel o pm e n t
i s a b l e t o a c c o u n t for t h e S ta r k e ff e c t t h a t i s t h e spl i tt in g up o f
, ,

t h e s p e c tr a l l in es a s a r e s ul t o f t h e a c t ion o f a n e x t e rn a l e l e c t r i c
fi e ld on the e l e c t r on s e m i t t in g the l in e s F or a s w e m a y.
,

r e m e m b e r , t h e o r i gi n a l Thomson m o d e l h ad co mpl e t e ly f a il e d

jus t a t t h i s p oin t A n d how d o m att e r s s t a n d a s r e ga r d s th e

.

Z eem a n e fiec t , pl it tin g up of sp e ct r a l l in e s a s a r e s ul t of

th e S

a n e x t e rn a l m a gn e t i c fi e ld ? Co uld t h e n e w m o d e l e x pl a in
t h e se ph e n o m e n a a s we ll a s t h e ol d ? B o t h qu e st i on s h a v e
fo r t u n at ely b ee n a n swe r ed i n t h e a ffir m a ti v e A s r e g a r d s the .

t k
S a r e ec t ff P S Eps in
,
. t
. e 27 5 i n a n i mp ort a n t p a pe r su c c e e d e d
, ,

in d e m on st r a t i n g t h e foll o win g : if w e c alcul a t e th e m o t io n of

t h e e l e c t r on u n d e r t h e i n flu e n c e of t h e n u c l e u s a n d t h e
e x t e r n a l fi e ld a c c or d i n g to t h e m e t h o d s usu a l i n ce l e st i a l
,

m e c h an i c s a n d t hen c hoose f r o m a m on g a ll m e c h a n i c a lly

,

p os sibl e m otio n s t he a ll owa bl e sta tion a ry orb i t s b y a pplyin g

t h e m od e r n qu a n t um r ul e s for s e ve r a l d e gr e e s o f f r e ed o m a n d ,

if t h i r dly w e a ll o w t he e l e c t r on t o l e a p f r o m o n e of t h e se
, ,

s t a t i on a r y p a t h s i n t o a n o t h er wh e r e by w e l i m i t t h e in fi n it e
( ”
n umb e r o f p os s ib l e p a ss a g es b p r i n c i pl e of se l e c t ion
“
y a

p r e se n tly t o b e di sc us s ed) t h e n t he Bohr fr e qu e n cy fo r mul a ( 9 2 )

,

gi ve s wit h th e m ost a dm ir a bl e a c c u r a cy a n d c o mpl et en e ss both ,

a s r e g a r d s p o s i t i o n a n d n umb e r a ll th e c o mp on e n t s o f t h e
,

r e s olv e d l in e s a s ob s e r v e d b S t a r k i n t h s e s o f hyd r og e n
y e c a

a n d p o s i t i v e h el i um Th i s a s t on i s h i n g r e s ul t mu st be r e
.

ga r d e d a s a fu rt h e r s tro n g supp ort of the c or r e c tn e ss of

B ohr s m o d e l a n d it s s ys t e m of qu a n t a The t h eo ry o f t he
’

e x pl an a t i o n o f t he Z eem a n e ff e c t h a s up t o the p r e s e n t n ot

b ee n qu it e so s ucce ssful It i t r e
s u
. t h a t D y e b e 277 and
 SE LECT IO N OF R U BIN O W ICZ A ND B O H R 99

So m m erfi e l d 27 8h a ve b een a bl e to d e ri v e the n or m a l Zeem a n

e ffe c t ( d i vi s io n o f t he o ri gi n a l l i n e i n to a t ri pl et wh e n t h e

l i n e of ob s e rv a tion i s p e rp e n d ic ul a r t o the l in e s of for c e) by

c a l c ul a t i on f r o m t h e m o d e l The e x pl a n a t ion h owe v e r of
.
, ,

t w o i mp ort a n t ph e n o m e n a i n t h i s fi e ld ha s n ot y e t b ee n
a c co mpl i sh e d : fi r stly th e a n o m a l ou s Z eema n e ffe c t a n d i t s
,

l a ws (Ra n ge P r es ton ru l e) a n d s e c on dl y the fa ct d i s c ove r e d

-

, , ,

by P a schen a n d B a ckjm t h a t e v e n i n th e c a s e o f l i n e s wi t h a
c o mpl i c a t e d fin e s t ru c tu r e th e n o r m a l t ri pl e t i s fo r m e d a s
-

t h e m a gn e t i c fi e ld gr o w s F u rt h e r in v est i g a t ion wi ll it m a y
.
,

be h o p e d u n r a ve l t h os e diffi cul tie s

,
.

§ 9 T he P ri nci p les
. of S e l ecti on of R u b i n ow i c z a nd B ohr

In a s much a s the for e goi n g c o n s i d e r a ti on s d e a l o n ly wi t h

t h e p os i tio n o f l i n e s i n t h e S p e ct r um i e w it h t h e i r fr equ enc y ,
. .
,

w e a r e s t ill c on fr o n t e d w i t h th e p r obl e m o f t h e i r f or m o f
vi b r a t io n i e t h e i r i n te n s i t y a n d p o l ari s a t i on Mor e ove r t he
, . . .
,

i mp o r t a n t qu e st i o n h a d y e t t o b e a n sw e r e d wh e t h e r a l l l e a ps ,

o f t he e l e c t r o n f r o m a n y o n e s t a t i o n a r y p a t h t o a n y o t h e r

a r e p o s s i bl e or wh e t h e r t h e n umb e r o f a ll o w a b l e t r a n s i t i o n s
,

“ ”
mu s t b e l i m it e d by s o m e p ri n c i pl e o f s e l e c ti on Th i s .

a l s o i s fu n d a m e n t a lly a qu e s t i o n of i n t e n s i t y fo r t h e po s it i o n
, , ,

m a y b e r e ga r d e d a s f oll o ws : the fo r b i dd e n t r a n siti o n s co rr e

sp o n d t o z e r o i n t e n s i t y The s o lu t i o n o f t h i s wh ol e c o mpl e x
.

of p r o bl e m s h a s b e e n g r e a t ly a dv a n c e d qu ite r e c e n t ly In .

the fi r st pl a c e A R u bi n ow i cz 28° by a pply i n g th e l a w of t he

, .
,

c o n s e r va t i o n o f th e m o m e n t o f m o m e n t um ( i m u l s m omen t
p ) -

t o t h e s y s te m a t o m r a d i a t e d w a v e ar r i v e d a t a p ri n c i pl e ,

o f s e l e c t i o n a n d a r ul e o f p ol a r i s a t i o n o f t he f o ll o w i n g f o r m

i n a t o m s of the hyd r o g e n t yp e wh i ch a r e r e m o v e d f ro m th e ,

i n flu e n c e o f e xt e r n a l fi e lds of f o r c e t h e a z i mu t h a l qu a n t um ,

n umb e r n o f t he e l e c t ro n [se e f or mul a c a n o n ly a l t e r by

0 ,
1 or
,
1 wh e n e m i ss i o n t a k e s pl a c e
, In t he fir s t c a s e .
,

the l igh t r a d i at e d i s l i n e a r ly p o l a ri s e d i n t h e t w o o t h e r ,

c a s e s c ir c ul a r ly The p o s i t i o n o f t h e pl a n e of t h e o rb i t
.

r e main s u n ch a n g e d du ri n g t he p ro c e ss of e m i ss i on In .

t h e c a se o f a t o m s d i ffe ri n g f r o m t h e hyd r o g e n t yp e a n d ,

of m o r e c o mpl i c a t e d s t r uc t u r e t h e po s i t i o n i s l e s s s i mpl e ;
,

if w e se t t he tota l m o m e n t of m o m e n t um of a ll t h e
m a s s e s for m i n g p ar t of the s y s t e m ( w e k n o w t ha t t hi s
 1 00 T HE Q U A NT U M T H EORY

i mpuls e re m a in s c on sta n t du ri n g th e m ot i on ) , e qu a l to a

*
wh ol e n umb e r n t1 m e s 1t 1s
j u s t t he c ha n ge s i n thi s
, ,
5 ,

*
n u m ber n du r i n g t he e m i s s i on wh i c h mu st b e l i m it e d by t h e
p ri n c i pl e o f s e le c t io n i n t h e s a m e m a n n e r a s i n t h e c a se , ,

a b o v e t h e a l t e r a t i o n s i n t h e a z i mu t h a l qu a n t um n umb e r o f
,

t h e i n d i v i du a l e l e c t r o n i n i t s l e a p s w e r e l i m i t e d H er e a l s o .
,

z er o ch a n g e i n th e a z i mu t h a l qu a n tum n umb e r gi v e s l i n e a r
pol ar i s a t i o n ch a n ge s b y i 1 o n t h e o t h e r h a n d l e a d t o
, , ,

c i r c ul a r p ol a r i s a t i o n In pl a c e of t h e o r b i t a l pl a n e w e ge t
.

the i n va r i a bl e pl a n e ( a t r i ght a n gl e s t o t h e t o t a l m o m e n t s
“

o f m o m e n t um o r i mpul se m o m e n t s ) t he p o si t i o n o f wh i ch i n
-

sp a c e r e m a i n s u n al t e r e d If fi n a lly t he a t o m i s e x p o se d to
.
, ,

a n e x t e r n a l fi e ld s a y a h o m o g e n e o u s e l e c t r i c fi e ld
, ( ark
S t
e ffe c t) o r a h o m o g e n eo u s m a gn e t i c fi e ld ( Zcem a n e ffe c t h
) t e n , ,

as w e k n o w o n ly t h a t c o mp on e n t o f t h e t ot a l t u r n i n g
,

i mpul se r e m a i n s c on st a n t du r i n g the m ot i o n o f t h e m a s s e s
f o r m i n g p a r t s of the a to m wh i c h i s p a r a ll e l t o th e e x t er n a l
l
fi eld . If we se t t h ese c mp o on e n t s of i mpuls e vi
l
i
—
t hr
en ,

on ly t he a l t er a t i o n o f th i s n u m b e r u 1 wi ll b e l i m i t e d by the
pr i n c ipl e of s e l e c ti o n (t h a t i s the a l t e ra t i o n s mu s t b e 01 i
,

The p r i n c i pl e o f sel e c t i o n i s t hu s c l e a r ly w e a k e n e d i n i t s
a c t i on b y t h e e x t e r n a l fi eld a n d c a n i f fi e ld s of ir r e gul a r
, ,

s t r e n gt h a n d d i r e c t i o n a c t o n th e a t o m b e c o m e c o mpl e t e ly ,

illu s o ry a s fo r e xa mpl e i n t he c a s e o f e l e c tr i c d i sch a r g e s

, , , .

B y m e a n s o f e n t i r e ly d i ffe r e n t co n s i d e r a t i o n s N B 0hr 281 , .

a r ri v e d a t r e s ul t s wh i ch c o i n c i d e i n e s s e n t i a l s w i t h t h o s e o f
, ,

R u bi now icz b u t e x c e e d t h e m gr e a tly i n r a n ge

,
B ohr s t a rt e d .

f ro m the f a c t t h a t i n t h e l i m i t for l a r g e qu a n tum n umb e rs ,

wh e n t h e s uc c e s siv e s t a t i o n a r y s t at e s of th e a t o m d i ffer v e r y
l i tt l e i n th e e n e r gy t h e y i n volve the fr e qu e n c y t h a t t he ,

e l e c t r on e m i t s i n i t s p a ss a g e b e t w e e n n e i gh b o u r i n g s t a t e s

b e c o m e s i d e n t i c a l wi t h t he r at e of r e volu t i on i n t h e s t a t i o n a r y
o r b i t ?82 The e l e c tr o n t h e r e f o r e e m i t s a cc or d i n g t o B ohr s
’
,

fr e qu e n cy c o n d it i o n t he s a m e l i n e t ha t i t s e n d s ou t a c c or d
,

i n g t o t he c l a s s i c a l t h eo ry o f e l e c t r o n s In o t h e r w or d s f or .
,

ver y hi gh qu a n tu m n u m ber s the qu a n tu m theor y p a sses over ,

“
( B h P ri n c i pl e o f Co rr e S o n
’

i n to the cl a ssica l theor y o r s .

p
d e n c e or Ar gu i n g fro m thi s p r i n c i pl e , B ohr p ro
 SE LE CT I O N OF R U BIN O W ICZ A N D B O H R 1 01

c eed s a s foll ows : a cc or d i n g t o c l as s ic a l m e ch a n i c s t he m o t io n ,

o f the e l e c t r o n i n B ohr s a t o m m a y b e r e p r e s e n t e d a s t he s up e r
’

p o s it i o n oi c o mp on e n t h a rm o n i c v i b r a t i o n s o f t h e f r e qu e n c y ;
i l l
7
2
01
2 wf ( 1 03 )
H e re 1 ,
7
f wh o l e n umb e r s wh i c h i n g e n e r a l m a
T are
y
h a v e a l l v a lu e s b e tw ee n co a n d co ; t he w
,
wf a r e

c e r ta i n c o n s ta n t s whi c h d e p e n d o n t he c h a r a ct e r of t he
m ot i on : f i s the n um be r of de g r e e s of f r e e d o m L e t t he .

a mpl i t ud e of t h e p a r ti a l v i b r a t i o n ch a r a c t e r i s e d b y t h e
n um b e r s 7 t o Tf b e A d T h e n a c c or d i n g t o c l a s s i c a l
1 ,

e l e c t r ody n a m i c s m i s t h e f r e qu e n c y o f t he r a d i a t e d p a r t i a l
,

w a v e (7 1 and A 3 f m a s u r e of i t s i n
T
f) 1
A f i s a e

t e n si t y O n t he o t h e r h a n d t h e f o ll o wi n g r es ul t i s d e r i v e d
.
,

fr o m the qu a n t um th eo r y (Bohr s fr e qu e n cy for mul a) for h i gh ’

qu a n t um n um b e r s : i n t he t ra n si t io n fr o m a n i n i ti a l st a t e
c h a r ac te r i se d by t he qu a n t um n um b e r s m m m i n to a
1 2 f ,

fi n a l st a t e c o r r e sp on di n g t o the qu a n t um n um b e r s n
a l i n e o f f r e qu e n cy

q ( 1
m -
n1 ) a
1
m
( 2 n2 <
1>
)
2
m
( f nf wf ) ( 1 04 )
is e m i t te d . H e r e t he
qu a n ti ti e s 1 f (0 (O a re t he sa m e

c o n sta n t s a s i n B u t a c c or d i n g t o B ohr P r i n c i pl e
’

, s of

A n a l o gy for h i gh qu a n t um n um b e r s m
, q . H e n ce t h er e
foll o ws fr o m a c o mp a r i s on of ( 1 03) w i t h ( 1 04 )

i . e . the “
cl a ssica l
p a r ti a l v ibr a ti on
( 7
1
T
f ) corr esp ond s to
tha t qu a n tu m tr a n si tion , i n w hi ch the u a n tu m n u m ber s a l ter
q
by ex a ctly 7 1 T
f T h e
p ol a r i sa ti on a n d
. i n ten si ty f
o the

w a ve emi tted
d u r i ng thi s qu a n tu m tr a nsi tion ma y be ca lcu l a ted
fr om the for m of vi br a tion a nd a mp li tu d e of the cor r esp ond i n g
“

”
c l a ssi ca l a t i l osci ll a ti on T h i s p r i n c i pl e wh i c h ha s be e n
p r a .

d e r ive d for h igh qu a n tum n umb e rs i s e x t r a p ol a t e d b y B ohr

wi t h gr e a t bo ld n e ss o ve r t he r e gi o n of a ll qu a n t um n um b e r s .

Thu s t he i mp ort a n t p r i n c i pl e of c o rr e s p o n d e n c e i s o b t a i n ed .

If i n t he d e v e l o pm e n t of t h e e l e c tr o n i c m o t i o n i n t e r m s o f
p a rt ia l v i b ra t i o n s t he te r m (7 1 , 7 2 5) i s m i s s i n g ,
t h e n
t he co rr e s p o n di n g tra n s i t i o n

"l l ”52 — 752

1 02 T HE Q U A NT U M T H EORY

is p r e s e n t H en c e t h e r e foll o ws fo r e x a mpl e for a to m s

n ot .
, ,

o f t h e h yd r o g e n t yp e i n a fi e ld f r e e f r o m f or c e t he l a w tha t ,

the a z i mu tha l qu a n tu m n u mber ca n i n a ll emi ssion s on l y cha nge

by 1 or 1 b ot h o f wh i ch l e a d t o c i r c ul a r ly p o l a r i s e d
,

r a d i a ti on Th i s l a w i s s o m e wh a t m o r e l i m i t e d i n f o r m t h a n
.

t h at o f R u bi now i cz .

B ot h t h e p ri n c i pl e s o f s el e c ti o n a n d t he r ul e s for th e
p ol a ri sation a n d the i n t e n s i t y h a v e stoo d t he t e st of c o mp a ri
son wi t h e x p e ri m e n t R u bi now i cz h i m se lf sh o we d t h a t hi s
.

p r i n c ipl e of sel e ct io n a n d th e r ul e of p ol a ri sation a r e in a gr e e

m e n t wi th P a schen s m e a s u r e m en t s of t h e fin e st r u c t u r e of
’
-

t h e h e l i um l i n es a n d fu rt h e r wi t h t h e ob se r va t i o n s of t h e
,

S ta r k e ffe c t a n d t h e n o r m al Z eem a n e ffe c t P S Ep s tei n 283 . . .

and H A Kr a mer s
. .
m we n t s t ill fu rt h e r a n d w e r e a bl e t o ,

p rov e b y p r ofo u n d in v e sti ga t ion s b a s e d on B ohr s Th eo ry th at

,
’

t h e c a l c u l a t i o n s o f i n t e n si t y a l on g t h e l in e s sk e t c h e d a bo v e
we r e a l so i n su r p r i sin g a g r e e m e n t wi t h ob ser v a t i on Fin a lly .
,

S omm erfe ld a n d Kossel 285 i n a n i n t e re st i n g s t udy h a v e a ppl i e d

t h e R u bi n ow i cz p ri n c i pl e o f s e l e c ti o n t o s p e c t r a d i ffe r i n g fr o m
th e hyd r og e n t yp e a s w e ll a n d h a v e s h own t h a t i t i s a b l e t o
,

e x pl a i n why c e rt a i n s e r i e s a pp e a r m o r e r e a d ily a n d a r e m o r e

f a v ou r e d t h a n o t h e r s a s i t w e r e a n d t h a t b y t h e s e l e c t i o n o f
, , ,

the p oss ibl e t ra n si ti on s i t s et s a l i m i t t o t h e mul t i pl i c it y

“
,

o f p o s s i bl e c o mb in a t i on s in a m a n n e r wh i ch so i t a pp e a r s , ,

e n t ir e ly a gr e e s wi t h e x p e r i e n c e .

§ ro. Col l isi on of Elec trons on the B as i s of the B o hr A tom

W h il e i n t h i s w a y , t h ro ugh t h e i n te rp r e t a t i o n a n d u n r a ve l l
i n g o f t h e u n i ve r s e a n d t h e a lm o st b e wil d e r i n g a bu n d a n c e o f
s p e c t r o s c o p i c o b se r v a t i o n s , t he c o n v i c t i o n o f t h e c o rr e c t n e ss

of B ohr m i c m od e l d e e p e n e d m o r e a n d m o r e a s e r i e s o f
’

s a to ,

o b s e r v a t i o n s o f qu i t e a n o t h e r k i n d b e c a m e k n o w n a n d c o n t r i

but e d c o n si d e r a bly t o t he c on sol i d at io n o f B ohr s Th e o ry ’

.

Th e se w e r e t he i n ve s t i g a t ion s a l r e a dy m e n t ion e d e a r l i e r i n
c o n n e x io n wi t h t h e l i gh t qu a n t um hyp ot h e s i s
-
whi c h d e a l t ,

wit h t he c oll i sion o f f r e e e l e c tr on s wi t h ga s m ol e c ul e s a n d

atom s . Th e se r e s e a r c h e s w e r e c o n du c t e d p a r t i c ul a r ly b y
J r a nck a d G Her tz a n d i n s u c c e ssio n by a c o n side ra bl e
F. n 286 .
, ,

n umb e r of A m e ri c a n i n v e st i g a t or s i n a s y st e m a t i c m a n n e r .

The m a n i f old r e s ul t s o f t h e se i n t e r e s t i n g r e se a r ch e s m a y b e
 CO LLI SI O N OF E LE C T RO N S 1 03

sk e t c h e d he re s c h e m a t i c a ll y b y a s im m e e x a m pl e Wh a t .

h a v e w e to ex p e c t wh e n e l e c t ro n s c oll i d e wi t h a B ohr Atom

A s a s i mpl e t yp e of B ohr a t o m l e t u s c h o o s e a m o d e l i n wh i c h
,

z e l e c tro n s r e volv e a ro u n d a z fold po s itive l y c h a rge d n u c l e u s

-

i n s ta t i o n a r y qu a n t u m p a t h s The n a t u r e a n d s p a t ia l a rr a n g e
.

m e n t o f t h e se p a t h s a s w e ll a s the d i strib ut ion of the

,

a m on g t he i n d i v i du a l p a t h s wi ll b e l e f t O p e n an d w e ,

FIG . 10
.

m ak e o nl y the si mpl ifyi n g a ss ump tio n tha t one elec tr on— t he

s o c a ll e d va l e n c y e l e c t r on — r evol ves a l one i n t he ou ter most
-

or bi t 1
( ) (see F ig
”
. Le t t h i s b e t h e n or m a l u n e x c it e d
“
,

s ta te o f t h e a to m .Th e h y d r og e n a to m (z 1 ) i s a s w e k now , ,

c on s t it u t e d i n t h i s w a
y a n d o f t h e n e u t r a l c o mpl i c at e d a to m s
, , ,

t he a t o m s o f t h e v a p o u r s of t he a l k a l i m et a l s Li N a K Rb
( , , , ,

a d di t io n of e n e r gy t he l c t ro n
e e is “
ra i se d fr o m it s n or m al
1 04 T HE Q U A NT U M T HEORY

or b i t ( )
1 t o a h igh e r
b it ( t h a t i s on e h a v in g m or e e n e r gy)
or , ,
”
a n d so f o rt h a n d i f i t f a ll s
s a y i n t o t h e or b it ( )
4 “
,

f r o m t h e s e b a c k i n to o rb i t t h e n t he 1 2 3 l i n e of th e
, ,

s o c a ll e d
-
A bsor p tion ser i es of the u n ex ci ted a tom
-

( p ri n c ip a l

s e m i tt e d h e f r e qu e n c i e s o f t h e l i n e s e m i tt e d a r e
s e ri e s
) i T .

r e gul a t e d by B ohr s f r e qu e n c y c on d i t i o n i e t h a t th e l o s s
’
. .

o f e n e r gy W nW1 i n cu r r e d i n p a s si n g fro m t he n th t o the

fi rs t o rb it i s e qu a l t o a qu a n tum hv 1 of t he l i ne e m itt e d : n,

( 1 03 )
Th e addi t ion a l e n e r gy r e qu i r e d t o r a i se th e e l e c t ro n t o t h e
“

h i gh e r e n er gy l ev e l c a n b e ob ta in e d i n tw o wa y s : fi r s tly by
a b s or p t io n of e x t e r n a l r a d i a t i o n se c o n dly a n d t h a t i s t he c a s e
(
w e a r e d e a l i n g wi th h e r e ) b y e l e c t r o n i c i mp a c t If e x t e r n a l .

r a d i a t i o n o f f r e qu e n cy V f a ll s up o n t h e a t o m a qu a n t um
al ,

hum o f t h i s r a d i a tio n i s a b so r b e d a n d i s u s e d t o r a i se th e
e l e c tr o n f ro m t he e n e r gy l e v e l W t o t h e h i gh e r l e v e l W 7,
1
W1 +7 hvm In f a ll i n g f r o m t h i s t o th e o ri gi n a l l e v e l th e
.
,

e l e c t r on t h e n e m i t s t h e l i gh t c o rr e s p o n d i n g to t h e l i n e a b s o rb e d .

Th e c i r c um st a n c e i s fu rt h e r n ot e wort hy t h a t t h e e l e c t r o n , ,

wh e n i t i s r a i s e d to the l e v e l ha s n o other choi ce t h a n t o

r e t u r n t o t he i n i ti a l l e v e l wh e r e a s f r o m o rb i t n m ak e
, ( )
4 i t c a

o n e of t h r e e po s s ib l e t r a n s i t i o n s — t o and If ,

t h e r e fo r e t h e a to m h a s a b so rb e d l i gh t c orr e sp on d i n g t o t h e
,

l i n e V2 I fr o m t he ex te r n a l ra di a t ion i t wi ll r e e m i t t h i s l i n e
, ,
-

wi th i t s full c o mpl e m en t of e n e r gy The fi r st l in e of the .

a b s o rp t ion s e r i es i s t h e r e for e i n c o n t r a s t w i t h a l l ot h e r l i n e s
, , ,

a s o c a ll e d r eson a n ce li n e
-

If the e n e r gy r e qu i r e d t o r a i s e t he e l e ctr on i s fu r n i sh e d by
t h e i mp a c t o f a n o u t s i d e e l e c t r o n t h e n — a s F r a n ck a n d H er tz
,

we r e t h e fi r st to p r ov e — th e i n t r udi n g for e ign e l e c t r on wi ll b e

r e fl e c t e d f r o m t h e a t o m p e r f e c t ly e l a s t i c a ll y a c c or d i n g t o t h e
(
m e c h a n i c a l l a w s of e l a st i c i mp a c t) a s l on g a s i t s e n e r gy ,

r e m a i n s b e l o w a c e r t a i n c r i t i ca l v a lu e E B If thi s e n e r gy .

va lu e i s r e a c h ed t he i mp in g in g el e c t r on l o s e s a ll i t s e n e r gy
, ,

a n d gi v e s i t up t o th e e l e c tr o n o f t h e a t o m wh i ch h a s b e e n

st r u ck
( i n e l a sti c
“
W h a t d o e s t h i s m e a n a c c or din g

t o B ohr s v i e w o f t h e a t o m ? O bv io u sly E R i s n ot h i n g o t h e r
’

th a n W s
a
W1 t h a t i s t h e e n e r gy wh i c h i s n e c e s s a r y to r a i s e
, ,

t h e e l e c tr o n f ro m i t s n or m a l sta t e i n t he a t o m to t he or b i t
 CO LLISI O N O F E LE CT RO N S 1 05

l
e ec t r on i c i mp a c t , wh i c h a dd s e n er gy of

m mu st t h e r e fo r e be t he e m i ssi on of
a to

the re so n a n c e l in e If t h i s vi e w r e p r e se n t s t he k e r n e l of the
.

m a t te r t h e n t he e n e r gy E R m u s t b e c on n ec t e d wi t h th e
,

f r e qu e n c y V2 1 o f t he r e so n a n c e l i n e by the qu a n t um re l at io n
,

E3 Il l /
2, 1 ( 1 07 )
Th i s l
r e a ti on s h ip c e ll e n tly v e r ifi e d by ex p e ri m e n t
h as be en ex .

Thu s Ta te a n d F oote 23 7 fo r e x a mpl e fin d in t h e c a s e o f , ,

so d i u m t ha t t he fi r s t i n el a s t i c e l e c t r o n i c i mp a c t t a k e s pl a c e
,

w h e n t h e i m p i n g i n g e l e c t r o n i s a c c e l e r a t e d b y a p ot e n t i a l
of V3 2 2 vo l t s t he so c a ll e d re so n a n c e p ot e n ti a l
,
-
T he .

e n e r gy c o m mu n i c a t e d b y t h i s p o t e n t i a l t o t h e i mp i n g in g
e l e c t r on i s

e VR x

3 00 3 x 10 2

O n t he o t h e r h a n d t h e r e so n a n c e ,
l in e that is u n de r c on

s i d e r a t i o n h e r e i s t he D l i n e h e n c e -

3 10 10

—
5 893
-

16 5

W e t hu s see t ha t t h e l i ( 1 07 ) i s fulfill e d wi t h g r e a t
r e at on

a cc ur a c y The s a m e h old s fo r p o t a s si um V v l
.
( B o t s ,

4
ER 24 7 10 2
, A2 1 7 68 5 huz1 10
In t h e c a se of ga se s (h e l i um n eo n e t c ) a n d the
t he i n e rt , ,
.

v a po ur s of m e r c u r y z i n c a n d c a dm i um s i m il a r qu a l i t a t i ve a n d
, ,

qu a n t i t a t i v el
e r a t i o n s — wit h so m e m od ific a t ion s— o c c u r Th e .

e x c i t a t i o n b y e l e c t r on i c i mp a c t o f t h e m e rc u r y r e s o n a n c e l i n e
, ,

1 2 5 36 1 0 5
t h at is d i s c o v e r e d b y F r a n ck a n d
-

H er tz an d a l r e a dy r e fe r r e d t o p r e se n t s a ch a r a c t e r i st i c
, ,

ex a mpl e .The ob se r ve d r e son a n c e p ot e n t i a l i s h e r e 4 9 vo l t s ,

whil e fr o m t he r e l a t ion

the va lue VR vol t s i s d e du c e d .

If t he e n er gy of t he i mp i n gin g e l e c t r on i s in c r e a se d be yon d
”
E R t he n a n
, in e l a s t i c i mp a c t a c co mp a n i e d by co mpl e te
“
,

l o s s of the e ner gy is to be e x p e c te d e ve r y t i m e a s so on a s E
,
1 06 T HE QU A NT UM T H EORY

ha s be com e qu a l to W e W1 ( n 3 4 5 7, B y t h e se , ,

va ri o u s a ddition s of e n e r gy t he e l e c tr on a tta c h e d to t he a to m
i s r a i s e d s u c c e s si v e l y t o t h e 3 r d 4 t h 5 th l e v e l of e n e r gy
, , .

If fi n a lly E E GO
, ,
WOO W1 t he n the e n e rgy of t h e ,

i mp i n gi n g e l e c t r on i s ju st s u ffic i e n t t o r e m ov e th e e l e c t r o n
a tt a c h e d t o t h e a t o m t o i n fi n i t y i e t o i on i se t h e a to m ,E CJO
. . .

i s t hu s t he i o n i s a t i on e n e r gy a n d th e vol t a g e c o r r e s p on d i n g
,

3 00 700
t o i t , Voo
5 is c a ll e d t he i oni sa tion p oten ti a l . F rom

the l
r e a t i on
( 1 06 ) w e ge t i mm e d i a t e ly t h e i mp o r t a n t e qu a tion
o VGO
ky m , 1
3 00

Tha t i s to sa y the i on i sa tion ener gy i s equ a l to the qu a n tu m

,

w hich cor r esp ond s to the l a st l i ne of the a bsor p ti on ser i es , tha t i s ,

to the “
ser i es li m i t . Thi s qu a n tum l
r e a t i on h as a sol be en
ex c e ll e n t ly fi r m e d i n a ll c a se s For so di um for e x a mpl e
c on .
, ,

Ta te a n d F oote fo u n d : Voo
. vol t s wh i c h gi ve s a n ,

i on i s at i o n e n e r gy o f t h e v a lu e E CJo On t h e
o t h e r h a n d t h e l i m i t o f t h e p r i n c i p a l se ri e s ha s t h e w a v e
,

l e n gt h Koo 1 2 413 fr o m wh i c h hvoo 1 10 4 2

,

i n st r ik i n g a gr e e m e n t wi t h t h e v a lu e of E co
F o r m e r c u r y v a p o u r t he l i m i t i n qu est i o n of the p r i n c i p a l
,

s er i e s A F r o m t h i s f o ll o w s a cc o r d i n g t o
GO ,

1 0 4 v ol t s wh i l e t he m e a su re m e n t s of v a r i ou s
wor k er s ga v e t he v a lu e 1 02 t o 1 03 vol t s ( Ta te B er gen , ,

D a vi s a n d Gau c her ; H u ghes a n d D i xon B i shop Fro m

a ll t h e s e e x a mpl e s wh i c h c o uld b e c on s i d e r abl m u l t i pl i e d
, y ,

t h e c on c lu si o n m a y b e d r a wn w i t h c o n vi n c i n g c l e a r n e s s t h a t
t h e B ohr c on c e p t i o n s h a v e l a i d b a r e t he n a t u r e o f t h e c on
s t r u c t ion a n d t h e m o de of a c t i on of the a to m wi t h u n
p r e c ede n t e d lu c i d i ty .

E ins te i n D e d u cti on P l a nck s L a w of Ra d ia ti o n the

’
of
’
§ 11 . s on
Ba s i s o f the B ohr A t o m

U n d e r t h e se c ir cum st a n c e s t h e s ugge stio n n a t u r a lly a ri s e s to

r e fo u n d t h e l a w o f bl a c k b o dy r a d i a t io n b t a k i n g a s t he el e
y
-

m e n t a ry ab so rb i n g a n d e m itti n g s tr u c t u r e B ohr s m od e l i n ’

pl a c e of the l i n e a r o sc ill ato r use d by P l a nc k E i n stei n 389 ha s .

t ak e n t hi s st e p . In a h i ghly i mp o r ta n t st udy b e i n ve sti g a t ed

 PLA N CK S LA
’
W OF R A D IA T IO N 1 07

t he e qu il i b r i um of en er m o m e n tum b e t we e n bl a c k b ody
gy and
-

ra d i a t i o n a n d a g e n e r a l i s e d B ohr m o d e l wh i c h s t r i pp e d o f a l l
, ,

s p e c i a l p ro p e rt i e s h a s o n ly t o fulfil t h e qu a n t u m c o n d i t i o n o f
,

b e i n g a b l e t o a s s um e a d i s c re te s e r i e s o f d i ffe r e n t s ta t e s For
.

h b w h
t e in t e ra c tio n e t e e n t e ra a t o a d i i n n d t h e a t o m — a b so r p t io n

m — n st e i n i n t ro
( E i n s tr a h l u n g) a n d e i ss i o n
( A u ss tra h l u n g) E i
du c e s t h e foll owin g s i m pl e hyp oth e se s : th e f re qu e n c y of t he
e m i ssi o n s i e t h e t r a n s i t i on s a c c o mp a n i e d b y l o ss o f e n e r gy
,
. .
, ,

o f t h e a to m f r o m a c o n d i t i o n h gh r e n e r gy E
( )
2 o f i e 2
,
t o ,

a c o n d it io n l w r e n e r gy sh a ll f o ll o w t h e s a m e
( )
1 o f o e E 1 , ,

s t a t i st i c a l l a w a s t h a t wh i c h g o v e r n s t h e d i s i n t e g r a t i o n o f

r a d i o a c t i v e bo d i e s i e t he n um b e r o f t r a n si t i o n s 2
,
. . 1 i n th e
t i m e d t o r a s w e m a y sa y the n umb er o f a to m s ( 2 ) t h a t
, , ,
d is
”
in t e g r a t e i n t h i s t i m e i s p r op o r tio n a l t o d t N 2 wh er e N , ,

d e n ote s t he n umb e r of a to m s m o m en t a r ily i n t h e s t a t e

B u t a c co r d i n g t o E i n stei n a d i ffer e n t l a w r e gul a t e s t he
, ,

p ro c e ss e s c a ll e d i n to e x i st e n c e by t h e e ffe ct o f e x t e r n a l r a d i
a tion . U n d e r th e i n flu e n c e of e x t e r n a l r a d i a t io n t w o t h i n g s
m a y h a pp e n : e it h e r a n a t o m m a y p a s s fro m sta t e ( 1 ) t o s t a t e
‘

( ) y
2 b
”
t a k in g up e n e r gy t h i s i s ,t h e p r o p e r p os i t i v e a b s o r
p
t ion . O r t he c a s e m a y a l so o c cu r t h a t a s a r e s ul t o f t h e
, ,

ph a se r e l a tio n b e t we e n th e fi e ld of t h e e xt e r n a l r a d ia tion a n d
-

t he a to m t h e a t o m l o se s e n e r gy t h r o ugh t h e a c t io n o f th e i m
,

p in gi n g ra di a tio n a n d h e n c e p a s se s f ro m st a t e ( 2 ) t o st a te ( 1 )
,

n e ga ti v e The ra t e a t whi c h b o t h k i n d s o f
t ra n s i tion a r e re p e a t e d i s t h e n p ro po r t ion a l t o t he i n t e n si t y
K o f th e e x t e r n a l r a d i a t ion t he n umb e r of t r a n si tion s 1
,
2
a s s o c i at e d w i t h p o s it i v e a b so rp t i o n i n t he t i m e d t i s t h e r e f o r e

p rop o rt ion a l t o N l d t K t h e n um b e r of t r a n si t io n s 2 1 a s
soc ia t e d wi t h n e g a t iv e a b s or p ti o n i s p r op o r t io n a l t o

H e re N 1 i s the n umb e r of a t o m s m o m e n t a ri ly i n t h e s t a t e
N 1 a n d N 2 a r e d e te r m i n e d b y t h e l a w s of d i st r ib u t io n k n o wn
f ro m the t h eory of ga se s a n d sta t i sti ca l m at he m a t ic s a n d e n
l a r ge d in c o n fo r m i t y wi t h t h e qu a n t um t h eo ry T h e r e foll ows
.

fro m t he e n e r gy e qu il ib r i um b e t we e n i n c o m i n g a n d o u t goi n g
- -

ra d i a t io n a t t h e t e mp e r a t u r e T
1 08 T HE Q U A NT U M T H EORY

wh e r e k i s Bol tzma n n s c on st a n t a n d A i s a c o n s t a nt i n d e
’

p en de n t oi th e t e mp e r at u r e F ro m Wi en s D i spl a c e m e n t Law
.
’

( )
4 i t f o ll o w s,
fi r s tl y t h a t A i s p r o p o r t i o n a l t o v a n d s e c o n dly
3

tha t E 2 E 1 i s p r o p o r ti o n a l t o v If t h e r e fo r e w e wr it e
.
, ,

E, E, ht ( 0)
1 1

we re o c gn i se i n t h is e x p r e s sion B ohr s f r e qu e n c y c on di tion

’

In t h i s w a y K a ss um e s t he fo r m o f P l a n ck s L a w o f Ra d i a
’

t i o n a r i s i n g i n a s u r p r i s i n gly s i m pl e a n d e l e g a n t m a n n e r f r o m
,

a m i n i mum o f hyp o t h e s e s o f a g e n e ra l c h a r a c t e r E i n stei n

.
,

i n pu r su i n g a n d d e e p e n i n g t h e s e c on c e p t i o n s by wr it in g d o wn
t h e e x p r e ss io n fo r th e e qu i l ib r i u m o f t h e m o m e n t a i n a dd i ti on
t o t h e e n e r g i e s o f t h e i n co m i n g a n d ou t g oi n g r a d i a t i o n w a s l e d
- -

t o t he r e m a r k a b l e c o n c lu si o n t h a t th e r a d i a ti o n o f B ohr a to ms
c a n n o t t a k e pl a c e i n S ph e r i c a l w a v e s a s t h e c l a s s i c a l t h e or y
,

of e l e c t r on s r e qu i r e s , bu t t h a t th e p r o c e ss o f e m i s sion mu st
h a v e a p a r t i cul a r d i r e c ti on l ik e th e sh ot fr o m a c an n on We .

c a n n o t f a i l t o r e c o g n i s e t h a t t h i s b ri n g s t h e c o n c e p ti o n t h a t

r a d i a t i o n h a s a qu a n t um l i k e st ru c t u r e l i gh qu n t um hyp o
-

( t a -

t h e s i s) w i t h i n r e a l i s a b l e b o u n d s .
 CH A P TE R V II

T he Q u a nt u m T h e o ry of R o nt g e n S p e ct r a

§ 1. T he A n a ly si s of R ent gen S p ec tra

A RA L LE L wi t h t he d e v e l opm e n t of the s c i e n c e o f O p t i c a l
s p e c t ra a t h eo ry of ROn t ge n S p e c t r a ha s b ee n d e v e l o p e d o f
,

l ate y e a r s up on th e s a m e b a s i s Th i s t h eor y ha s al r e a dy s h e d
.

mu c h l ight on t he s tru c tu r e o f a t o ms a n d t hu s fo r m s a
d e s ir a bl e ex te n s i on o f t he t h e ory of op ti c a l sp e c t r a Th e .

i n ve st i g a t i on s o f Ch B a r kl a W H a n d W L B r a gg Moseley
.
,
. . . .
,

and D a r w i n S i eg
,
b a h n a n d F r i m a n 29° a m o n g ot h e rs , ha v e ,

s h o w n t h a t by t h e i mp a c t of c a t h o d e ra y s up o n t h e a n t i

c at ho d e of a ROn t ge n t u b e t w o k i n d s o f ROn tge n r a ys a ri se

fi rs t t he so c all e d i mp a c t r a d i a tion (B r em ss tr a hlu n g) c on
,
-
“

s i s t i n g o f a n e x t e n s i v e a n d c on t i n u o u s r a n ge o f wa v e l e n gt h s f -

( s i m il a r t o t he c on t i n u o u s b a c k g r ou n d o f v i s ibl e s p e c t r a ;
)
s e c o n dl y t he
, c h a r a c t e r i s t i c r a d i a t io n a typ i ca l l i n e s ec tr u m
p
,
-

t h e st r u c t ur e of wh i c h d e p e n d s so e sse n t i a lly o n t h e m a t e ri a l
o f t h e a n t i c a t h od e t h a t a gl a n c e a t t h i s s p e c t r um su ffic e s us
-

to d e du c e i m m e d i a t e l y a n d u n m i s ta k a b ly t h e n a t u r e of t he
m a te ri a l of whi ch t he a n t i c a t h o d e i s c omp os e d Thu s a l on g
-
.

s i d e th e O p t i ca l S p e c t r um a n a ly s i s o i B u n sen a n d Ki r chhofi a
'

Ron t ge n o r X ra y a n a ly si s p r e s e n t s i t s e lf
-
It ha s fu rt h e r .

b e e n s h o wn t h at t he c ha ra c te r i sti c X ra y sp e c trum i s a -

el y a tom i c p r o er t n d i n d eed a n a ddi ti ve one If we

p u r
p y a , , , .

e x a m in e fo r e x a mpl e t h e X r a y S p e c t r u m
, ,
-
w hi ch i s e m itte d ,

by a n a n ti c a t h o de of b ra s s ( c o pp e r
-
z i n c ) w e fin d the ,

l i n e s of bo th copp e r a n d z i n c u n a l t e r e d a n d o ccupyi n g t he
sa m e po s i ti o n s a s if o n ly o n e m e t a l w e r e p r e se n t in t u r n N0 .

n e w l in e s a pp e a r A c c o rdi n gly w e a r e l ed to suppo s e th a t

.

t h e l i n e s p e c trum ar i s e s i n t h e a to m s o f th e a n t i c a t h od e a n d
- -

i s g e n era te d t h e r e b y t he i mp i n gi n g e l e c t r o n s o f t h e ca t h od e
1 09
1 10 T HE Q U A NT U M T H EORY

ra ys . Th e fu rt h e r i mpo rt a n t fa c t a pp e a r e d th a t t he l i n e s o f
t he ch a ra c t e ri s ti c S p e c t rum m a y be a rr a nged i n ser i es ju s t ,

l ik e t h o se of t he o p t i c a l s p e c tru m Thus w e h a v e di s c ov e r e d
.

up to t he p r e s e n t a s h o rt wa v e K—se ri e s a l o n g wa ve L s e ri e s
-

,
- -

a n d a s t i ll l o n g e r w a v e M—
-
s er ie s .

The m os t c u ri ous f e a t u r e of t h e s e S p e c tr a i s t h e i r c o n n ex ion ,

by a d e fi n i t e l a w w i t h t h e a to m i c n umb e r of t h e i r e l e m e n t i n
,

t h e p e r i odi c s y st e m If w e pl ot t he p osi ti o n of a c e r t a in l i n e
.

fi r st l i n e K e K— r t h e s u c c e ss i v e
( y
s a t h e o f t
,
h s e ri e s
) fo

e l e m e n t s o f t h e p e r io d i c s y s t e m a p e r f e c t ly r e gul a r ro r e s
, p g
s i v e s h i ft i s r e v e a l e d : t h e l i n e a dv a n c e s w i t h i n c r e a s i n g

a t o m i c n umb e r s t e a d i ly t o wa r ds t h e s h o r t e r w av e s Th e r e .

u l a r it y o f t h i s a dv a n c e i s s uch t h a t w e c a n r e c o g n i s e g a p s o r
g
fa l se p o sit ion s of e l e m en t s i n t he pe ri o d i c s yst e m i mm e di a t ely
by a n ex c e ssi v e jump N ow a cc or d in g t o t h e hyp ot h e si s
.
, ,

a l r e a d y m e n t i on e d o f R u therfor d
, v d B r ock a n d B ohr t h e
,
. .
, ,

a t o m i c n umb e r o f a n e l e m e n t i s n ot h in g o t h er t h a n t h e

n umb e r o f i t s n ucl e a r c h a r g e t h a t i s t h e n umbe r o f e l e m e n

, ,

t a r y p o si t iv e c h a r g e s o f i t s n u c l e u s If to t h i s w e a d d the
.

ph e n o m e n on ju st d i s c us se d a c c or d i n g t o whi c h the s t e a dy
,

a dv a n ce o f t h e n u c l e a r c h a r g e i n t h e se r i e s of t h e e l e m e n t s i s

r e fl e c t e d i n t h e s t e a dy d i spl a c e m e n t o f t h e X ra y l i n e s t h e n -

w e a r e for c e d t o t h e v i e w tha t the or i gi n of the X r a y sp ectra -

m u st be loca l i sed i n the i mmed i a te n ei ghbou r hood of the n u c l eu s ,

tha t i s i n the i nmost p a r t of the a tom

,
Fo r i n t h i s r e gi on t h e
.

n ucl e us cl ea r ly h a s t h e gre a t es t p o w e r a n d i s l e a st d i s t u r b e d

b y e x t e r n a l e l e ct r o n s a n d h e n c e i t i s h e r e t oo t h a t t he g r o wt h
, , ,

o f t h e n ucl e a r c h a r g e wi ll m a k e it s e lf m ost f e l t .

The c o n n ex io n b et w e e n th e p osit io n o f th e X r a y l i n e s a n d -

t he a t o m i c n um b e r 2 w a s fi r s t f o r mul a t e d by G M o se l ey
2 91 . .

H e f o u n d for t h e f r e qu e n c y of K ( fi r s t l i e of t e n
,
h K —se r i e s )

fi s l n e o f t he L s e r i e s t h e e mp i r i c a l r e l a t i o n
and L ,( r t i )
-

Ne

Ne
2
3

wh er e N i s t h e R y d ber g n um b e r .

Th e s i m i l ar i t y o f t h e s e r e l a t io n s , wh i ch ar e o n y a p p r o x i
,
l
 T H E A N A LY SIS O F R ONT G E N SPE CT R A 111

m a t e ly v a l i d wit h Bohr s f or mul a ( 9 3) fo r t he s eri e s o f t he

,
’

h y dro g e n t yp e i s so str ik i n g t h a t i t w a s a n ob vi ou s s te p t o
,

s e e k t o fin d t h e e x pl a n a t i o n o f t he Ren t g e n s e r i e s by a r gu i n g

o n t he b a s i s o f B ohr s m o d e l
’
.

T ih s p ro b l e m w a s a t t a c k e d ch i e fly by W K os sel 292 A .
, .

Somm er fe ld 293
,
L Vg
e a r d.
294 P D e b ye 29
,
5 J K r oc 296
. a n d A , .
,
.

Sme k a.l 297 A n d t hu s i n a dd i t i o n t o t he t h e o r y o f t he o p t i c a l

,

s p e c t ra wh i ch t ak e t h e i r o ri gi n a t t h e p e r i ph e r y of t h e a t o m ,

a t h e o r y o f t h e Ron t g e n s p e c t r a h a s a r i s e n wh i ch l e a d s us

FIG . 11 .

i n t o t he i n m o s t gi on s of t he a t o m A cco r d i n g to t h i s th e or y
re .

w e m a y p i c tur e to o u r se lves i n g e n e ra l t e r m s t h e e m i s s io n
, ,

o f t he Ron t g e n s p e c t r a a s f oll o w s : w e c o n s i d e r a n e u t ra l

B ob/r a to m c on s i s t i n g of a z f old n ucl e u s a r ou n d whi ch

,
-

z e l e c t r o n s r e v o lv e T h e s e 2 e l e c t r o n s m a y b e a rr a n g e d i n
.

di ffe re n t ri n gs Th e i n n e r m ost s i n gl e qua n tum r i n g t he so

.
,
-

c a ll e d K r i n g c a r r i e s l e t u s sa y P1 e l e c t r o n s in i t s n o r m a l
’

, , ,

s ta t e ; l e t t he s e c on d r i n g t he L ri n g b e a t w o qua n t um r i n g
,
-

,
-

o c c up i e d by 7 e l ec t r o n s t h e t h i rd t h r e e qu a n t um th e M ri n g
12
- -

, , ,

w i t h P3 e l e c t r on s a n d so o n (F i g
,
The qu e s t i on wh e the r.
1 12 T HE QU A NT U M T H E O RY

we c an r eac g oa l wi t h t h i s c o n c e p ti on of the r i n g by
h ou r

a s sum i n g t h e qu a n tum n um b e r s t o m c r e a s e a s w e o o u t w a r d s
g ,

a n d wh e t h e r w e a r e t o t a k e t he r i n g s a s co pl a n a r o r i n c l i n e d

t o o n e a n ot h e r w i ll b e l e ft o p e n The p r e p a r a t i o n fo r t he .

e m i s s i on of t h e K—s e r i e s c o n s i s t s i n t hi s t h a t b t h dd i t i
y e a on ,

o f e n e r gy — wh e th er by a b sor p ti o n of e x t e r n a l r a di a ti o n o r b y
e l e c t r o n i c i mp a c t — a n e l e c t r o n o f t he K r i n g 1 s r e m o v e d t o i n -

fin i t y t h a t 1 8 t he a t o m i s s o t o S p e a k i o n i s e d
, , , i n side i e ,
“
,
”
. .

i n th e K r i n g -
If t h e e n e r gy of t h e a t o m b e f o r e t h i s i n n e r
.

i on i s a t ion W0 a n d a ft e r t he i o n i sa t i o n
, WK th e n t h e ,

a m o u n t WK W0 o f e n e r gy mu st b e p r ov i d e d H e n c e e v e r y .

r a d i a t i o n t h e e n e r gy qu a n t um o f wh i c h s a t i s fi e s t h e c o n di t i o n
,

hv 2 WK W0 c a n o n b ei n g a b s orb e d e ffe c t t he t e ar i n g of th e
,

e l e c t r o n ou t o f t h e K r i n g If w e a ll o w t h e v o f t h e e x t e rn a l
-
.

r a d i a t i o n t o g r o w s l o wly f r o m s m a ll v a lu e s t h e n a t t he p o i n t , ,

M , a s udde n i n cr e a s e of t he a bso rp t i on oc cu r s ,

b e c a us e fr o m t h i s p o i n t o n w a r d s the e x te r n a l r a di a n t e n e r gy
i s u se d fo r th e i o n i s a t i o n o f th e K r i n g Thu s a n a bsorp
“ -

tion ba n d e x t e n d s f r o m V
-
V I; t o w a r d s h i gh e r f r e qu e n c i e s t he
,

e dg e o f t h e b a n d ly i n g a t V K Th i s ph e n o m e n o n o f th e e dg e
'

”
o f t h e a b sorp t i o n b a n d ha s a l r e a dy b e e n i n t e r p r e t e d a b o v e
-

i n th e se n s e o f the hyp o t h e s i s of l i gh t qu a n t a If t h e a dd i t i o n -

o f e n e r gy i s p r o vi d e d b y t h e i mp a c t o f a s tr a n g e e l ec t r on ,

c o m i n g f r o m wi t h o u t t h e n i t s e n er gy m u st b e E
, WK W0 ,

that i s E > t ,
a r e l a t i o n wh i c h w e h a v e a l r e a dy d e du c e d
, ,

e a r l i e r f r o m t h e s t a n dp o i n t o f t h e qu a n t um hyp o t h e s i s o f l i gh t .

B y i o n i s a t ion o f t he K r i n g t h e a t o m i s n o w p r e p a r e d fo r
-

K e m i ssi on
-
If n ow a n e l e c t r o n f a ll s f r o m t he 2 qu a n tum
.
-

L r i n g i n t o th e 1 qu a n t um K r i n g fill i n g up s o t o sp e a k t he
-
- -

, , ,

p r o duc e d t h e r e t h e n the fi r s t l i n e o f t h e K se r i e s K
g pa -

, , , ,

w i ll b e e m i tte d If o n the o t h er h a n d t he ga p i n t h e K r i n g
.
-

i s fill e d b y a n e l e c tr o n o f t h e 3 qu a n t um M ri n g o r t he - -

4 qu a n t um N —r i n g K,, o r Kr r e sul t r e s p e c t i v e ly
-

,
The p os i t io n .

i s qu it e a n a l o g o u s a s r e g a r d s t h e L a n d M s e r i e s If b y the -
.
,

a dd i ti o n o f e n e r gy ( a b so r p t i o n o r e l e c t r o n i mp a c t) a n e l e c t r o n -

o f t h e L r i n g i s b a tt e r e d 05 t h a t i s if t h e L r i n g i s i o n i s e d
-

,
-

t h e n t h e a t o m i s p r e p a r e d for th e e m i s si on o f t he L s e r i e s -
.

If n ow t he ga p i n t he 2 qu a n tum L ri n g i s fill e d b y a n
, ,
- -

e l e ct r on o f th e 3 qu a n t um M ri n g t h e fi r s t l i n e o f t h e L s e r i e s
- -

,
-

,
 FI N E ST R U C T U RE O F
-
R ONT G E N LI N E S 113
L , , sul t s ; if it i s fill e d by a n e l e c tr on of the N ri n g t he
re -

se c o n d l i n e o f t he L s e r i e s Ly r e s ul t s (t he n o ta t ion i s n ot
-

, ,

qu i t e c on s iste n t b u t w i ll s e rv e t he p r e se n t pu rp ose ) a n d so ,

fort h .

The c o n v e r se ph e n o m e n o n t o l i n e e m i s s i o n v i z l i n e a b sor p , .

t i o n w i t h wh i ch w e a r e a c qu a i n t e d i n vi s i bl e sp e c t r a a pp e a r s
, ,

a t fi r s t s i ght t o b e m i s s in g h e r e Th a t i s h o we v e r a s W .
, , .

Kosse l ” 3 r e ce n tly s howe d a n e rror It i s t ru e t h a t t he e j e c t e d , .

e l e c t ro n o f the K r i n g fo r e xa mpl e ca n n ot i n g e n e r a l b e
-

, ,

c a ught up o n the L M or N r i n g b e c a u se a l l pl a c e s o n t h e m -

a r e a l r e a dy o c c up i e d A n a b so r p t i o n o f t he l i n e s K K5 K,
.
, , , ,

i s t h e r e fo r e i n t h i s c a se i mp o s si bl e B u t th e e l e c t r o n o f t h e .

K ri n g c a n c e rt ain l y c o m e t o r e st on a n u noccu p i ed qu a n t um
-

or b i t o u t s i d e t he o c c up i e d r i n g s t h a t i s o u t s i d e t h e su r f a ce , ,
”
o f t he a t o m In t h i s p r o c e s s a l in e i s a c t u a ll y a b sorbe d “
.
,

n a m e ly t h a t l i n e of wh i c h t h e hv i s e qu a l to t h e e n e r gy
,

d i fie r e n c e b e t wee n t he K r in g a n d t h e fi n a l o rb i t o f t h e e j e c t e d
'
-

e l e c tro n Th i s r e fin e m e n t of ou r c on s i d e ra t i on s s h ow s t h en
.
, ,

t h a t t he e l e c t r on f ro m t h e K r in g doe s n o t n ee d to be ra i s ed -

i mm e d i a t e ly t o i n fi n i t y bu t t h a t l i n e a b so rp t i on s m a y o ccu r
,

b e fore t he e dge of t he b a n d of a b sor p t ion i s r ea che d .

§ 2 . T he F ine -
stru ct u re of Ro nt gen L in es

It i s p a rt i c ul a rly n ote wort hy t h a t Sommerfeld succ eed ed

a l s o i n t h e fi e ld of X ra y sp e c t r a i n e x pl a i n i n g t h e fin e -

s t ruc t u re of t he l i n e s b y c a ll in g i n t he a id of t h e t h e o ry o f

r e l a t i vi t y Thu s fo r e x a mpl e t he 2 qu a n t um L orb i t i s

.
, ,
- -

” ’
“
d o ubl e ; it c an o ccu r a s a c i r cl e (n U n 2 ) or a s a n ,

ll p ( H e n c e t h e l i n e wh i ch i s e m it t e d
’
e i s e 299 n 1 n ,

by the el e c t r o n o f wh i ch t he L r i n g i s the i n it i a l o rb it n a m e ly -

, ,

K i s a d ou b l e t ( K a n d
, ,
In ju s t th e s a m e w a y t h os e
, ,

l in e s for wh i c h t he L orb it i s the fi n a l orb it o f the e l ec t ro n

-

a r e d o u b l e t s n a m e ly t h e l in e L m o r e e x a c tl y wh i ch
, ( ,
t o ,

L 5 i s a dd e d t o m a k e a d oub l e t ; fu rt h e r Ly wh i c h f or m s ,

a d o u b l e t wi t h L a a n d so f or t h ,
Th e d i s t a n c e be t wee n t he .

co mp on en t s of t he do ubl et s (e x p re s s ed i n fre qu e n c ie s ) co m e s
o u t a c c ord i n g to S onmwrf eld s T h eo r y as a pp ro xi m a t e ly
’
ro
, p ,

po rt io n a l t o the fou rt h p owe r of th e a to m i c n um be r 2 H e n ce .

he r e in t he X ra y re gi on wh er e w e a r e d e a l in g for the m o st
,
-

p a rt wi t h e l e m e n t s h a vin g fa ir ly high a to m ic n umbe rs the ,

8
11 4 T HE Q U A NTU M T H EORY

do ub l e t s ppe ar m a c r os cop i c a lly e nl a r ge d as c omp a re d wi th

a

t he m i c r oscOp i c hyd ro g e n d o ubl e t (z D u r i n g t he e m i s

-

s i o n of X ra y s t h e e l e c t ro n a pp r oa c h e s v e r y n ea r t o t he
-

h i ghly ch a r ge d n u c l e u s a n d h en c e th e r e l ati vi sti c e ffe c t s of

-

th e r e solu t ion of the l i n e s a r e mu c h gr e a t e r t h a n i n t he c a se

o f th e o p ti c a l S p e c t ra in wh i ch t h e e l e c t r o n i s m o vi n g a t t h e
,

s u r f a c e o f t h e a t o m wh e r e it i s a lm o st e n t ir e ly sc r e e n e d f ro m
,

th e a c t i on of t he s t r on g n u c l e us b y t he r e m a i n i n g e l e c t r o n s .

Wi th t he h e lp of the foll ow i n g r e l ation d e duc ed t h e or eti c ally

a n d a d a p t e d t o e x p e r i m e n t a l e vi d e n c e ,

(z

S ommer eld f bl e t o c a lcul a te the hydrogen d oubl et fro m

w as a -

t he ob s e r ve d L d oub l e t s a n d c o mp a r e i t wi t h t he r e sul t s o f
-

e xp e ri m en t The a gre e m e n t i s v e ry s a t i sf a c t o ry
. .

T h e D i s tr i b u t i on o f E l ect r o ns a m ong t he Ri ngs O bj e cti ons

3. .

t o the Ring arra nge me nt of E l ec t rons -

The qu a n ti ta t i v e c alcul a tion of the S i mpl e st c a s e n a m ely , ,

t h e e m i s s i on o f K l e d D ebye t o t he co n clus i on t h at t he
, ,

K r i n g in th e n or m a l s t a t e c on si s t s of t hr ee e l e c tro n s
-
To .

t hi s Kroc b y e l ab o ra t i n g t he c a lcul a t ion

,
a dd s the c o n ,

c l u s io n t h a t t h e L r in g c on t a i n s i n i t s n or m a l st a t e n i n e
-

e l ec t r o n s Wit h t h e se tw o d is t rib u tion n umb ers P1

. 3 , ,

9 9 t h e p o si t i o n of K c ould b e r e p r e s e n t e d a s a fu n c t i on
12 , ,

o f t h e a t o m i c n umb e r 2 fo r a l l e l e m e n t s Th e e m i ssion of K .
,

t a k e s pl a c e a cc or d i n g t o t he foll ow in g obvi o u s s ch e m e

Ion i sa t ion of the K—rin g .

) E m i ss i on of
s t a te 3 l 8

The t w o d i str ibu t ion n umb er s ( B esetz u ngsz a hlen) thu s fou n d
for th e t w o i n n e r m os t ri n g s e x c it e ou r a tt e n tio n F or o n .

t h e b a s i s o f t h e P e r i od i c Sys t e m wi t h i t s p e r i od s of e igh t
we o ught to ex pe ct ,
a ccor din g to Kossel , the n umb e r s 2 and 8 .
 DI ST R I BU T I O N OF E LE CT RO N S 1 15

The s t ra n ge
cu rr e n c e o f t he n umb e r s 3 a n d 9 b e c o m es
oc

a n o bj e c t i o n wh e n w e c o n s i d e r t h e c a s e of s od i um
, (2

H e r e a cc or di n g t o Kossel w e sh o uld e x p e ct t he n umb e r s 2

, , ,

8 1 si n c e i n a l l p r o b a b il ity a n e l e c t ron ( t he v a l e n cy e l e c tro n )

, ,

r e v o lve s a l o n e a s i n t he c a se of a l l a l k a l i m e t a l s a r o u n d t he
, ,

o u t s i d e qu a n t um o r b i t M ri n g c s mp b l
( ) In a n
y a-
e i t i s i . o s s i e

t h a t t h e t w o i n n e r m ost r i n gs toge t h er S h o uld i n t he nor ma l ,

s ta te c o n t a i n 1 2
, 3 9 ) e l e c tr o n s If w e a t t e mpt t o go .

a s t e p fu r t h e r s t ill o n t he b a s i s o f Kr oo s n umb e r s 3 a n d 9
’

a n d t o s e t up a f or mul a w hi ch r e p r e s e n t s fo r a l l z s t he
’

po si ti on o f L i n c on for m i ty wit h o b se r v a tion a n d t h e r e b y

, ,

to d e t e r m i n e t he n umb e r o f e l e c tr o n s 103 o n t h e M r i n g w e -

fin d a s A Smeka l 300 sho w e d t h a t t hi s m o d e of r e p r e s e n t a ti o n

,
.
,

i s i mp o s s i bl e wi t h a n y c o mb i n a t i o n 3 9 p g N or d o w e fa r e , ,
.

b e tter if w e i n cl i n e t h e v a ri ous ri n gs t o o n e a n ot h e r a n d t a k e ,

t h e ir i n t e r a c ti o n i n to a cc o u n t Th e s u s p i ci on i s for c e d up on
.

us ,
t h a t p e r h a ps th e wh ol e c o n c e p ti o n o f t h e a r r a n ge m e n t
i n t o pl a n e r i n g s doe s n o t c o r r e sp o n d w i t h fa c t b u t th a t r a t h e r , , ,

t he e l e c tr o n s i n the a t o m f or m sp a ti a ll y s ymm e tri c a l figu r e s .

Thi s su s p i c i on i s v e ry mu c h s tr e n gt h e n e d by a s e ri e s of p r o
f ou n d i v e s g a t o s c a r ri e d o u t by M B or n a n d A L a nd e
n t i i n 80 1 . .
’

F oll owi n g o n M B or n s i n v e s ti g a t i on s of t he dyn a mi c s o f

’
.

t he c r y s ta l l a tt i c e wh i ch w e di s cu s s e d i n d e t a i l e a r l i e r i n
-

co n n e c ti on wit h t he a t o mi c h e a t of sol i d s the t w o in ,

v e sti ga to r s a s k e d t h e m se lv e s t he qu e s t i on wh e t h e r i t i s ,

po ss i bl e t o bu ild up t he cub i c c r yst a l l a t ti c e of the a l k a l in e -

h al id e s ( Na Cl N a B r N a I ; KCl KB r KI e tc ) fr o m i on s o f
, , , , ,
.

B ohr a to m s b y t a ki n g i n to a c c o u n t o n ly t h e mu t u a l e l e c tr o
‘

s t a t i c for c e s ; a n d wh e t h e r t h i s m e t h o d if po ss ibl e wo uld , ,

e n a b l e t h e m t o p r o ph e s y t h e c r y s t a l p r o p e rt i e s ( l a t t i c e c o n -

st a n t co mp r e ssibil ity) f r o m the a t o m i c m od e l s of t he t w o

,

co n sti tu e nt i on s The a n swe r t o t hi s qu e s ti o n ha s b e e n on

.
,

t h e wh ol e in t he a ffi r m a t i v e
, B u t wh e n t he c a l c ul a ti on of
.

t he co mp r e ss ibi l i t y of t h e se c r y st a l s w a s c a r ri ed o u t t h e ,

r e m a rk a b l e r e s ul t m a n i f e ste d i t se lf t h a t c r y sta l s a r e f ou n d t o

b e t oo s of t t h a t i s i n su ffi c i e n t ly ri gi d if t h e co n c e p t i on o f t he
, , ,

r in g a rra n g e m e n t o f e l e c t ro n s i n t h e a to m i s m a in ta i n e d
-
On .

t he o th e r h a n d w e ge t goo d a gr ee m e n t wi t h t h e ob se r v a t i o n s
,

if foll o wi n g B or n w e in t ro du c e t he hyp ot h e si s t h a t t he
, ,

e l e c t ro n s a r e a rr a n g ed spa tia ll y A c o mpl e x o f e i ght e l e c tr o n s

.
,
1 16 T HE QU A NTU M T H EORY

as o c c u r s in di um p ot a ssi um e t c d oe s n ot t h e r e for e occupy

so , ,
.
,

a pl a n e 8 r i n g ; t h e e i gh t e l e c t r o n s d e s c r i b e p a t h s of cu bi ca l
-

sy m m e tr y In to t h e still ob s c u r e r e gion of t h e se sp a t ia l
.

e l e c t r o n p a t hs A L a,
nd é
.
3°2 h a s m a d e so m e s ucc e s sful i n
c u r si o n s .

Fr o m al l th a t h a s b een sa i d it w ould a pp e a r to be c er ta i n
t h a t i n d ea l i n g w i th R on tgen sp ectr a , too, w e ca n no l onger be
con ten t w i th the a r r a n gemen t of the e l ec tron rin
i n p la n es,
gs

a n d t h a t t h e w h o l e qu a n t i t a t i v e t h e or y o f t h e Ron t g e n se r i e s ,

i n c lud i n g S ommerfel d s fin e s t r u c t u r e o f t he K a n d th e L
’
-

d o ub l e t s , mu st b e b u i l t up o n a f r e sh f ou n d a t ion .
 CH AP TE R VIII

P h e no m e n a of M o l e cu l ar M o d e l s

§ r . D is p e r s i on a nd M a gnet o -
r o ta ti on of th e H 2 M ol ec u le

H I LE t he X ra y Sp e c t ra a n d t h e s p e c t r a o f t h e O p t i c a l
-

s e r i e s a r i se f r o m t h e a tom s o f t h e e l e m e n t s ( a n d h e n c e

t h e ir t h e o r y l i n k s up w i t h t h e a tom i c m od el s) t h e r e i s a se ri e s ,

o f ph e n o m e n a wh i c h i n t h e c a se o f po ly a t o m i c s u b s t a n c e s
, ,

a r e p e c ul i a r t o t h e m o l e c ul e s a n d t h e t h e o r y of wh i c h
, ,

t h e r e fo r e i s fo u n d e d o n t h e m o l e cul a r m od e l s
,
Ch i e f a m o n g .

t h e s e a r e t h e n or m a l d i sp e r s i o n t he r o t a t i o n o f t h e pl a n e o f
,

p ol a r i sa t i o n i n t he m a g n e t ic fi e ld ( m a g n e to r ot a t ion ) a n d -

, ,

fu r t h e r th e g re a t a n d c o mpl ic a t e d s u bj e c t of ba nd sp ectr a
,
-
.

U p t ill a fe w y e a r s a go d i sp e r sio n a n d m a gn e to r o t a t io n h a d
,
-

b e e n e x clu si v e ly t r e a t e d f r o m t h e s t a n dp oi n t o f t he Tho m son

m od e l t h a t i s w i t h t he h elp of qu a s i e l a st i c ally b ou n d
, ,
-

e l e c tr o n s an d
,
t h i s e x pl a n a t i o n h a d s e r v e d i n t u r n a s a
p o we r ful s upp ort fo r t h i s m o d e l N e v e r t h e l e ss d i sc r e p a n c i e s
.
,

i n t h e se t h e or i e s h a d l on g be e n k n o wn F o r e x a mpl e .
,

m e as u r e m e n t s c a lcul a t e d up o n t he b a s i s of t he d i sp e r s i on
t h eo r i e s o f D r u d e Voi gt o r P l a nc k l e d t o v a lu es fo r t he r a t i o
, ,

of th e ch a r g e t o t he mass
p a r i son wi th t h e d ire c t m e a su r e m e n t s
of th e e e
( h )qu
l c t r on i
me
h i ch ,
in c om

a n t i ty ( b a se d
of t i s

upon t he de fl e c tio n of t h e c a t ho d e o r B r a y s in the e l e c t ri c -

a n d m a g n e t i c fi e ld s
) wh i c h w e r e m u ch too sm a ll W h e n .
,

h ow e v e r t he Thom son m o d e l b e ca m e d i spl a c ed by t he

,

R u therfor d B ohr m od e l a n d t he s ucc e ss e s o f t he B ohr a t o m i c

-

m od e l i n c r e a se d a t a n u n d r e a m e d of r a t e t he qu e s tion a r o s e
-

wh et he r a n u n obj e c t i on abl e t h eo r y o f di s p e rs i o n a n d m a gn e t o
ro t a t i on c ould n o t b e fo u n d e d up on t h e se n e w v i e w s Th e .

difli c u l t po si tio n i n to wh i c h w e a r e b ro ugh t by t h i s p robl e m

, ,

1 17
118 T HE Q UA NT U M T H EORY

a r i se s fr o m the f a c t t ha t w e d o n ot a c tu a lly k n ow a S i n gl e
i n sta n c e o f the e xa c t m a n n e r i n wh i c h a p olya t o m i c B ohr
m ol e c ul e i s b u il t up fr o m i t s n ucl ei a n d e l e c tro n s The .

e xa c t k n o wl e dg e o f t h i s s t r uc t u r e a n d t he m o t i on o f a l l t h e
,

e l e c t r o n s i s a b s o lu t e ly n e c e ss a r y i f w e d e si r e t o k n o w h o w
,

t he mo l e c ul e r e a c t s up on e x t e r n a l w a v e s ( d i sp e r si o n ) It i s .

t r u e t h a t W Kossel 3°3 h a s i n a d e t a i l e d s t udy a l r e a dy

,

r e f e rr e d t o a b ov e p o i n t e d ou t t h e g e n e r a l gu i d i n g l i n e s a l o n g
,

wh i ch f ro m t he ch e m ic a l p oi n t o f V i e w t h e bu ildi n g u p of
, ,
-

t he a t o m f r o m m ol e cul e s mu s t b e c a r r i e d ou t b u t t h e d e t a i ls ,

o f t h i s c o n st r u c t i o n r e m a i n o p e n O n l y i n a fe w o f t h e
.

s i mpl e s t c a s e s h a v e d e t a i l e d m ol e cul a r p i c t u r e s b e e n c o n

s t r uc t e d a n d c l o s e ly t e s t e d Thu s B ohr a s w e r e m a r k e d i n
.
,

d i s c u ssi n g the a t o m i c h e a t of g a s e s h a s a l r e a dy p r o p os e d a
,

m o d e l of t he d i a t o m i c h y d r oge n m ol e c ul e It ha s t he f oll ow .

i n g c on s t r uc t i on ( see F i g t w o si n gl y p o si t i v e n ucl e i ( t h a t
.
-

i s e a c h c o n si s t i n g of o n ly a s in gl e p os i t i v e ch a r g e ) a r e
,

s e p a r a t e d b y th e d i s t a n c e 2 b In t h e v e r t i c a l pl a n e wh i c h
.

b i s e c t s t h e l i n e j o i n i n g t h e n u c l e i t w o e l e c t r o n s r ot a t e
, ,

d i a m e tr a lly o pp o si t e o n e a n ot h e r o n a c i r c l e of d i a m e t e r 2a
,

~
.

Th e e qu il ib r i u m o f t he Co ul o mb a n d t h e c e n t r ifug a l fo r c e s
r e qu i r e s t h a t a b /3 B y m e a n s of t h i s r e l a t i o n a n d by t h e
.
,

qu a n tum c on d i t io n t h a t e a ch e l e c t r on mu st h a ve the m o m e n t
of m o m e n tum 11 ,
the m od e l is co mpl e te ly d e t e r m i n e d in all
2 71
“

i ts d i m e n sio n s a n d S p e e ds It w a s t h i s m o de l wh ic h w a s
.

th e fi r st t o b e p r op o s e d : i t w a s e x a m i n e d by P D eby e 304 .

wi t h r e fe r e n c e t o i t s d i sp e r si on On a c c ou n t o f i t s sym
f
.

m e t r i c a l s tr uc t u r e the m ol e c ul e p o s s e s se s n o e l e c t r i c a l m o
m e n t i n it s n or m a l s t a t e If o n t he ot h e r h an d i t i s s tr u ck
.
, ,

by a n e x te r n a l l i ght w a v e the m otion of i t s e l e c t r o n s i s

,

p e r i od i c a lly d i s t u r b e d ; t h e y d e p a r t f ro m t h e n or m a l qu a n tum
p a t h f a ll i n to fo r c e d vib r a t i on a n d t hus g e n e r a t e a n e l e ct ri c
, ,

m o m e n t wh i c h ch a n ge s p e rio d i c a lly i n s t e p wi t h the e x t ern a l

wa v e Thu s t h e or i gi n a l m ot io n of t h e p r i m a r y w a v e i s
.

c h a n g e d a n d d i s p e r s i o n r e s ul t s
,
We m a y c on c e i ve t h i s a s
.

fol l o Ws : L e t c b e t he v el oc i t y o f t he p r i m ar y w a v e i n va cu o r
.

Th e o s c ill a t i o n s o f t he e l e c t r o n s g e n e r a t e a s e c o n d ar y w a v e
whi c h S pr e a d s o u t f ro m t h e m ol e c ul e s A ll t h e s e s e c on d a r y .

wa ve s c o m bi n e wi t h the p r i m a ry wa v e t o a fo r m n e w wa v e
 T O BO H R S MOD EL
’
O BJEC T I O N S 119

wh i ch m ov e s wi th th e a l te r e d v e l o c it y q t he v a lu e o f whi c h ,

d e p e n d s o n the f re qu e n c y o f the p r i m a r y w a v e B u t ju st .

t h i s i s t h e ph e n o m e n o n o f d i s p e r s io n Th e e l e c t r on i c vi b r a .

t i o n s wh i c h o ccu r h e r e a r e n o t o s c ill a t i o n s a b o u t p o s i t i on s o f
e qu i l i b r i um a s i n t he ca s e o f t h e qu a s i e l a s t i c m o d e l
, bu t -

o sc ill a t i on s a bo u t s ta ti on a r y p a ths Mor eov e r h e r e the for c e .

, ,

h old i n g t he e l e c tro n s a s O pp ose d t o t he u su a l c l a s s i c a l

,

t h e o r i e s o f d i s p e r sio n i s a n i sotr op i c ( t h a t i s t h e e l ec t ro n i s
, ,

h eld b y d i fle r e n t f or ce s i n d iffe r e n t di r e c ti on s) ; a bove a l l by ,

mea n s of this a n i sotr op y i t w a s p ossi bl e to exp l a i n a w a y the

,

d i sa gr eemen t i n the va l u e o f i , w hich ha d p r evio u sl y been

fou n d to be too sma l l ; an d D ebye s uc c e e d e d , on t he b a si s of

t he n or m a l v a lu e of i ,
in d e duc in g f ro m t he t h eo r y t he

o b se rv e d d i sp e r si on c u r v e of hyd ro g e n t h a t i s t he c u rv e
, , ,

wh i c h s h ows ho w i t s c oeffi c i e n t o f r e fra ct io n d e p e n d s o n the

wa v e l e n gt h
-
It S h o uld be n o t e d t h a t i n t he fo r mul a fo r t he
.

c o e fii c i e n t o f r e f r a c t i o n n o s i n gl e c o n s t a n t i s a r bi t r a r y b u t
‘
, ,

th a t t h e d i s p e r s i on for mul a i s m a d e up e n t i r e ly o f u n i ve r sa l
c o n st a n t s .

Usi n g t h e sa m e m e t h o d ( c a lculu s o f d i s t u r b a n ce s ) P ,
.

S cherrer 3°5 h a s c a l c ul a t e d t he r o t a t i o n o f th e pl a n e o f
po l a ri sa t io n wh i c h l i n e a r ly p ol a r i se d l i gh t u n d e r goe s i n i t s
p a ss a ge t h r ough hyd roge n u n d e r th e i n flu e n c e o f a m a gn e t i c
fi e ld H i s e ffo r t s w e r e e qu a lly s u c c e s s ful
. .

§2 . O bj ecti ons t o B oh r
’
s M od e l of th e H y d r o g e n M ol ec u l e

In p i te of t he s ucc e sses wh i c h the B ohr m o d e l o f t h e

s

hyd r oge n m ol e cul e ha s w o n a l i s t of w e i gh t y O bj e c t i o n s t o

,

i t ha s a c cumul a t e d i n th e c o u r s e o f t i m e Th a t t h e c on .

t r i b u t i o n wh i c h t h e r ot a ti o n ( m o r e a c cu ra t e l y t h e r e gul a r ,

pr e ce s s io n ) o f t h i s m o l e c ul e m a k e s t o t h e m o l e cul a r h e a t a t
l o w t e mp e ra t ur e s d oe s n o t c orr e s p o n d wi t h t h e o b s e rv a t io n s
,

o f E uc ken h a s b e e n s h o w n b y P S Ep s tei n a s w e h a ve
, . .
,

a l re a dy m e n ti o n e d A l s o a t h i gh t e mp e r a t u r e s wh e n t h e
.
,

o s c ill a t i o n s o f t h e t w o n ucl e i r e l a t i v e ly t o o n e a n o t h e r co n

t r i bu t e to t he m o l e c ul a r h e a t n o a gr e e m e n t be t w e e n t h e o r y
,

a n d o b se r v a t i o n h a s b e e n fo u n d i n t h e c a s e o f t he B ohr m od e l ,

a s G La s ki 30° r e c e n t ly s h o w ed
. .
1 20 T HE Q U A NT U M T H E O RY

F u rt h e r , t h e m o de l mu s t p o s s e ss i n c o n s e qu e n c e of t he ,

r e v o lv i n g e l e c t r on s a n a lm o s t fi x e d m a g n e t i c m o m e n t p a r a ll e l
,

t o t h e a x i s of t h e n u c l e us t h a t i s t o s a y i t mu s t be e qu i v a l e n t
, ,

t o a m o l e cul a r e l e m e n t a r y m a g n e t wh i c h e n d ea v ou r s t o s e t ,

i t se lf i n a n e x t e r n a l m a g n e t i c fi eld p a r a ll e l t o t h e l i n e s
, ,

of f or c e H ydr o g e n ough t t h e r e fo r e to b e p ara m a g n e t i c

.
, , ,

wh e r e a s i t i s d i a m a gn et i c .

A n o t h e r v e r y i mp ort a n t ob j e c t i o n to wh i ch N er n st i n ,

p a r t i cul a r d r e w a t t e n t io n i s t he foll o wi n g : i f w e c a l c ul a t e ,

t h e w o r k wh i c h i s n e c e s s a r y t o s e p a r a t e t he m ol e cul e i n t o
i t s t w o a t o m s t h e S O c a ll e d hea t of d i ssoc i a ti on w e ge t 307 t h e
,
-

v a lu e ,
c a l o ri e s On t he o t h e r h a n d L angmu i r 308 f ou n d
.
,

c a l s Isna r di 3°9
.
,
c al s J F r a nck P Kn ipp i ng .
, .
,
.

a n d Thea Kr uger ( 0 0 c l c a s e t he
3 1 0 i 5 7 ) a s In an
y .
,

c a lcul a t e d h e a t of d i s s o c i a t io n c o m e s ou t 2 5 p er c e n t t oo .

s m a ll 3 10 .
3

F a lly W
i n ,
L en s 3 1 1 h a s r e c e n t l y i n cr ea s e d t h e ob j e c t i o n s
.

t o t h e h yd ro ge n m o d e l b y a n i mp o rt a n t on e b a se d o n a
t h e o r y o f b a n d sp e c t r a wh i ch w e S h a ll d i s cu ss b e l o w
-

,
He .

p r o v e d t h a t t he b a n d l i n e s o f h y d r o g e n a n d n i t r og e n c a n
-

e x h i b i t t h e o b s e r v e d Ze em a n e ffe c t on l y if these m ol ecu l es ,

p o sses s n o mom en t of m om en t u m a r ou n d t he n u c l ea r a x i s
‘
.

Th e f a c t th a t t h e t w o e l e c tr o n s i n B ohr s m ol e c ul a r m o d e l
’

r e v o lv e i n t h e s a m e s e n s e h o we v e r e n d o w s i t w i t h ju s t s u c h
, ,

a m o m e n t o f m o m e n t um On the w hole the B ohr mod el d oes

.
,

not seem to cor r esp on d to r ea l i ty t h e a r r a n g e m e n t o f t he t w o

n ucl e i a n d e l e c t r o n s mu s t pl a i n ly b e qu i t e d i ffe r e n t NO .

s a t i sf a c tory m o d e l ho we v er ha s y e t b e e n fou n d
, , .

§ 3 M od e l s
. of Hi ghe r M ol ec ul e s

Ma tt e r s a re nob e t t e r i n t he c a s e of m o d e l s o f t he m or e
c o mpl i c a te d m o l e c ul e s It i s t r u e t h a t S omm er eld 31 2 a n d
. f
F P a u er
.
3 13 h ave a sol wo r k e d
d i sp er s i on ou t t he t h e o ri es of

a n d m a g n e t o r o t a t i o n i n t h e c a se o f t he m o r e ge n e r a l B ohr
-

m od el s ( N 2 a n d 02 ) wh ic h a r e c o n s t ru c t e d o n t he l in e s of t h e
hydr o ge n m o de l A c c o r di n g to S ommerfel d fo ur e l e c t r o n s
.
,

r e v o lv e a b o u t t h e l i n e j o i n i n g t he t w o n u c l e i i n t h e ca s e o f

O x y ge n e a ch o f wh i c h a c t s w i t h a n e ff e c t i v e c h a r g e
, 2c ; i n
t h e c a s e o f n i t r o g e n a r i n g o f S i x e l e c t r o n s r ot a t e s a b o u t t h e
,

nu cl e a r ax i s wh i l e the n ucl e i c a rr y t r i l e e ffe ct i v e ch ar ge s

, p .
 Q U A NT U M T H EORY O F BA N D SPE CT R A -
12 1

f
S omm er el d w a s a bl e t o o b ta i n a gr e e m e n t w i t h O b se rv a t i o n o n ly
b y s e t t i n g up fo r ea ch e l e ct r o n of a va l e n cy r i n g of its e l e c tr o n s -

t h e u n a cc ou n t a b ly s t ra n g e qu a n t um c o n d i t i o n m o m e n t of
h
m om e n t um n ,
u n d oub te dl y a m o st u n s a t i sfa c t ory
ul d L ki 1 4 O b t a i n e d b e tt e r r e sul t s w i t h so m e
res t G .er a a s 3

wh a t d i ffe r e n t m o de l s whi ch Sh e c h o se i n su c h a w a y t h a t
,

t he S p e c i fi c h e a t o f t he t w o g a s e s a t h i gh t e mp e r a t u r e s a g r e e d
w i t h t h e o b s e rv a t i o n s o f P i er 3 1 5 A c c o r d i n g t o h e r i de a s t he
.
,

n i t r o ge n m o l e c ul e mu s t c on s i s t of t w o se v e n fo ld p o s i t i v e n ucl e i -

e a ch o f wh i c h i s c l os e ly s u r r o u n d e d b y a l qu a n t um r i n g o f -

t w o ( o r t h r e e ) e l e ct r o n s Th e v a l e n c y r i n g i n t he c e n t r a l
.

ve rt i c a l pl a n e i s 2 qu a n t um a n d c o n t a i n s t e n (or e igh t)
-

e l e ct ro n s A n a l o go u sly the o x yge n m o l e cul e c o n s i st s of t w o

.
,

e i gh t f o ld p o s i t i v e n ucl e i e a c h e n c i r cl e d by a 1 qu a n t um r i n g
-

,
-

o f t w o ( o r t h r e e ) e l e c t ro n s wh e r e a s t h e 2 qu a n t um v a l e n cy
,
-

r i n g c o n t a i n s t we lv e ( o r t e n ) e l e c t r o n s The s a m e o bj e c t i o n s
.

a pply t o so m e e x t e n t t o t h e se m o d e l s o f S om m erfel d a n d L a ski

a s t o t h e hyd r o g e n m o d e l Fo r e xa mpl e t h e y g i v e n o a cco u n t

.
,

o f w h y o x yg e n s h ould b e p a r a m a g n e t i c a n d n i t r o g e n o n t he , ,

o th er h a n d d i a m a g n e t i c Mo r e o v e r t h e a b o v e m e n t i o n e d
, .
,
-

o bj e c t i on o f L en z a ppl i e s i n full f or c e t o t h e se m o d e l s ; fo r

t h e y a ll p o s s e ss m o m e n t s o f m o m e n t um a r ou n d the n u c l e a r
a x is. In c o n c lus i on w e f e e l b o u n d t o a dm i t t h a t t he e x a c t
,

c o n sti t u t io n o f e ve n the s i mpl e st m o de l s i s a t p r e se n t u n kn o w n

to us .

§4 . T he Q u an tu m T he ory of Ba nd -
s pe ct r a

To clud e t h i s c h a p te r w e s ha ll t u r n o u r a tt e n t i o n t o t he
c on ,

ba n d sp ectr a a n d c o ll e c t t o ge t h e r S h o r tly wh a t t he qu a n t um
-

t h e o r y h a s b e e n a bl e t o a s s e rt a b ou t t h e m up t o t h e p r e se n t
t im e . Th a t t h e y be l o n g t o m o l e c ul e s a n d c o mp ou n d s m a y
n o wa d a y s b e r e g a r d e d a s c e rt a i n The fi r st a tt e mp t t o co n.

s t ru c t a l o gi c a l qu a n t um t h eo r y o f b a n d S pe c t r a w a s u n d e r -

t a k e n b y K S chw a r z schi ld 3 16 w h o c l e a r ly r e c o gn i se d t h e
.

i mpo rt a n c e o f t h e r o t a t i o n o f t he m o l e c ul e i n t he p r o du c t i o n
o f t h e s e S p ec t r a H i s c o n c e p t io n s m a y b e d e fin e d a s foll o w s
. _

a s y s te m o f e l e ct r o n s r e v o lve s a t a d e fi n i t e qu a n t um d i s t a n c e

a r o u n d a m o l e cul e wh i ch i t s e lf r o t a t e s a c c o r d i n g t o qu a n t um

co n di t io n s t he a ssump t ion b e i n g m a d e fo r t he sa ke of
,
1 22 T HE Q U A NT U M T H E O RY

Simpl i c it y t h at t he m ot i o n o f t he e l e c t ro n s i s n ot i n flu e n c e d
by t he m oti on of t he m o l e c ul e If E 0 i s the qu a n t um e n e r gy .

of t he e l e c tr o n s E t h e qu a n t i s e d r ot a ti o n a l e n e r gy o f t he
, ,

m ol e c ul e t h e n E 0 E
, E i s t h e t ot a l e n e r gy of t h e s y s t e m
, .

If t he t hr e e c h i e f m o m e n t s o f i n e r t i a of t he m ol e cul e J a re
e qu a l t o o n e a n o t h e r t h e n i t f o ll o w s ju s t a s i n
, t h at ,

2
n 2
h
8 71 J
- 2

wh e r e n d e n ote s t he r o t a ti on a l qu a n t um n umb e r . Th e r e f or e
2
n h ?
E E0

If ,
n ow , th e
yst e m p a s s e s f ro m on e qu a n tum st a t e h a v i n g
s

t he e l e c tr on i c en e r gy E 0 a n d t h e r ot at i on a l qu a n t um n umb e r
n i n t o a n o t h e r qu a n t um s t a t e h a v i n g t h e e l e c t r on i c e n e r gy E
'

0
a n d th e r o t a t i o n a l qu a n t u m n umb e r n t h e n i t f oll o w s f ro m
’

,
’
B ohr s f r e qu e n c y fo r mul a ( 9 2 ) t h a t t h e f r e qu en c y of t he l i n e
r a di a t e d i s g iven b
y
'
EO E 0
'

(
2
n )h
— 2
n
V
h a ar ( 1 14 ) f

If w e k ee p q ua n t um n um b e r s wh i ch o ccu r h e r e ex c e p t
a ll t he ,

i n g n c on s t a n t a n d a ll o w n t o vary t h en w e ge t a s e r i e s o f
, , ,

l in e s p rogr e ssin g t o wa r d s t he viol et a n d h av in g the fr e qu e n c ie s

v a bn 2
( a an d b a re c o n st a n t s ) ( 1 1 5 )
Th i s i s for mul a wh i c h ha d a l r e a dy b een gi v en e mp ir i c a lly
a

b y D esl a nd r es 3 17 a n d wh i c h i s a pp r ox i m a t e ly t ru e for th e l in e s
,

of m a n y b a n ds .

F oll owi n g Schwa r zschi ld T H eu r l i nger 3 18 a n d W L enz 319 , . .

,

i n p a r t i cul a r h a v e fu r t h e r d e v el op e d a n d r e fi n e d t he qu a n t um
,

t h e o r y o f b a n d sp e c t r a Fo r e xa mpl e L en z h a s p i c t u re d t he
-
.
,

m ol ec ul e a s a symm e t ri c a l t op h a vi n g t w o m o m e n t s of in ert ia
a n d a r o t a t i on a l r i gi d i t y m m e n t of m o m e n t um ) a r o u n d th e
( o

ax i s o f t he figu r e a n d h e n c e d e a l s f r o m t h e o u t s e t w i t h a re gul a r
,

p r e c e ssion of th e m ol e c ul e i n pl a c e of a r ot a t i on U sin g .

B ohr s f r e qu e n c y fo r mul a a n d a ppl y in g t he p r i n c ipl e s of

’

se l e c t i o n h e Ob t a i n e d t h e fo ll owi n g g e n e r a l f or mul a fo r t he
,

l in e s of a b a n d
v a bn cu
2
( a, b, c ar e c on s t a n t s ) ( 1 16 )
 Q U A N T U M T HEORY O F BA N D SP E CTR A -
1 28

whi c h i s o be yed a c co r din g t o H eu r li nger in t he c a se o f the

, ,

so c a ll e d
-
c y a n o ge n l in e s o f n it ro ge n for ex a mpl e In , .

a dd i t i o n t o t h e l i n e s gi v e n b y L en z s Th e o ry r e qu ir e s the
’

o ccu rr e n c e o f t h e se ri e s gi v e n b y t he fo r m ul a

v
(
a
g
) 071
2
( 1 1 7 )
fo r t he c a se tha t the mo lecu l e r ea ll y p ossesses a fi n i te momen t
of momen tu m a bou t i ts a xis o wh fi
i
f gc h f o ll o w s
u r e . A s e ri e s

t h i s l a w d o e s no t h o w e v e r e x i s t i n t h e cya n o g en b a n d s a o
, , ,

c o r d i n g t o H eu r l i n ger L en z d e duc e s fr o m t h i s t h e c on c lu s io n
.

a l r ea d y m e n t io n e d t h a t t he n i t r o ge n m o d e l d o e s n o t p o s se s s
,

a r o ta t io n a l ri gi d i t y a bo u t it s a x is B y c a l c ul a t in g t he .

Z eem a n e ffe c t s of th e b a n d l in es a n d c o mp a r in g th e m wi t h ,

o b s e r v a t ion L en z w a s a bl e t o c o n fi r m t h i s a n d t o e x t e n d i t to
, ,

t he hyd r o g e n m ol e c ul e .

Th e i n fr a r e d Bj err u m a b so rp t i on b a n d s of t h e d i a to m i c a n d
-

p olya t o m i c ga s c o mp o u n d s wh i ch w e ha d di s cu ss e d a t l e n gt h
,

i n Ch a p te r V b e l on g t o t h e g e n e r a l t yp e o f b a n d S p ec t r a
,
If -
.

w e a r e t o d e du c e t h e m f r o m a t h e o r y c on si st e n t ly fou n d e d on
qu a n t a — a n d n ot a s w e d id e a r l i e r h alf a c c o r d in g to t h e
, ,

qu a n t um h a lf a cc o r din g t o th e c l a ss i c a l t h e or y— w e mu s t
,

foll o w c l os ely the c ou r s e pu r s u e d a bo ve wit h t he d iffe r en c e ,

t h a t i n pl a c e o f t he e n e r gy of th e e l e ct r on i c s y s t e m t h ere w ill
,

a pp e a r t h e en er y of the a toms 320 wi t h wh i c h t h e r o t a t i on a l

g ,

e n e r gy of t h e m ol e cul e i s c o m b in e d a s a fi r s t a pp r oxi m a t i o n , ,

a dd i t i v e ly Th e l o gi ca l c a r r y i n g o u t o f t h i s ca l c ul a t io n ( in
.

whi ch B ohr s fr equ en c y fo r mul a a n d t he p r in c i pl e of c orr e

’

S p on d e n c e a r e a ppl i e d ) wh i c h w a s u n d e rt a k e n by H eu r l i n ger 321

,
”
a n d t he a u t h o r 322 gi ve s for t he stru c tu re of t he flu t e d a h
,
“

so rp t i on ba n d s a n a r ra n ge m en t of l in e s wh i ch a t fi r s t S ight
doe s n ot a pp e a r to a gree wi th t he b e a utiful a n d e xa c t m e a sur e
m e n t s o f Imesfif é The t h eory gi v e s for t he p o s it ion of the
a b s o r p t i o n l i n e s a f o r mul a

= ,
O i ( 8)
1 1

a nd t h e r e fo r e
qu ir e s t h at a ll n e i ghbo u r in g l in e s b e eq u i
re

d i sta n t in c lud in g th e tw o i n the mid d l e (n

,
O n t he o t he r
h a n d Imes ob se r va t i on s s h o w wi t h in dub it a bl e c l ea rn e s s t h a t
’

t he i n te rv a l b e tw ee n t he t w o m i ddl e l i n e s i s tw i ce a s gre a t a s
12 4 THE Q U A NT U M T H E O RY

t h e i n te r v a l b e t w e e n a ll n ei ghbo u r i n g l i n e s . Th i s a pp a r en t
c on t r ad ic t ion i s e x pl a i n e d a s A Kr a tzer r e c en tly
, .
m‘I S h o we d ,

i n a s u r p r i si n g f a s hi on if w e t a k e i n t o a c c ou n t th e i n tensi ty
,

o f t h e a b sor p t i on l i n e s a c c o r d i n g t o B ohr s P r i n c i pl e of A n a l o gy
’
.

Fo r i t t h e n a pp e a r s t h a t t h e fi r s t a b sorp t i o n l in e t o the ri gh t
o f t h e m i ddl e vo l i n e n a m e ly t h e l i n e
-

, ,

h
V = V +
0
8a

( wh i ch i s d e r i v e d f r o m f or mul a
( 1 1 8 ) y b se t t i ng n O and

u sin g t he p o s iti ve S i gn fo r th e s ec on d t e r m ) i s o f va n i shi n gl y

sma l l i n ten si ty Th i s l i n e i s g e n e r a t e d wh e n t h e m ol e c ul e
.

p a s se s o v e r f ro m a n i n it i a l r ota t i on l e ss a n d vib r a t io n l e s s s ta t e
in t o t h e fi n a l s t a t e i n wh i c h th e t w o i on s os c i ll a te r e l a t i v e ly
t o o n e a n ot h e r w i t h o n e qu a n t um a n d i n wh i c h a t th e s a m e , ,

t i m e th e m ol e c ul e r o t a t e s a s a wh ol e wi t h on e qu a n tum
,
Th e .

r ot a ti o n l e ss a n d v ib r a t i on l e ss s t a t e h a s h o we v e r a v a n i s h i n gly , ,

s m a ll p r ob a b i l i t y ; t h e n um b e r o f t r a n si t i on s f r o m t h i s i n i t i a l

s t at e e r s e c on d a n d t h e r e f o r e t h e i n t e n s it y o f t h e c or r e s p on d
p ,

i n g ab sor p t i o n l in e i s h e n c e v a n i shi n gly s m a ll

,
B y th e d i s .

a pp e a r a n c e o f t h e fi r s t l i n e t o t h e r i gh t o f t he m i ddl e p o s i t i o n

v
0, t h e s t ruc t u r e o f t h e l i n e s a s ob se r v e d by Im es i s a c t u a lly

r e p r o du c e d a s o n e m a
, y e a s i ly r e c o g n i s e ; i n t h e f o r mul a t h e ,

m iddl e Of the l i n e s tr uc tu r e i s d i s pl a c e d f ro m th e p o in t v0
t o t he ri gh t b y the a m ou n t Th e a b s or p tio n l i n e s group
t h e ms elv e s e qu i d i st a n t ly a nd s ymm e tri c ally on b ot h Si des of

g
th e m i ss i n g m iddl e v v
— Th i s s tat e of a f airs f
gg j
.
, 0

m ay b e ex p r e s se d by wri t i n g ,
in for m a l a gr ee m e n t wit h
V = V
'

o i
'

5
4 21
7
0 1 :

wh e r e
h
”0 2
8 7r J
F r o m t he c o n sta n t in te r v a l b et wee n n ei ghbou ri n g l i n e s ,
nam e ly
h
4”e
( 1 2 0)
t he m o m e n t of i n ert ia o f t he r o ta t i n g m ol e cul e can be c al

c u l a t e d wi th gr ea t a c cu r a cy 825 .
 CH AP TE R IX

T he F u t u r e

N t he p r e c e d in g p a g e s t he a u t h or ha s a t t e mp t e d t o gi ve
i n br oa d o u tl i n e t he m o s t i mp o rt a n t f e a t u r es o f t he
do c t rin e of qu a n t a i t s o r i gi n i t s d e v e l o pm e n t a n d i t s
, , ,

ra m i fi c a t i o n s .If w e n o w s u r v e y t h e wh ol e st r uc t u r e a s ,

i t s ta n d s b e fo r e u s , f r o m i t s f o u n d a t i o n s t o t he h i gh e s t s t o r y ,

w e c a n n o t a v o i d a f e e l i n g o f a d m i ra t i o n a dm i r a t i o n fo r t h e

fe w w ho c l e a r S i ght e dly r e c o gn i s e d t he n e c e s s i ty fo r t he n e w
-

d oc tr i n e a n d fough t a ga i n s t t r a dit i o n , thu s l a yi n g th e fo u n d a

t i o n s fo r t he a s to n i sh i n g s u c c e sse s wh i c h h a v e S p r u n g f r o m
t he qu a n t um t h e or y i n so sh o r t a t i m e .

N o n e t he l e ss , n o on e w ho st ud i e s th e qu a n t um t h e or y
w i ll b e S p a r e d b i tt er d i s a pp o i n t m e n t F o r w e mus t a dm i t
.

t h a t , i n s p i t e of a c o mp r e h e n s i v e f o r mul a t i on o f qu a n t u m
r ul e s , w e h a v e n o t c o m e o n e s t e p n e a r e r t o u n d e r s t a n di n g

t he h e a r t o f t h e m a t t e r Th a t t h e r e a r e di sc r e t e m e c h a n i c a l
.

a nd l c t r i c a l sy s t e ms c h a ra c te ri se d by qu a n t um c o n d i tio n s
e e ,
”
a n d m a r k e d o u t f r o m t h e i n fi n i t e c on t i n u i t y o f c l a s s i c a lly

p os si bl e s t at e s a pp e a r s c e r t a i n Bu t wh e r e d oe s the d e e p e r
, .

c a u s e l i e wh i c h b r i n g s a b o u t t hi s d i s c o n t i n u i t y i n n a t u r e ?
,

W i ll a k n o wl e dge of t he n a t u r e of e l e c tr i c it y a n d o f t he c on
s t i tu t i o n of t he e l e c t r o m a gn e t i c fi e ld s e rv e t o r e a d th e r i ddl e ?

A n d e v e n if w e d o n ot s e t o u r se lv e s so di s t a n t a goa l t h e r e ,

r e m a in s an a bu n d a n c e of u n a n s we r e d qu e st i on s . The
de c i sion ha s n ot ye t b ee n m a d e a s t o whe t he r a s P la nc k s
, ,
’

firs t t h eory r e qu ir e s o n ly qu a n t um a ll o wed st a te s e x is t ( o r

,
-

ar e s t a bl e r wh e t he r a c co r d in g t o P la nc k s s e co n d fo r mul a
)
’

, o ,

t io n t he i n t e r m e d i a t e s ta te s a re a l so p o s s ib l e
,
W e a re sti ll
.

c o mpl e t e ly i n t he d a r k a b o u t t he d e ta i ls of t he a b s o r p t i o n

a nd e m i s si on p r o c e ss ,a n d d o n ot in th e l ea st u n d e r s ta n d

12 5
12 6 T HE Q U A NT U M T HE O R Y

why t he e n er gy qu a n ta e j e c t e d e x pl o s i v e ly a s ra d i at i o n
S h o ul d f o r m t h e m se lv e s i n to t h e t r a i n s of w a v e s wh i ch w e

ob se r v e fa r a w a y f r o m t h e a t o m . Is r a d i a t i o n r e a lly p r o
p ga a t e d i n t h e m a n n e r cl a i m e d b
y t h e c l a s si c a l t h eo r y
,
o r

ha s i t a l so a qu a n t um ch a r a c t e r ?
Ov e r a ll t h e s e pr ob l e m s t h e r e h o v e r s a t t he p r e se n t t i m e
a my s t e r i o us obscu r i t y . In S p i t e o f t h e e n o r m o u s e mp ir i c a l
a n d t h e o r e t i ca l m a t er i a l wh i ch l i e s b e f o r e u s t h e fl a m e o f
,

t h o ugh t wh i ch S h a ll i llum i n e t h e o b s cu r i t y i s s t i ll w a n t i n g .

L e t u s h o p e t h a t t he d a y i s n o t fa r d i s ta n t wh e n t he m i gh t y
l a b ou r s o f ou r ge n e r a t i on w i ll b e b r ought to a succ e s s ful
con clus ion .
 M a t he m a t i c a l N o t e s a nd R e fe r e n c e s

O L a mmer a n d E P r i n gs he i m , W i e d e m A n n 63 , 3 9 5 ( 1 8 9 7 )
1 . . . .

V erh an d l d d e u t sc h p h y s i k a l G e s 1 8 99 , pp 2 3 , 2 1 5 ; i bid , 1 9 00, p 1 6 3

. . . . . . . . .

Of a l so 0 L u mm er a n d E J a hn ke , D ru d e s A n n 3 , 2 8 3
. . . an d O . .

L u m mer , E Ja hn ke a n d E P r i n gs he i m , D ru d e s A n n 4 , 2 2 5
. . .

s M P l a n ck , V orl e su n g e n ii be r d i e Th e o r i e d er War m e s t r a h l u n g
. .

( L e i p zi g 1 0 .

v e l o c i t y of l i gh t i n va c u o (c )

4 , Cf
f o r e x a m
. p l e ,
M P l a nc , V o r l esu n g e n u b e r W a rm est ra h l u n g
. k
17 .

5 G . G
Ki r c hhoff, e sa m m e l t e A b h a n d l u n g e n ( J A a rt h , L e i p zi g . . B
pp 5 7 3 c l seq
. e r l i n er A k a d e m i eb e r i c ht e , 1 8 5 9 , p 2 1 6 ; P ogge n d A n n
. B . . .

109 2 7 5 ,

0 L u m me r a n d W Wi e n , W i e d em A n n 56, 4 5 1
6 . . Cf a l so . . .

0 L a mmer a n d F Ku r l ba u m , V e rh an dl d d e u t s c h p hy si k a l G e s 1 7 ,
. . . . . . .

1 06
7 Of N o t e 5 . .

8 L B o l tzma n n , Wi e d e m A n n 22 , 2 9 1
. . .

OJ S tefa n , W i e n er Ber 79 , 39 1
. .

10Th e S tef a n B ol tzm a n n L a w i s d e d u c e d a s f ol l ow s : L e t t he e n ergy

-

o f b l a c k b o d y r a di a t i o n a t t h e t e m p e ra t u r e T , wh i c h i s e n c l os e d i n a
-

s p a c e o f v ol u m e V h a v i n g a m o va b l e p i s t on , b e U = Vu , wh er e u i s

t he p a t i a l d e n si t y o f t h e r a d i a n t e n ergy Th e p r es su r e e qu a l i n
“
s
”
.
,

a l l d i r e c t i o n s wh i c h t h e r a d i a t i on e x er t s u p o n th e p i st o n a n d w a l l s i s
, ,

a cc or d i n g t o e l e c t r o d y n a m i c s p §u If w e s u pp l y t o t h i s sy s t e m a t
, .

t h e t e m p era t u r e T ( t h a t i s i s o t h e r m a l ly) a n a m ou n t o f h e a t d Q t h e n
’
, ,

i t s e n e r gy i n crea s es b y d U a n d the r a d i a t i on d o e s w or k p d V i n p u s h
,

i n g b a c k t h e p i s t on Th e r e for e a c cor d i n g t o t h e fir s t l a w of th e rm o
.
,

d y n a m i c s a n d o w i n g t o t h e t w o r e l a t i o n s a b o ve
,

d Q dU + pdV = ad V + Vd u
g ar d V + Vd u
’
§ u .

A c c or i n d g to t h e s e c on d law of t h e rm o dyn a m i c s , i f
? m u st b e a co m

p l et e d i ff er en ti a l H en c e th e f o l l o w i n g r e l a t i on h ol ds
"
.

B d
£7 6 ) G) (T
a
" m

?
7 E ad T
1 du __
1
_
Td T T 2
du T
1
 1 28 T HE Q U A NT U M T H E ORY
du u
w 10 i n t e gr a t e d g1v e s u aT ‘
dT T

wh e r e a is a c on s t a n t . N ow , as we c a n e a sil y s e e , t h e t ot a l ra d i a ti on
a)

K
f
0
Kd is d i st i n g u i sh e d fro m th e d e n s i ty of r a d i a t i on u on l y by

a f a c t or ( s ee M P l a n ck L e ct u r e s i n R a di a ti on
c on s t a n t .
,

h e n c e th e t ot a l r a d i a t i o n i s p r o p or t i on al t o t h e f ou r t h p o we r of t h e
a b s ol u t e t e m p e r a t u r e a n d t h i s i s t h e S tef a n B o l tzm a n n L a w -
.

1 1 W Wi e n S i t zu n gsb e r d A k a d d W i s s e ns c h B erl i n 9 F e b 1 89 3
.
,
. . . . .
, .
,

p 5 5 ; W i e d e m A n n 52 1 3 2
. . Of a l so M a x A br a ha m Th e ori e
.
,
.
,

d er E l e k t ri zi t at II § 4 3 M P l a n ck V orl e su n g e n u b e r d i e
'

.
, ,

T h e o r i e d e r W ar m e s t r a h l u n g ( L e i p zi g pp 6 8 cl seq W Wes tp ha l . . .
,

V e rh a n dl d d e u t s c h p h y si k al G e s 1 9 1 4 p 9 3 ; H A L or en tz A k ad
. . . . .
, . . .
, .

d Wi ss e n sc h A m st er d a m 1 8 M ay 1 9 01 p 6 07
. . , , . .

12 F orm u l a ( 4 ) of t h e t e x t ( M en s L a w o f D i sp l a c e m e n t ) m a y b e
’

o b t a i n e d b y m ea n s o f a S i m p l e d i m e n s i o n a l c a l c u l a t i o n as L Hopf , .

r e c e n t l y s h ow e d i n t h e N a t u r wi ss e n s c h a f t e n
”
(8 1 09 1 1 0
“
, ,

W e a ssu m e t h a t K d e p e n d s onl y on ,, T a n d t h e v el oc i ty o f l i gh t c u, , .

T h e d i m e n s i on s o f K a r e o b t a i n e d f r om t h e f a c t t h a t ac c or d i n g t o
,, ,

e n er gy
2 Wd V
s u r fa c e x t i m e

F ro m t h i s i t f ol l o w s t h a t
[ m l
If w e se t
m
K ,, c o n st . u Ty o
f

t h en ,
re m e m b eri n g t h a t T h a s t h e d i m e n si on s o f e n e rgy , w e ge t
—2
rm
mv y
zy 2
]
m
‘

[t 1 4
‘

2
[m i ] c on s t i
- ' -
.

3”
2
c o n st [ m y Z x 2“
J Z
l
‘ ‘

1
‘

. t

He n c e x = 2 ; = 1 ; z =— 2

whi c h gi ves u s, K = c on s t,, . if

.
T .

Th i s r e l a t i on is n ot , h ow e v e r , as we S h al l se e , gen e r a l l y v al i d . In f a ct ,
w

it wo u l d g i ve no fin i t e va l u e for K 2 K, d v , . Bu t , a cc o r d i n g t o th e
O
S tef a n -
B o l tzma n n L aw K 7 T 4 H e n c e t h e c on s t a n t of K y m a y .

st i l l d e p en d on a d i m e n si o n l e s s c om b i n a t i o n o f t h e f o u r v a ri a b l e s

v, T, c h ere fore w e s et c on s t f ( v
If, t "
c§ h e n t h e a rg u m e n t
t
7 ,
.
, .

of th e f u n c t i o n f m u st h a v e t h e d i m e n si o n 0 . If, f u r th er w e r em e m b e r ,

t h at

—3
[m l 8 5
t J
-

,
 N O TE S A ND REFERE N CES 129
it t h e n fol l o ws t ha t
— mv P “
K t
[t f 11 t n m B.
l ‘w
t 50
]
- - -
. .

[t
-

E - T’l

— 3w
; fl = 3w ; ( = 2w .

H
] 1
en c e c o n st ?“ w
c
q
°
.
7 ;
V T

12
()
” 2
Th e r e f ore T 5 {C T i l
0
.
1
<)
T c
2
T
. F

or , fin al l y ,

pl o t K
( ) 1 fu n cti on o f y k e ep i n g T con st a nt
1 8 If w e as a th e
, ,
02
v
T
m ax im u m of h
t is cu rv e— if on e is p re se nt— l i es a t th a t p oi n t a t whi c h
an y
0 . Th i s gi v es

(a 1m 1
()
V
3F _ 1 .

t T

wh er e l
F i s th e d i fferen t i a l coe ffi c i en t o f F wi th respec t t o t he a rg u m e n t .

Th i s i n wh i c h on l y o c c u r s a s u n k n own gi ve s a d e fi ni t e v a l u e
V
e qu a ti o n , ,
T
z
"ma x
j
v
In ot h e r w or d s , for v vma x , it f ol l ows t h at c on s t .

S T
14 W Wien Wi e d
.
, . A nn .
58 6 6 2 ,

0 L u m mer P r i n gshe im , W i e d A nn 63 , 3 9 5 Dru d a s ’

15 . and E . . .

A n n 3, 1 5 9
. V e rh d d e u t sc h ph y s G es 1 , 2 3 a n d 2 1 5 . . . . .

Th e t ot a l r a d i at i on e m i t t e d p e r se c on d fr om 1 c m i n on e d i re c t i on i s ,
2
.

by for m u l a ( 1 )

A c c or d i n g t o t h e S tef a n ol tzm a n n L a w , S i s p ro p ort i o n a l t o T4 , th er e

-
B
for e S « T ( Th e c on s ta n t of p ropor ti on ali ty 0 i s r e l a ted t o t he
‘
.
'

oc cu rri n g in
c o n sta n t 7
( )
3 b y t h e e q u a t i on n ) Th e a b s ol u t e .

m easu re m en t o f 8 g ave t h e o l l o f w g
in v al u e s for '
a , in c hron ol ogi ca l or d er :

ac cor d i n g to F Ku/r l ba u m
.
[ Wi ed e m . An n .

65 7 46
, V e rh a n d l . d d e u t sc h
. .

p h y si k a l G e s 14 , 5 7 6 , 7 9 2
. .

12 acc or d i n g t o S Va len t i n e r [ A n n (1 Phy s

-

. . . .

31 , 255 39 4 89 ,
~
= 5 90 1 0 12 din g W Ger la c h A d Ph ys
d
.
acc or to .
[ n n . . .
 T HE Q U A NT U M T HEORY

a 53 0 .

$ 4
] ac c or di n g to E . B a u er
Phy s
and M . Mou l i n
[ So c F ra n c . de . Nr . 301 , 2 3 -

10
-
12 a c c or d ing t o Ch . F ér y [ B u ll S oc F ra n c . . .

Ph y s 4 .

10
-
12 a c c or d i n g t o Ch F er y a n d M D r ecg . .

[ J o u rn d e Ph y s ( 5 ) 1 5 5 1
. .
,

10 12 a c c ordi n g to G A S ha kesp e a r [ Pr o c R o
y . . . .

S oc .
( A ) 86 ,
1 80
a cc ord i n g t o W H Westp ha l [ Verh an dl . . .

d de u t ch p hy sik a l G es 14 9 8 7
. s . . .
,

6 05 1 0 12 ac c or d i n g t o L P u cci a n ti [ Ci m ( 6 ) 4 3 1
-
-
,
. .
,

a cc or di n g to Keen e [ Proc . R oy . S oc .
( )
A
88 4 9,

-
l2 a ccor di n g t o W H Westp ha l [V erh a n d ] . .
,

d d e u t sc h p h y sik a l G es 15 8 9 7
. . . .
,

10 12 a c c or d i n g t o W Ger l ac h [ Ph y s Z e i t s ch r
-

. . .

17 , 1 50
As d s Wien s L a w of D i spl a cem en t th e r e l a ti on ( 5 a ) w as t e sted
re gar
’
,

a n d f ou n d t o b e c o n fi r m e d F r o m F i g 1 i n wh i c h E , i s p l ott e d a s a . .
,

fu n c t i on of A for di ffere n t va l u es o f A w e see c l a rly h o w th e m a x i m u m ,

e

o f t h e c u rv e b ec om es d i sp l a c e d t o w a r d s S h or t e r w a ve l e n gt h s a s t h e -

t e m p era t u r e r i s e s .

F or th e c n st a n t on t h e r i gh t h a n d si d e of re l a t i on ( 5 a ) th e m e a s u r e
o -

m e n t s g a v e t h e f ol l o w i n g v a l u e s
c on s t 02 9 4 [ cm d eg ] a c c ord i n g t o O L u m mer a n d E P r i n gshe i m
. . . . .

[V e rh and l . d d e u tsc h
. . h
p y s i k a l . Ges 1 , 2 3 .

and 21 5

ac c or di n g to F . P a sche n [ D ru d e s An n ’
.
6 6 57 ,

02 9 1 1 a c c or di n g t o Cob le n tz [ B u lL Bu r . of Sta n d 10, .

10O L u m mer a n d E
. . P r imgs he i m , Ve rh a n d l . d deu t sch
. .
p h ys i k al .

G e s 1 , 2 15
.

17 F P a sche n , . e rl i n er Be r 18 99 , pp 405 , 9 5 9
B . . .

1 8 M P la nc , A b so rp ti o n u n d E m i ssi on e l e t r
. k We ll en d um h Re son an z k . .

Si tzu n gsb er d e rl A a d d Wi SS 2 1 Ma rc h 1 8 9 5 , pp 289 —3 01 ; Wi ed e m

. .B . k . . . . .

A nn 57 , 1 1 4 — fi b e r e l e t r Sc hwi n un g en we l c h e d urc h Re k
g
-
.
, .

so n a n z e rre gt u n d d u rc h S t ra h lu n g g ed am pf t w e rd en S i tzu n gsbe r d . . .

Be rl A a d (1 W188 2 0F eb r 1 8 9 6 , pp 1 5 1 1 7 0; Wi ed e m A n n 60, 5 7 7 5 9 9
. k . . . . .
-
. .
-

Ub er i rreversi b l e St ra hlu n gsvorgan ge ( 1 Mi t tei lu n g ) Si t zu n gs

-
. . .

b er d
. erl Ak a d d Wi s s , 4 F e b r 1 89 7 , PP 5 7 —6 8
. B . . .
( 2 Mi tt eil u n g ) i bi d ,
. . . . . .

8 Ju l y 1 89 7 , pp 7 1 5 7 1 7 ( 8 M i tt
.e il u n g ) i-
b i d 1 6 D. ec 1 8 9 7 . P P
. 1 1 2 2 . .

1 14 5 ( 4.M i tt e il u n g ) ibid 7 J u l y 1 89 8 , pp 4 4 9 4 7 6 ( 5 M i t te il u n g) i bid , .

-
. . .

1 8 May 1 8 99 , pp 44 0 4 80 ( S u pp l em en t ) ibi d , 9 May 1 9 01 , pp 5 44 55 5 ;

.
-
. . .
-
 N O T ES A N D RE FERE N CE S 18 1
Drud es A n n 1 , 6 9 1 2 2 .
( S u pp-
l e m en t ) D ru d es A nn 6 , 8 18 —831 . .

— E n tropi e u n d Te m pe ra t u r st ra h l en d er Warm e Dr ud es A n n 1 . .
,

7 1 9 — 7 37
1 9 In pl ac e o f t h e m e a n va l u e , wi t h res p ec t to ti m e , of t h e e ne rg o f a
y
s i ng le o sc i ll a t or , w e m a y u se t h e sp a ti a l m e an va l u e o f t he m o m en t a r
y
e n e rgy o f a w h o l e s ys te m con si s ti ng of ver y m a ny osci l la tor s .

20In t h i s s ec on d , m ore d i ffi c u l t p a rt o f t h e c a l c u l a ti on , P l a nc t a es h i s k k
st a n d u pon t h e se c on d l a w o f t h erm o dy n a m i c s , a n d see s , f ro m t hi s v i e w , k
t o d e te rm i n e a ph a se qu an t i ty S o f t h e osc i ll a to r , wh i c h po ssess es t h e
-

well nown prope rty o f t he en trop y , t h a t i t i n c rea se s in al l i rreversi b l e

-
k
proc esse s H e a rri ved a t the so lu ti on
.

H
E
Bu { ( y)
l oge
a

Thi s fu nc ti on possesse d P l a n ck s howe d th e requ i re d pro pe rty of en

, as ,

t ro py b u t i t w a s n o t t h e o n ly f u n c t ion wi t h t h i s pro pe rty

, A n d i n f ac t .

i t a ppe are d l a te r t h a t i n t h e d e du c ti on o f t h e a b ov e e x p re ssi on a read il y

, ,

su gg es te d b u t u n j u sti fi e d su ppo si t i on h a d b e e n m a d e Th e e x pressi on .

gi ve n i n th e t ext f orm ul a fo r t h e m e a n e n er gy U f o l lo ws f rom S b y

,

a pp l yi n g t h e sec on d l a w i n t h e f orm

dS = d U or ۤ 1

T dU T

21 L a m me r a n d E P r i n gshe i m , V e rh an dl d d eu t sc h ph ysi kal

O . . . . . .

Ges 1 9 00, p 1 6 3
. . .

22 M P l a n ck , V erh d d eu tsc h phy s Ges 1 9 00, p 23 7 It i s o f

. . . . . . . .

hi stori c i n te rest to n ote t ha t P l a nc k h ad a lready , in a so m ewh a t earli er

pa pe r ( V erb d d eu tsc h phys G es 1 9 00, p
. . a rri ve d a t t h e t ru e
. . . .

l a w of ra d i a ti on b y a pu re ly f orm a l a l te ra ti on o f Wi en s f orm u l a , whi c h

’

w a s n ot f ur t h er ex pl a i n e d Cf a l so Ann d Ph ys 4, 55 3 . .
4 , 56 4 . . .

6, 8 1 8 9 , 6 29
23 Le t N osc ill a t o rs b e p rese n t L e t t h e t ot a l en ergy to b e di vi d e d
.

a m on g t hem b e UN N (7 Th e sta te or ph ase of t he oscillato r .

“ ”

sys te m t h e p rob a b ili t y o f whi c h i s to b e c a l c ul a te d i s t h e n d efin e d b y t h e

, ,

f ac t t h a t N osc ill ators possess th e en ergy UN We di vi de UN i n to P .

e n er gy e l e m e n ts so t h a t 6 ,

Th e nu m ber of possi b le ways of di stri bu ti n g P b a lls am on g N b ox es i s ,

however ,

(N + P 1) l
W
-

(N
Thi s i s t h ere fore t he prob a b i li ty o f t h e s ta te , wh i c h c orre s o n s p d to t h e
dis tri b u ti on o f P en ergy elem en ts am on g N osc il l a tors . P E hr enfes t an d
.

H Ka m er l i ngh On nes gi ve a very si m pl e d ed u c ti on

.
- o f t h i s fo rm u la i n

Ann d Ph ys 46 , 1 021
. . .

Th e ru le m en ti oned in th e text , whi c h i s d u e to B ol tzma nn , st a tes

18 2 T HE Q U A NTU M T H EORY
t ha t th e e n tropy SN of the o sc i ll a to r sy st e m is c on nec te d wi t h th e prob
a b il i t
y W hy t he f u n d a m e n t a l re l a t i o n
SN k l og W
where k i s a c on sta nt .

In t h i s t h eorem o f B ol tzma nn th e f ol l owi n g l aw o f t h e growt h o f e n

tro py ( sec on d l a w o f t h e rm o dyn a m i c s i s con t a i n e d : i f a s ste m p a sses
) y
from a n i m prob a b l e c on di ti on i n to a m ore prob ab l e on e t hen b y t hi s ,

t ra n si ti on W a n d t h e re fore t h e e n t rop S i n c re as e s If w e h ere i n se rt t h e

, y , .

v a l u e o f W a n d si n c e N a n d P a re v e r
y l arge n u m b ers us e S ti r l i n g s
’
, , ,

a pproxi m ati on f orm u l a

l oge ( N !) = N (l og N 1) e

t h en , i f we se t f or P , N 2 , we get b y an e asy c al c u l a ti on
6

SN Ji N
{( 1 log
( 1 g
6
) g l og
e e

»
and h en ce t h e e n tropy S o f on e osc ill a to r b ec om es

g a g /9
k
{( l + 2
e ) ( l og 1 Q
e ) e \ 6

Bu t ac c or di n g to th e S ec on d L a w ( see n ot e 20)

dS 1
“ “

db
’

If we c a rr
y ou t th e di fferen ti a ti on on t h e l ef t h an d Si d e an d sol ve th e t e -

su l t i n
g rel a t i on , ,
b et w ee n U T a n d wi th re spec t to U we ge t th e ex c, ,

pres si on (9 ) of th e text .

24 Of t h e p a pe r b Ka mer li n gh Onne s d i n th e
y E hr enfest an d c ite
-
.

p revi ou s n ote .

25 T hi s l a w is e ssen ti a ll y i d en t i c a l wi t h B o l tzma nn s H Theo rem ’

-
. Cf .

L B ol tzma rm , V orl e su n g en ii b er
.
Ga st heori e Bd I p 3 8 .
, . Si t
zu n gsb e r d W i en er A a d d Wi ss
. . k . . .
( II) 7 6, 37 3 Cf . a l so P .

E hr enfest P h y s Z ei t sc h r 15, 6 5 7
, . .

26 H R u ben s
. F K u r lba u m , Si t zu n gsb e r d
an d er l A a d ( 1 W i se
. . . B . k . . .

1 9 00, p 9 2 9 ; An n (1 Phy s 4 , 6 4 9
. . . .

27 F P a schen , A n n d Phy s 4 , 2 7 7
. . . .

28 L Hol bor n a n d S Va len ti ner , A nn (1 Phys 22 , 1

. . Coble n tz, . . .

Physi ca l Re vi e w , 31 , 3 1 7 ( 1 9 1 0) E a isch , An n d Phys 35, 5 4 3 . B . . .

E Wa r bu r g, G L ei thau ser , E Hu p a an d C Mu l ler , A nn (1 Phys 4 0,

. . . k . . . .

609 E Wa r bu r g an d C Mu l ler , Ann d Phy s 48 , 4 1 0

. . . . .

29 W N er n s t a n d Th Wu lf , B er d d eu tsc h ph y s G es 21 , 2 9 4
. . . . . . .

30L or d R a y le i gh , Ph i l Ma g 49 , 5 3 9 . .

31 Th e S tef a n B ol tzm a rm con st an t of t ot a l ra d i a ti on

-
i ntrod u c e d
in n ote 1 5 , h as t h erefore th e va l u e

v :
 N O TE S A N D REFERE N CES 188
32 1 n d e r to d e t ermi n e the c on st a nt s h a n d k whi c h occ u r i n th e
or

ra d i a t i on f o rm u l a w e c a n i n st ea d o f u s i n g th e eq u a t i on : m
, ,
T ax .

c o n st . c om p ar e ot h e r re l a t i o n s w i t h the m e a su r e m e n t o f t h e t o t a l
,

r a d i a ti o n F or e x a m pl e w e c a n p roce e d a s fol l ow s : A t a c o n st an t
.
,

t e m pe r a t u re T w e m e as u re t h e r a t i o o f t h e i n t e n si ty o f r a d i a ti on for t w o
di ffe ren t wa ve l e n gt hs A ] a n d A2 (i soth erm a l m eth od) N ow t h i s r a ti o
-
.

i s a ccor d i n g t o ( 1 5 )
,

1
-
, whe r e C

F r om th i s re l a ti on , si n c e e v e ry t hi n g e xce pti n g C i s kn own C t h a t i s , , ,

1 m ay
2
1
be ca l cu l a te d . A n oth er m e th o d i s t h e f oll ow i n g : w e m ea su re for

a fixe d w av e l e n gt h A t h e r a ti o of th e i n te n si ty o f r adi a t i on a t t w o
-

di ffe re n t tem pera t u res TI a n d T2 ( i sochrom a t i c m et h od ) Th en i t fo ll ows .

th a t
C
m m
Ei ) r

:
e 1
Ha) s 0

Thi s i s from whi ch 0 t ha t

a r el a t i on c a n aga i n b e c a l c u l a t e d ,
.

Wi th t he h e l p of t hes e m eth o d s t h e re se a rc h e s for ex a m pl e o f , , ,

Wa r bu r g a n d h i s c c workers c i te d i n n ot e 2 8 h ave yi eld e d v a l u e s fo r

-

C whi c h li e i n c l ose p roxi mi ty to C Thi s va l u e wa s t a k e n

b y N er ns t an d Wu lf ( see n o te 2 9 ) for t h e i r c ri t i cal i n ve s ti g a ti on .

F or t h e cons tan t o f Wi en s L a w of D i sp l a c e m e nt i n th e for m A m T

’
ax

b w e wo u l d a c c or di n g l y ge t fr om ( 1 6 )

a v a l u e s m a ll e r , t h ere f ore t h a n t ha t g i ven

,
m e a su re m e n t ( s e e by d i re c t
no t e W h e t h e r Wa r bu r g s va l u e , 0 1 4 30, o r t h e m e a su r e d v a l u e s
’

o f b(> or b o th , a re se ri ou sl y a ffe c t e d b y ex p e ri m e n t a l e r r or , o r

wh e t h e r a f t e r a ll — a s N e r n st a n d Wu lf m a i n t a i n P la nck s f o r mu l a i s -
’

n o t ri gh t , m u s t b e l e ft fo r th e f u t u re t o d e c i d e .

83 M . P la nc k A n n d Phys
, . . .
4 5 53
,

84 1 i w e a pp l y B o l tzm a nn s 8 k l og W ( q u ot e d i n n o te
r e l a ti o n
’

wh i c h c onn ec ts t h e e n trOp y S wi t h t h e p rob a bi l i ty of sta te W, t o on e

g ra m m e m o l ecu l e of a n i d e a l ga s , t h e n b y cal c u l a ti n g t h e pro b a b i l i ty of
-

a c e rt a in s ta te , i s a c e rt a i n d i st ri b u t i o n o f v e l oc i t i e s a m on g th e
. .

m ol ec u l es , w e arri v e a t th e f ol l owi ng va l u e for th e e n t ropy of t h e ga s

S kN ( i} l o ge U l og V) c o n st .
18 4 T HE Q U A NT U M T HEORY

( Oh , for ex a m ple , M . P l a nck , L e ct u re s on th e T h eory of Ra di a ti o n

He re
N i s t h e n u m b er o f m o l e c u l e s i n a gra m m e
m ol e cu l e (A voga d/r o s n u m b e r) , U t h e e n ergy , V th e vo l u m e
’
of t h e ga s .

N ow , a c co rd i n g t o th e S e c on d L a w of Th erm ody n a m i c s ,

m u st b e a c om pl e t e di ffere n ti a l where , p an d T den ote p re ssu re an d

t e m p e ra t u re of t h e ga s . He n ce th e rel a ti on

m u st h ol d . Thi s g i ves
9 i c e .
p

If we co m p a re t h i s wi t h t h e e qu a ti on of s ta t e o f a n i d ea l ga s i n t h erm o
RT
dyn am i cs , p w e ge t for t h e a b s ol u t e ga s c o n st a nt R th e v al u e
V
R = kN

from whi c h form u l a ( 1 9 ) of th e t ext fol l ows .

SB M P la nck A nn ( 1 Ph s
.
y 4 5 64 56 6
, . . .
,
-

3° Com p a re for ex a m p l e th e t a b l e o f t h e v al u e s of A vo ad ro s n u m b e r ’
, g
, _

gi ve n i n t h e r e p or t o f J P err i n a t t h e S ol v a y Co n gress i n B ru sse l s

.

[ A E u cken D i e Th e ori e d e r S t rah l u n g u n d d er Q u a n te n

.
,
.

A b h a n dl u n g e n d er B u n s en G ese l l sc h a f t N r 7 W i l h K n a pp H a ll e-
.
,
.
,

3 7 R A M i l l i k a n Ph i l M a
. .
g ( 6 ) 34 1 3 , . .
,

38 1 bi d f rom t h e va l u es gi v en b y Mi l l i ka n fo r th e e lec tron i c c h a rg e

.
,

e x ( e l ec t r o s t a t i c u n i t s) a n d f r o m t h e e l ec tr o ch e mi c a l

c on s t a n t F : 1 01 0 e l e c tr os t a ti c u n i t s t h ere f ol l o w s for ,

A voga d r o ’
s n u m b er the va l u e N 6 06 1 7 1 023 .

Of" for e x a m p l e ,
39 W . G i bbs E lem en t s of St a t i st i cal
’
M e c h an i c s ,

Ch a p te r V .

40Th e t erm “ m e an v a lu e m a y b e t a k en f
a s r e e r ri n g to tim e or to
S p a ce . If w e s el e c t a d efin i te a t om , a n d f ol l o w it a l on g t i m e u pon i ts
zi
g za g p a t h , a n d fr om t h e m ean o f t h e va l u es wh i c h i t s ki n et i c e n ergy
-

a ss u m e s i n t h e c ours e of t i m e w e e t t h e
“
t i m e m ean If o n th e
g
-

, , .

o th e r h a n d we se l e c t a l ar e n u m b er o f i d e n t i c a l a t o m s o f th e s at a
, g g a

p a rti c u l a r i n st a n t a n d a g a i n f or m t h e m e a n of t h e va l u es of t he ki n e ti c
.

e n e rgi e s wh i c h t h e se a t o m s p o sse ss a t t h e i n st a n t i n est i on , w e ge t

qu

th e s p ac e m ea n ” -
,

4 1 If x i s th e e l on g a t i on of th e osci ll a to r e l e c t r on v i bra t i n g w i t h th e
( )
n a t u r a l fr equ e n c y , t h e n x A si n ( 2 1n d) , wh e re A i s th e a m p l itu d e a n d
t t h e ti m e t h e m e a n ki n et i c e nergy b e com e s

ff :
i m 1 m m 2 1m ) 2
c os
2
( 2 1m d
) m
i ( 2 1rvA
)
2
.
 N O T ES A ND REFERE N CE S 18 5
Th e m ea n pote n ti a l e n er gy i s
§ m ( 2 1rv) 5m ( 2 1ruA ) i m ( 2 1r vA )
2 2 2 2
( 21rv l )
2
x Si n .

Hen c e ,
as s t at e d , L : V: i . e . the m ea n ki n eti c e n e r gy : the m ea n
po te n t ia l e n er gy .

H Je a ns , P h i l Ma g 10, 9 1
. . .

“H . A L or en tz, P roc K o n Ak a d
. v We t , A m st er d a m 1 9 08 , p 666
. . . . . . .

—Th e t h eo r of e l e c t ro n s Te u b n e r L e i p zi g Ch II
y ( , . .

44 A E i n stei n a n d L Ho , A n n (1 Ph s 33 , 1 1 05
.
pf .
y . . .

45 A D F okker , A n n ( 1 Phy s 43 , 8 1 0
. . . . .

46 M P la nc k , B e r d B e rl A k a d d W i s s , 8 J u l y 1 9 1 5 , p 5 1 2
. . . . . . . . .

4 7 H A L or en tz
. . D i e Th e ori e d St r a h l u n g u d
. u a n t en ; A b b a n d . . . Q
l u n g e n d er D e u t s c h e n B u n se n e s el l s c h a f t N r 7 v A E u c ken -
G . . . . . .

Hall e , W Kn a pp 1 9 14 pp 1 0 et seq
. . .

( 8 By a su i t a b l e m o d i fi c a t i o n o f c l a ssi c a l st a t i s t i c s i n t h e s e n se o f the

q u a n t u m t h e ory , w e ca n o b t a i n t h e e x p r e s si o n ( )
9 f o r t h e m ea n e n er gy

o f a n o s c i l l a to r i n t h e fol l owi n g m a n n e r wh i c h i s w o r th y of n o t i c e .

L e t a n u m b e r N o f si m i l a r osc il l a t ors w i t h t h e m ost v a ri e d v a l u e s fo r

t h e e n erg y b e g i ve n W e r e qu i re t o fin d h o w g r e a t i s t h e p rob a bi l i t y
.

w , t h a t a n o sc i l l a t or p o s se ss a c e rt a i n e n e rgy v a l u e U ; o r , ot h e r w i s e
e x pr e s se d , h o w m a n y o f t h e N o s c i l l a t or s p o s s e ss t h e e n e r g y U In .

o r d e r t o a n s w e r t h i s q u e st i o n , w e fi n d i t b e s t t o t a k e fi r s t o f a l l th e

s t an dp oi n t o f G i bbs m e c h a n i c s , t h a t i s , of
”
c l a ssi c a l
’ “
s t a t i st i c a l

s t a t i st i c s In p l a c e o f t h e s p ec i a l c a s e i n q u e sti on , n a m el y , t h a t of t h e
.

l i nea r o s c il l a t or , l et u s c o n si d er a t on c e qu i t e g e n erall y a sys t e m of f

d egree s of ha ra c te ri se i t b y f ge n er al i se d c o ord i n a t e s
f r ee d o m , and c -

a n d b y t h e c orresp on di n g i m p u l se s o r m o m e n t a p l p g pf
ql qz Qf .

( H e r e t
, h e i m p u l se p i i s t h u s d e fin e d : fo r m t h e ki n e t i c e n e r g y o f

l z t h en
g
( i
th e sy st e m a s a f u n c t i on of th e g en era l i se d v el o c i t i es g} ,
t
pg
25 In p a rt i c u l ar th e l i n e a r o s c il l a t or ( vi b ra t i n g e l e c t ron ) wil l
Qt
,

be d e sc ri be d b y a c o or d i n a t e q n am e l y t h e e l on ga t i on of t h e el ectr on
-

, , ,

dc
a n d t h e i m pu l s e p m In ge n e ra l t h e r e fo re 2f q u an t i ti e s a re
:
, ,
dt
n e c e ssa r y i n o r d e r t o d e fin e c om p l e t e l
y t h e m om en t a ry sta t e o f a
sy st e m He n c e w e c a n r ep re se n t t h i s m om e n t a ry sta te b y a p oi n t
.

ph a se poi n t i n t h e 2f di m e n si o n a l Sp a c e i n whi c h g1
- -

pf (o f t h e
pha s e s p ac e a re c o o r di n a t e s
- -
.

W e n o w c on s i d e r a n u m b e r N o f s i m i l a r s y s t e m s o f t h i s k i n d ,

whi c h a re i n t h er m o dyn a m i c e q u il i bri u m wi th a v ery l arg e r e se rv o i r

a t t h e t e m p e ra t u r e T Th e n t h e p r ob a b il i t y t h a t th e c o ord i n a te s
.
-

a n d i m p u l s e s l i e i n t h e s m a l l i n t e rv a l s
g1 q , + d gl e tc a n d , .
,

p, p1 dpl e t c t h a t i s t h
, a t t h e p h
. a s
, e ~ oi n t
p o f t h e s y s t em l i e
,

i n t h e el e m e n t d o d ql d q2 q d p l
dp 2 d p f o f t h e ph a s e ,

s p a oe i s ac c o r d i n g to Gi bbs
, ,

°
eTdo
w =
1 36 T HE Q UA NT U M T H E ORY
H e re E i s t h e e n e r gy o f t h e sy st e m , a n d k i s t h e c on sta nt d e fin e d i n
Th e i n t e gr a t i on i n th e d en om i n a t or i s t o b e t a e n ov er a l l k
po ss i b l e v al u e s o f th e 2f qu a n ti ti e s g1 p f, or , a s w e m a y sa y , ov e r
a l l p oss i b l e pha ses, or ov er th e wh ol e r e g i on of th e ph a s e sp a c e
“ -

c o n c er n e d .

Am on g t h e N sy st em s t h e r e a r e t h e n N w , wh os e ph a se p oi n t s l i e i n -

t h e e l e m e n t d o o f t h e ph a se spa c e T hi s i s ther efor e a

-
. d i s tr i bu ti on
of the N sy s tems over the p ha se sp ace Th i s d i st ri b u t i on i s c al l e d
-
.

Ca non i ca l ; i t r e p r e se n t s a g e n e ra l i sa t i on o f M a x wel l s f a m i l i a r l aw o f
’

di st ri b u ti on o f v el oci ti e s wh i c h m a y b e d e d u c e d from i t b y sp e ci a l
i sin g i t for t h e c a s e of t h e ga s a t om , t h a t i s , b y se t ti n g f = 3
-

Th e su m of al l p r ob a b il i ti e s i s n a t u r al l y 1 In d e e d , i t i s a t on c e .

cl e a r t h a t

F or t h e m e a n v a l u e of th e e n er gy E w e ge t

E =2Ew f Ee ” do

_ E
e
” do

If w e a ppl y t h i s e q u a ti o n t o th e l i n ea r o sc il l a t o r we

2 1,
( m Pg
E
l /
“
2

2 1r’ y 2m g2 .

If w e i n tro du ce t h e a u xi li a ry v ari a b l e s 5 an d d efine d by

E wy g N Qm /

~ p
_ _

/2 m
an d h en c e dgdp
w e ge t
U ” 2
E 77

a nd , t he re fore , it su gg ests i tse l f to u s to wri te

5 $2 v 008

.
n J U sin in
where c is a p aram etri c a n gle If w e i n te rpre t ga n d n as Carte si an c o
.

o rdi n a te s of a poi n t i n the pl ane th e n J U a nd 7’ are t he polar c o o rdi n a te s

,
-
 N O TE S A ND REFERE N CE S 187

as we kn ow t hu s,

d td n fi fe d a d s i d Ud s

He n c e

ll
U U

d Ud ¢ U6 d U
0
2 1r

f [
a
M'
e d Ud <p
=0 ¢ =o

in a gr e em en t wi th Th i s i s t h e s ta n dpo i n t o f c l a ssi ca l s ta ti s ti cs .

Th e qu a n tu m s ta ti s ti cs o f t h e osc i ll a to r m a y b e i m m edi a te ly de du c e d
f ro m t h i s , i f we el a b ora te t h e c a n oni c a l l a w of di stri bu tion

”
e d gdp
in a su i t a b l e m a n n er

to a, w e ge t

U + dU .

f
e f ec te d by l a yi n g do wn t he con di t i o n : E s h a ll o n l y b e a b l e to a ssu m e the
v al u es c on t ai n e d in the n arro w i n te rva l s b e t we e n U0 a n d U0 a, U1 an d

UI a , g e n era lly U a n d
and n Un a. T hen dU a , a nd t h e in te gra l i n
the d e nom in a to r c ha n ge s i n to a su m . Th u s i t fo l l o ws t h a t

w n wn
a
188 T HE Q UA N T U M T HEORY
u n al te re d Hence
w n i s t he ca non i ca l d i s tr i bu tio n u nc ti on e ner a l i sed
f g
.

f or qu a n tu m con d i ti on s , a n d h
e n c e , a m on N osc i ll a tors a g
a ve a n , h
e n er gy o f the va lu e Un .

We now ge t for t h e m e an e n er gy

U
EU n wn
n

S
g
U

2
kT
8

If we se t ET for c o n ve n i en ce , x, t h en

“
“
1 e

Fu rt h er ,

-
na;
3 :
m“
( 1 K )
from whic h we ge t

in a gre em en t wi t h (9 )
Th e c a non i c a l di stri b u ti on m a y b e st i ll fu rt h er gen era lise d b y t h e i n tro
du cti on of c ert ain wei ght f ac tors , wh ic h are i nten ded to express th e
“ ”

f ac t t h at t h e i n di vi du al qu a n tu m sta te s o f t h e syste m con si dered h ave ,

a p r i or i , di ff ere n t prob a b i l i t i es.Thi s h a pp en s , for ex a m pl e , if eac h qu an tu m
st a te m ay b e reali se d i n di ffere n t w a y s , a n d i f t h e n u m b er o f t h ese possi

b ili ti es o f rea li s at i on i s di ffe ren t for t h e d i fi eren t qu an tu m sta te s . Then ,

t h e di fferen t st at e s wil l h a ve d i ff e re n t wei ghts, an d a wei gh t fa c tor
” ”

Un
_
h a s to b e in clu de d i n th e e xp e r m en t al fu n c ti on e M ’ so t h at t he c an

o ni c al di stri b u ti on fu n c t i on assu m e s t h e f or m

it

kT
p
‘
n
= C p n8
;

.
kT

Here 0 de pe n d s on t h e te m pera tu re ; p n , on t he ot he r hand , doe s no t .

 N O T ES A N D REFERE N CE S 189
19 A . E i ns te i n , A n n d Ph y s 17 . 1 3 2 ( 1 9 05 ) 20, 1 9 9 ( 1 9 06 ) V e rha n d l
. . . .

d d e u t sc h p hy si k al G e s 11 , 4 8 2
. . . e ri c h t E i n s t e i n a u f d e m
. B
S o l v a y K o n g r e ss i n
-
B
r u ss el s 1 9 1 1 ; of A E u c en , D i e Th eo ri e d e r . . k
Q
S tr a hl u n g u n d d e r u a n t e n ; A b h a n dl d d e u t sc h u n se n e s el l s c h a f t ,
. . . B -
G
N r 7 (H all e , W K n a pp
. . pp 3 30 cl seq Cf al so W Wi en , . . . .

V orl e su n g e n ii b e r n e u e re Pr ob l em e d e r t h e or e t i s c h en Phy si ( Te u b n e r , k
L ei p zi g a n d e rl i nB 4 V orl e su n g H A L or en tz, L e s theo ri e s
. . . .

st a t i s t i q u e s e n t h e r m o d y n a m i q u e ( Te u b n er , L e i p zi g a n d e rl i n B
42 c l seq .

so A E i n s tei n , An n d Phy s 17 , 1 3 2
. . . .

51 A E i ns te in , Phy s Z e i t s c h r 10, 1 8 5
. . .

52 Th i s f o r m u l a m a y b e d e d u c e d a s f o l l ow s F i rst l y , fr om e E E
t h e fr eq u e n t l y u se d re l a t i o n

fi ft h , ( F )2 = E2 E
( ) ?

f ol l o w s . In or de r n ow t o c a l c u l a te t h e tw o qu a n t i t i e s E7
(m e a n o f the
s q u are s o f gy ) a n d ( E ) ( squ are of t h e m ea n
t he e n er 2
energy) whi c h ,

a r e kn own t o d i fi er f rom e ac h ot h er i n g e n e ra l w e d o b e st t o t a k e th e ,

st a n dp o i n t o f G i bbs s t at i st i c a l m e c h a n i c s ( se e not e A c c o rd i n g t o
’

t hi s t h e p r ob a b i l i ty t h a t t h e c c or d i n a t e s a n d i m p u l se s l i e i n t h e s m al l
,
-

i n t e rv al s q1 q, d ql e t c p l dp l e t c t h a t i s t h a t th e
, .
, , , , .

ph a se p o in t l i e s i n th e el em e nt dql d q2
-
d q lp l dp 2 dpy do
of t h e ph a se sp ac e -

E
kT
e da
w t

Th e n t h e m e a n of th e ene r g y f ol l ow s i n th e u su a l

Li k e wi s e ,

W e th e n fo rm

1
[E E
W ( ll
5 ’
H a
1 40 T HE Q U A NT U M T H E ORY
T h e re fore ,

dE
e
‘
k T2
dT

We a l so a r ri v e at the sa m e f orm u l a i f i n s te a d o f th e c l a s si c a l
“

c a n on i c al d i stri b u ti on fu n ct i on , w e st a r t f rom t h e q u a n t u m d i st ri b u t i on
fu n ct i on

58 Th e m e a n e n er gy di a t i on o f fre q u e n cy v i n t h e v ol u m e
of r a 1) is
E = vu d u y ,
wh e re th e m on oc hrom a t i c d e n si ty o f r a d i a t i o n i s

8 1rK y 8 l r h1/
‘ 3
1
c 03 2 3

kT _
1

P la n c k s L a w i s t a en a s t h e b a s i s ( Cf , for e x a m p l e , M P la nc ,
k k
’
if . . .

L e c t u res o n t h e Th e ory o f R a d i a t i o n , E n g l Tra n sl ) . .

A c c o r d i n g t o f o rm u l a ( 2 8 ) d e d u c e d i n t h e p r e v i o u s n o t e , i t t h e r e f o r e
f ol l ows th a t
hv
d u ll 2 4
8 1rh v vd ue fi '
2
5 z k T3 s vd v
dT

c
3
(
e
’°T
1 )
If w e el i m in at e T on th e ri ght h an d -
si de by su b stit u t i n
g
8 m" 3
f ol l o w s th a t
val u e 1 1 it
onl y
u y vd V o by

2 7
E . hu

Th e d t e r m o n th e ri gh t i s r e qu i r e d by th e U n d u l a tory Th e ory
s ec o n

for a t e a c h p oi n t of t h e v ol u m e v t h e m os t v a ri e d t r a i n s o f w a v e s o f
r a d i a t i on c r oss o n e a n ot h er s p a t h s w i t h e v e r p si b l e a m pl i t u d e a n d
’

y o s

pha s e The i n t erf e re n c e o f a l l t h es e wa v e s t h u s g e n e r at e s a t t h e p oi n t

.

c o n s i d e re d a n i n t e n si ty wh i ch v a ri es c on t i n u a l l y a n d h e n c e th e e n er gy
, ,

of the v ol u m e v a l s o v a ri e s . If w e c al c u l a t e t h e m ea n of th e sq u a r e

of th e e n ergy , i . e . H , w e fin d p re c i sel y th e se c o n d t erm of the a b ov e

for m u l a ( Cf for e x a m pl e H A L or en tz L e s the or i e s s t at i st iqu e s e n

. .
, , . .
,
’

th e r m od y n am i qu e ( Te u b n er L e i p zi g a n d B e rl i n ) 1 9 1 6 pp 1 1 4 c l s eq )
, , , . .

Th e fi rs t t e r m i s not h owe v e r e x pl a i n e d b y t h e c l a s si ca l u n d u l a t o ry
, ,

th e ory On t h e ot h e r h an d i t b e c om e s e n d o we d w i t h m e a n i n g i f w e
.
,

su pp o se t h a t t h e r a d i a n t e n e rg o n s i s t s o f a er t a i n wh o l e nu m b er
y c c
 N O TE S A ND RE F E RE N CE S 14 1
( )n fi n i t e e n e rgy c o m pl e x e s o f t h e v a l u e h F o r t h en E n h
of v.
'
y ,

a n d t h e r e f ore E n h wh e re n i s th e m e a n a bo u t wh i c h t h e n u m be r y ,

n v ari es If 8 n n b e t h e v a ri a t i on o f t h e n u m b e r n
. t h en i t ,

f ol l o w s th a t E E th wh e r e 3 8 Me
8 ” B u t a cc or di n g to e,
°
y .
,

a w e l l k n o wn l a w o f s t a t i st i c s 8 ( Cf fo r e x am pl e H A Lor en tz
-
n 3
.
, .
, , . .
,

l oc ci t . 26 a n d .
,
H e n c e 2 R h g z
E h Th i s i s ex a c t l y th e 3
y v.

firs t t erm i n th e a bo ve form u l a .

84 A E i ns te i n A n n ( 1 Ph s 17 1 44
.
y , . . .
,

55 J J Thom son Co n d u c t i o n o f E l ec t ri c i t y t h r ou h G a se s
. .
g , .

56 A E i ns te i n A n n ( 1 Phy s 17 1 4 7
.
, . . .
,

57 Of R P o hl a n d P P r i n gs he i m D i e l i c hte l e kt r i s c h en E rs ch e i n
. . .
,

u n g e n S am m l u n g V i e w e g H e ft 1 ( B r a u n s c hw e i g
.

58 A E i n s te i n A n n ( 1 Ph y s 17 1 4 5
.
, . . .
,

59 R A Mi l l i ka n Ph y s Z e i t s c h r 17 2 1 7
. .
, . .
,

so A c c or d i n g t o Poh l a n d P r i ngs he i m w e h a v e t o di st i n gu i s h be t w ee n ,

t h e nor ma l a n d t h e se le c ti ve ph ot o eff ec t : i n t h e c as e of t h e n orm a l -

e ff ec t th e n u m b er of e l e c t ro n s to rn o ff ( p er c a l ori e of t h e l i gh t e n e r gy -

a bso rb e d ) i s i n d e p e n d e n t of t h e ori e n ta t i o n o f t h e e l e c tri c al v e c t or of t h e

l i gh t wa v e a n d i n cre as e s s t a rt i n g fr om a n u pp er l i m i t o f t h e w ave
-

, ,

l e n gt h i n g e n eral u n i form l y a s t h e w av e l e n gt h d e c r e ase s

,
In th e c a s e -
.

o f th e se l e c t i v e e ff e c t o n t h e o t h e r h a n d wh i c h o n ly a pp ears wh en t h e
, ,

e l e c tr i c al v e c t or o f t h e li gh t w a ve p o sse sses a c o m p on en t v e r ti ca l t o t h e -

m eta l l i c su rf a c e t h e n u m b e r of e l e c t ron s to r n o fi ( p e r c a l ori e of li gh t

,

e n e rg y a b sorb e d ) s h o w s a d eci d e d m axi m u m a t a d e fin i t e w a v e l e n gt h -

.

5 1 0k B a r k l a Phi l M a g 7 54 3 8 1 2 ; 15 2 1 8
.
, Ja h rb d R a d i o ak . .
, , ,
. . .

t i vi t at u E l e kt r on i k 5 p 2 3 9 1 9 08 — O h B a r k l a a n d S a d l e r Ph i l M ag
.
, , .
,
. .
, . .

17 7 39 , O h B a r k l a Ja h r b d R a d i oa kt i v i t at u E l e kt ro n i k 1 9 1 0 p
.
-
.
, . . .
, , .

1 2 — M dc B r ogl i e C R 2 5 M a y a n d 15 J u n e 1 9 1 4 p 1 7 8 5 — Oh B a r k la
. .
, . .
, . . .
,

Phi l M a g 16 55 0 —E Wagne r A nn d Phy s 46 86 8

. .
, . Si t . . . . .
,

zu n gs b e r d b a y e r A k a d 1 9 1 6 p 3 3
. . . . , . .

52 D L We bster Pr o c Am eri c A ca d 2 9 0
. . Phy si c R evi e w 7
, . . .
, .
, ,

5 87
SS E . Wa gn er , An n . d Phy s . .
46, 8 68
64 0f .
, for exa m pl e , E . Wa gner Phy s , . Z e i t schr . 18 4 4 3 , Th e
v al u e t h a t Wa gner c al c u l a t e s for h i s : h 6 62 10 — 27
.

65 W D u a n e a n d F L Hu n t Ph ysi c R e vi e w 6 16 6
. . .
, .
, ,

56 A W Hu l l a n d M R i ce P r oc A m e ri c A c a d 2 2 6 5
. . .
, . . .
,

M E Wa gne r Ph y s Z e i t sch r 18 4 40 cl seq

. Ann , . .
,
. . (1 . Phys . 57 ,

401
ss F . D essa uer an d E . B ac k ,
B er . d d e u t sch
. .
p hy sik al G e s . .
21 1 68
,

F r a nc k an d G . Her tz V erh an d l d d e u t sc h
, . . .
p h ysik a l . G es .
16 ,

5 12
70Th e cr i t i c a l pote n tia l m ea su re d b y F r a nc k a n d Her tz am ou nted to
3 elec tro sta ti c u ni ts an d the refore the cri ti ca l en e rgy
7

of
:

th e
49

el e c tro n
vol ts

is
$6
0
,

10 -
10

300
 1 4s T HE Q U A NT U M T H EORY
Th e w ave -
le n g t h A of t h e m e rc u ry l i n e e m itt e d is

A 2 5 864 -
5 ,

He n c e w e m u s t ge t
—5
c a v) .
W
.

"
h l 'e h "

i
“

E
’ ‘

10
3 -
10
1 0—2 7

an d h
t is is ingood a g reem e n t wi t h th e r e su l ts o f oth e r m ea su re m en t s .

7 1 Cf f or e x a m pl e J S ta r k P ri n zi p i en d er A t om d y n a m i k II ( S
.
, , .
,
. .

Hir zel L ei p zi g
, Ch s IV a n d V . .

72 J S tar k B er d d e u t s c h ph y s G e s 10 7 1 3 ( 19 08 )
.
, . Phy s Z eit schr
. . . .
,
. .

8, 9 1 3 9 7 67
,

Ca n a l r a y s a r e po si t ively c h a rge d p arti c l e s o f m a t t e r , whi c h m ov e i n a

-

va c u u m t u b e i n t h e d i r e c ti o n : a n od e t o c a t h od e ; t h e l a t t er i s p i erce d

wi t h h ol es thr ou gh wh i c h t h e c a n a l ray s p a ss i n t o th e spa c e b ehi n d th e -

c a th o d e If w e g e n era t e s u c h c a n a l ra y s i n a v a c u u m t u b e fi ll e d wi t h
.
-

h y drog e n , w e fin d t h at th e seri e s l i n e s of hy dr og en are e m i tted N ow , .

i f w e o b se rve t hi s e m i s si on s p e c tr osc op i c a l l y fr om t h e fron t , t h a t i s, s o

“ ”

t h at t h e ca n a l ra y s a r e m ovi n g t ow a r d s t h e ob serve r, w e s e e , fir s t l y , a t
-

i s u su a l p l a c e i n t h e sp e c t r u m , t h e s h a rp s e r i e s l i n e ( l i n e o f res t ,
t “
in
t e n si t y o f s e c on dl y , w e s e e d i sp l a c e d t ow a rd s t h e vi ol e t , a

b roa d en e d st ri p ( l i n e of m o t i on , “
i n te n si t y of m ot i on
”
or
“
dyn a m i c
i n t e n si t y Th e se l i n es r e p re s e n t t h e s e ri e s l i n e e m i t t e d b y t h e
m ovi n g c a n a l ra y p a rt i cl es , whi c h i s d i s pl a c e d t o wa r d s th e r e gi on o f
-

hi gh e r frequ en c i e s on a c c ou n t of t h e D op p l er e ff ec t S i n c e th e c a n a l r ay s .
-

d o n ot p o sse ss a si n g l e u n i f or m v e l o c i ty , a n d si n c e p a rt i c l e s w i th a l l
p ossi b l e v el oc i ti es oc c u r, the di spl a c e d st ri p i s n ot sh arp , b u t sof t en e d
a n d b roa d e n e d Th e i s t h e re f ore e m i tt e d wh e n t h e
“
i n t e n si t y a t r e s t
.

k m o v i n g c a n a l p ar t i c l e s s t ri k e g ”
q u i c l y .
“
r e s t i n m o l e c u l e s ,
i e g a s . .

m o l ecu l e s whi c h a r e m ovi n g c om p ara ti v ely sl o wl y a n d i rr e g u l arl y , a n d

e x ci te these w em i t the s e r i e s l i ne s
”
Th e i n t e n si ty o f m ot i o n , on t h e
“
.

o t h er h a n d , i s e xci t e d b y t he u n i d i r ecti on a l l y m ov i n g ca n a l p a r ti c le s

the m se l ves , wh e n t h e y h i t gas m ol e c u l es -

.

N ow , i t i s very r e m ar k a b l e t h a t t h e i n t e rva l b e t w e en t h e i n t en si t y o f
r es t a n d t h a t of m o t i on i s n ot fill e d i n , b u t t h a t t h e e m i ssi o n of th e i n

te n si ty of m ot i on b e c om es o b serva b l e o n ly a b ov e a c ert a i n v e l oc i ty .

S ta r k i n t erp r e t e d t h i s f ac t i n te rm s of th e l i gh t qu a n t u m h yp ot h e si s -

t h u s : If firm) i s t h e k i n e t i c e n ergy o f a ca n a l r a y p arti c l e , a n d if t h e

? -

fra c t i on a §mv ( a 2
1 ) i s tra n sf orm e d i n t o a li gh t q u a n t u m hv u pon -

h m ol e cu l e , t h e n w e m u st h a ve hy m v ; t h a t i s, t h e
g
g
c ol li si on wi t a ga s
-

s pe ctral l in e of fre qu en cy if can be g e n erate d on l

y by c a n a l ra y s,
-
th e
2k} !
ve l o ci ty o f wh i c h 2
a m
Th e prop ort i on a l i t y b e t w e e n th e c ri ti c a l v e l oc i ty a n d /7 h a s be en
N 1
fa i rl y well b orn e ou t .

It s h ou l d he rem ar e d h er e t h at J S ta r k . k h a s l a t el y ab an don e d the

t h eo ry of li gh t qu an t a ( Cf J S ta r k , V erb
-
. . . . d d eu t sch physi k
. . . G e s 16, .

304
 N O T E S A ND RE FERE NCE S 1 43

, P h
S ta/r k
y s Z e i t s c.h r 9, 8 5 ,
3 5 6 .
— J S ta r k an d W . .

S teu bi n g, Ph y s Z ei t sc hr 9, 4 8 1 — J S ta r k , Ph s Z ei t sc h r 9 ,
. .
y . . .

8 89
In t h e se p a p e rs J S ta r k d e f e n d s th e vi e w t h a t t h e b an d sp e c t r a a re
.
-

e m i tt e d wh e n a “ val e n c e l ec t r o n b e l o n gi n g t o th e a tom or m ol e c u l e
y
i s p u sh e d ou t of i t s n orm a l p osi t i on a n d t h e n r e t u r n s a g ain t o i t s i ni t i al
po si ti on , c ou nt erb al an c i n g t h e w or k d on e i n d i spl ac em e n t If t h e .

e n e rg y of d e f o rm a t i on ( val e n c h g d gh
y e n e rg y ) E i s c a n e i n t o a l i t

q u a n t u m , t h en w e m u st have hp E, i . e . v
2 55 . All l i n e s of the

b a n d m u st t h ere f ore l i e b e l o w t h e e dg e u
2 . If t h e v a l en cy en e r gy
E i s c h a n g e d b y c h em i c a l proce sses , th e b a n d -
s p ec tr u m m u st b e d i s
pl a ce d accordi n gl y .

7l A E i ns te i n , A n n d Phy s 17 , 1 4 8
. . .

7 8 J S ta r k , Ph y s Z ei tsc h r 9 , 8 89 ( 1 9 08 )
. . A n n (1 Phy s 38 , 4 6 7
. . . .

Th e f u n d a m e n t a l l a w o f ph ot oc h e m i c a l d e c om p osi t i o n en u n c i a t e d b y
Sta r k a n d E i n s tei n s t ate s : If a m ol e c u l e d i ssoc i a t es a t a ll owi n g t o t h e
a b s orp t i o n o f ra d i ati on o f f req u en c y i f , t h e n i t wi l l a b sorb a n a m o u n t o f

e n ergy hv wh e n i t d i ssoc i a t e s Thi s . e n e rgy , t her e fore , re pre se n t s th e

h eat of rea c ti on , whi c h wi ll b e se t f re e u p on r ec o m b i n a t i on of t he
pro d u cts o f decom p osi ti on .

Th i s l a w w a s l a t e r d e d u c e d b y A E i n s te i n for t h e r a n ge of val i d i ty o f
.

Wi en s L a w of Ra d i a t i on wi t h ou t t h e a ssi st a n c e of t h e l i gh t qu a n t u m
’
-

hyp ot h e si s , by p u rely t herm ody n a m i c al m e t h od s ( Of An n d Phy s . . . . .

37 , 8 3 2 a n d 38 , 88 1

76 E War bu r g, B e r d e rl A a d d W i ss 1 9 1 1 , p 7 4 6 ; 1 9 1 3 , p
. . . B . k . . . . .

6 4 4 ; 1 9 1 4 , p 8 7 2 ; 19 1 5 , p 2 8 0; 1 9 1 6 , p 3 1 4 ; 1 9 1 8 , pp 3 00, 12 28
. . Cf . . . .

a l so
“
N a t u rwi ss e n sc h a ften , 5, 4 8 9
N E A L or en tz, Phy s Z ei tsch r 11, 1 2 50
. . . .

78 M P l a nc k , B er d d e u ts c h p hy si k a l G 6 8 13, 1 3 8
. . . . An n d . . . .

Phys 37 , 6 12
.

79 On ac cou n t of t h e c on t i n u ou s ( c l a ssi c al ) ab sorp ti on , a l l en ergy va l u es

of t h e os ci ll a t o r i n a n e l e m en t a r
y r e gi on ,
s a y b et w e e n We an d ( n 1 ) s,

a re e qu a l ly p r ob a b l e Th e m e a n en ergy i n t h e n t h e l e m e n t ary re g i on
.

i s , t h ere f or e ,

(
Z (n as .

F rom th e can oni ca l l a w o f di stri b u ti on e xt e n ded i n th e s en se of t he

q u ant u m t h eo ry , i t th e n fo ll ow s t h a t
144 T HE Q U A NT U M T H E ORY

( c f . n ote If w e fu rt h er se t a
s hv i t f oll o ws t h a t
hv
U —
2

In pl ac e of rel a ti on ( 7 ) of t h e t ex t w e ge t h e re

and d s t o P l a n ck s L a w of R a di a t i on
h
t i s le a
’
.

SO M P la n ck Si t zu n gsb e r d E gl Pre u ss A k a d
.
, d Wi s s 3 A p r il . . . . . . .
,

1 9 1 3 p 3 5 0; i bi d 3 0 J u l y 1 9 1 4 p 9 1 8 ; i bi d 8 Ju ly 1 9 1 5 p 5 1 2
, . .
, , . .
, , . .

81 A E i n s te i n a n d O S ter n A n n (1 Phy s 40 5 5 1
. .
, . . .
,

82 W N e r n s t V erh a n d l d d eu t sc h p h y s i k a l G6 8 18 8 3
.
, . . . . .
,

88 F . R i cha r z, W i ed em A n n 52, 4 1 0 . .

Re po rt b y P
84 . L a ngevi n a t t h e Sol va y Con gress in Brusse ls , 19 1 1 .

Of A E u c e n , D i e
. . k h
T eori e d e r St ra l u n u n d d er h g Q u an t en . A b h an d l . d .

deu t sc h Bu n sen .
-
G es .
, W
Nr 7
( K n a pp Ha l l e
. pp 3 1 8 e t seq
.
, . .

85 A E i n ste i n a n d
. , W J d e Ha a s V e rh a n d l d deu tsc h p hysik a l Ge s
. . . . . . .

17 , 1 5 2 , 2 03 , 4 20 — A E i n ste i n i bid 1 8 1 7 3
, , . W J de .
-
. .

Haa s , i bid , 18, 4 2 3 .

86 E ec , A n n d Ph ys 60
. B k ,
1 09 . . .

87 R e po rt b y P la/nc a t t h e S olv a y Con gre ss i n Brusse l s , 1 9 1 1

k Se e .

A E u c en , D i e Th eori e d e r St r a h l u n g u n d d er
. k u a n ten A b h an d l d Q . . .

d eu tsc h u nse n Ge s , N r 7 ( W Kn a pp , Hall e

. B -
. p 77
. . . .

88 If q i s t h e e l on g a t i o n o f a li n earl y vi b r a t i n g e l ec t ro n o f m as s m ( o s
c il l a to r ) a n d if i ts pe ri o d o f osc i ll a t i on , t h en t h e e n ergy o f t hi s configu r

a ti o n is
I

;
)
”
( 21 m) 2
q .

Th efirst te rm re pre sen ts t h e ki n et i c an d th e secon d th e pote n ti al en ergy .

N ow t h e i m pu lse ( t h e m om e n t u m ) i s p m
% . Th ere fore we m a y wri te
,

2 2
2 1r y mq?
 N O TE S A ND REFE RE N CE S 1 45
The . U = co n st , t h a t i s , t h ose c urv es i n t h e ph ase pl a n e , wh i c h
c ur ve s .
-

co rres pon d to t h e s ta te s o f cons ta n t en e r gy o f t he o sc i ll a tor , ar e t h ere fore

e l li pses wi t h t h e se m i ax es -

F or defin i te
a U we get a c om p l e te ly de fini te elli pse
va l u e of Th e .

phase poi n t -
of t h e osc i ll a tors wo ul d c o n t i n u a ll y re vol ve i n t hi s e lli pse ,

if t he e l ec tron , wi t hou t e m i tti n g or a b so rb i n g , w ere to ex ecu te pure h ar

m on i c osc i ll a ti on s for t h en i ts en erg y wou l d re m ai n perm an en t ly c on st an t .

If we a ll o w U to v a ry c on tin u ou sly , i e if w e g i ve i t o t h er a n d a g a i n . .

o t h e r val u es i n c on ti n u ou s su c ce ss i on , we
ge t an u n li m i te d m an i fol d o f
c on c e n tri c e ll i ps es .

Th e qu an tu m t heo ry , as f orm u l a te d i n ( 3 0) i n t h e te xt , se l e c ts fro m thi s

i nfini te m a ni fol d a d i s cr e te se t o f e l li pse s , a n d di sti n gu i sh e s t h e m as t h e
q u a n ti sed elli pse s w hi c h c o rres po n d, t o t h e c h arac t eris t i c s t a te s
”
of

t h e o scill a to r To t he se b e lon g th e
.
qu a n tu m e n e rgy v a lu es U0, UI, -

N ow th e n th e l li pse e n c l oses an a re a n h . Th e a rea of t h e n th e lli pse

is , however ,

hence we m us t h ave
%
l
_
nh i . s . U1; 3 ”b y

t ha t i s , i n the n th qu a n tu m s ta te the osci l la tor p osses ses a n a mou nt o f

e ner gy n e n hv .

89 A S om merfe l d , Phy s Z e i tsc h r 12, 1 05 7

.
— Re port b A
.
y . .

S ommerfe ld a t t h e So l va y Co n gre ss in B russe ls , 1 9 1 1 Of A E u c ken , . . .

Di e Theori e d e r S tra h l u n g u n d d er u an ten A b h an d l d d e u tsc h Q . . . .

Bu n sen Ges , N r 7 ( W Kn app , Ha ll e

-
. . p 2 52
. . .

90Re po rt b y S om merfe ld a t t h e So l va y Co n ress , 1 9 1 1

.

g .

9 1 A S om merf e l d a n d P De bye , A n n (1 Phy s 41 , 8 7 3

. . . . .

9 0i f o r ex am pl e , t h e rec e n t su m m ar b E S h d i D
8 y y c r b n ger , er .

E n er gi e i n h al t d er F es tk Orp e r i m Li c h te d e r n eu ere n F orsc h u n g Phys . .

Z ei tsc h r 20, 42 0, 4 50, 4 7 4

. A c om pl e te se t of re feren ces ae com

93 gram m e a tom of a su b sta n c e th e a tom i c wei gh t of whi c h is a

0n e -

, ,

i s d e fin e d as t h e q u a n ti t y a gra m m es o f t he s u b st a n ce F or e x a m p l e .
,

o n e g ra m m e a tom o f c o pp e r i s e qu a l t o
-
gra m m e s of c oppe r si n c e ,

i s t h e a t omi c w e i gh t of c o pp e r E xa c t l y ana l o g ou s i s t h e .

d efin i ti on o f the gra m m e m ol ec u l e (a l so ca l l ed -

On e gram m e
m ol ec u l e o f oxy gen i s 3 2 gra m m e s o f ox y g en f or t h e m ol ec ul ar wei gh t ,

If e i s t he s pec i fic hea tmi c we i gh t a , i t si gni fies

of a su b s ta n c e of a to

tha t one gr a mm e of the su b sta n ce requ i re s an a m oun t o f h ea t c to ra i se

i ts te m pera tu re b y 1 0
°
Hen c e we m u st comm u ni ca te to a gra m m e a to m
.
-

10
1 46 T HE Q UA NT U M T H EORY
of the su bs ta n ce , i . s. to a gra m m es o f C it ,
ea i n a n a m ou n t o f hea t
o rd e r t o ra i se i t s t e m pera tu r e b y 1 C i s t h e n c a ll ed t h e a tom i c he a t
°
C . .

94 Th e e qu a l i ty o f t h e m ea n p o t e n t i a l a n d t h e m e a n ki n e t i c e n e r gi e s i s
tr u e h e re a s i n t h e c a se O f th e l i n e a r P l a n ck osc i l l a t or ( vi b ra t i n g e l ec tron ) ,
o f n o te 4 1
. Thi s e qu a l i t y i s , i n g en era l , a l wa y s p re se n t wh en t h e f orc e s
.

whi c h a ct u p on th e a t om s a nd rest ore t h em t o t h ei r p osi ti on s o f rest

r o p o si t i o n s i i h v e di sp l a c em ent s of t h e
( ze ) a re l n e a r
f u n c t o n s o f t e r e l a t i
a t om s , t ha t i s , wh e n t h e f o rc e i s h p p
“ ”
q u a si e l a s t i c , t a t i s , r o o rt i o n a l -

t o t h e di spl a cem e n t f r om th e ze ro p o si t i on Cf i n t hi s c onn exi on . .

L B ol tzm a n n , Wi en er Be r 63
. 7 31 . a nd F R i cha r z, Wi ed . .

A n n 67 . 7 02.

9 5 D u lon g a n d P e ti t , An n d e c h i m e t d e ph ys 10, 3 9 5 . . .

96 Th e qu a n t i ty u su a l l y o b ta i n e d b y m e a su re m e n t i s n o t t h e a t om i c
hea t a t c on sta n t vol u m e C”, b u t th e a t om i c h ea t a t c on sta n t pre ssu re 019 .

F or t h i s we ge t va l u es whi c h i n g en era l fl u c tu a t e a b ou t t h e va l u e 6 4
c al / d eg
. Th e c a l c u l a ti on o f C, fr om 01, i s b a se d on th e t h erm o
.

dyna mi cal l y dedu c e d f orm u l a

013 — 0”

wh ere a i s th e cu b i ca l c oe ffici en t of t herm a l ex pa n si on , 1: t h e ( i so t h erm a l )

cu b i ca l c om pressi bi li ty an d V t he a t o mi c vol u m e
a t om i c we i ght
,

97 Fi g . we fin d
°
f or sil ver at 0 C .

a l u m in i u m 58 C
°
.

co pper 17 0
°
.

l ea d °
17 C .

i odi n e °
25 C .

zi n c 17 C
°
.

9S E . H We ber
P oggen d An n 147 , 3 1 1
.
, 154 , 3 6 7 55 3
. .

99 A s a p o s si b l e w a y ou t , t h e a ggl o m e ra t i on h yp o t h e si s , su pp ort e d b y

F R i c ha r z [ Marb u rg er Ber 1 9 04 , p
. C ene d i c s ( A n n d Ph y s 42 ,
. . . B k . . .

a n d o t h ers , h a s b ee n
133 p u t f o rwa r d A cc ordi n g t o t hi s , a s t h e .

te m pe ra tu re f a l l s t h e n u m b er of d e g ree s o f f ree d o m o f t h e sy ste m

di m in i she s b y f reezi n g i n , a s i t were , i n t ha t c erta i n l in a ges b ec om e
“ -
k
c o m pl e t el y ri gi d A c c ordi n g t o t h i s , h owever , th e c o m pre ssi b il i ty s h ou l d
.

d ec rea se grea tl y a s t he tem p era ture fal l s , whi c h , a c c ordi n g t o E Gr it .

nei sen s
’
m ea sure m en t s i s n o t t h e c a se [ V erb d d eu tsc h phy s G es 13 . . . . .
,

49 1 Com pa re a l so i n t h i s c onn exi on t h e re po rt of E S chr o .

d i nger qu ot ed i n n o t e 9 2 .

100A E i n s te i n , Ann d Phy s 22 , 1 8 0, 8 00

. . . .

1 01 Of A E i ns te i n , An n d Phy s 35 , 6 8 3 ff
. . a l so t h e re p ort b y
. . . .

E i n ste i n a t t h e Sol va y Con gr e ss i n Bru sse l s , 1 9 1 1 ; see A E u c ken , D i e .

Th e ori e d er S tra h l u n g u n d d er u a n t en Ab ha n d l d d eu t sc h B un sen Ges ,Q . . . .

-
.

N r 7 ( W Kna pp , Hal l e
. . pp 3 3 0e t seq . .

1 02 A E i ns te i n , A nn d Ph s 34 , 1 7 0, 59 0 35 , 6 7 9
.
y . . .

108 Th e n a t ure o f t h e d e pen d en ce of t h e f re u en c

q y v on t h e t h ree
 N O T ES A N D REFERE N CES 1 47

qu an ti ti es A , p, it m ay , ac cordi n g t o E i ns te i n ( loo c it ) , b e ob tai ne d b y a .

si m pl e di m e n si on a l c al c u l a ti on If we a ssu m e t h a t 1! d e pe n ds on l y on t he
.

t he bo y , td h en an e qu a ti on o f the foll o wi n g form m u st h ol d

V 2 C s m x
. dy . l€
z
o

C i s h ere a nu m eri c a l constan t ; to, y a n d z ar e nu m b ers w hi c h re m a i n to

b e determ i ned .

Th e di m en si on s o f t he frequ e nc y [ v] are [ t 1] th e d i m en si on s of m a nd
d a re [ m] an d [ l ] , a n d t he d i m e nsi on s of t h e c om press i b i l i ty or foll o w from
i ts de fini ti on :
i n cre ase i n vo l u me

f
[p I
:f 1
1 su r ac e
[ lm }
2
_ t
ressu re or ce

1
t [m
ad
ly u p s
]
" -

He n c e
a: z 0; y z 0;
from whi c h we get
—
x 8;
We have t h ere fore ,

Le t N b e A voga d r o s n u m b er , i e t h e n u m b e r of a tom s i n t h e gra m m e

’
. .

a to m Th en th e a to m i c w e i ght o f t h e b od y i s n u m eri c a l l y e qu a l to t h e
.

m ass of t he gra mm e a tom , i e -

. .

If w e i m a gi n e t h e a to m s arran ged u po n a cu b i c a l
si d e s d , t h e n t h e d en si ty m u s t s a t i sf t h e a t i on
y e qu

m
P
=
a§

d = m§ p
"
5

d
3 § = A _ 2
3
N p 3 §
p

from whi c h , it follows tha t

1 48 T HE Q UA N T UM T HEORY
E i nste i n dete rm i n es the fac to r 0 b y a ssu m i n g si m ply t h a t on ly th e
t w e n ty si x n e i gh b ou ri n g a to m s a c t u pon t h e d i sp l ac ed a to m
-
.

L i n de m a nn Phy s Z e i tsc h r 11 6 09 L i ndem a n n s

’
104 F A . .
, . .
,

form u la m ay b e shortly de du c e d t hu s : Le t r a si n ( 2 t) be the e lon g a 7ry

t i o n o f a n a to m whi c h i s vi b ra ti n g wi t h t h e a m pli tu d e a an d t h e frequ e n c y

v. Th e m e a n e n ergy o f thi s a t om i s

m dr m
( )
2

( zq r
2
( 27 W) 2
a 2 2
21r y
2
ma z
.

2 dt 2

A t t he m el tin g p oi n t , ac cord i n g t o L i nde ma n n s con c e pti on , a i s o f t h e

’
-

sa m e ord e r as d ( di s t a n c e a p a rt of a tom s) On t h e o t h er h a n d , th e m ea n .

e n ergy o f t h e a to m s a t hi gh t e m pe ra t u res 3 k T, or , a t t h e m el ti n g poi nt -

3kT s (
. Th e m e l t i n g po i n t , as a ru l e , i s h i gh
-

) F ro m t hi s i t fo ll ow s t h at .

2 1r z 2
y md = 3 k T:
2

c ons t Tfim id
V ‘ '
l
. ,

Bu t we h ave ( se e n ote 1 03 )

A .

He n ce
} A i N iA iN i i T3 A" l
- -

const . T p c o n st .
p .

105 E Gr une i sen , An n d Phys 39 , 2 9 1 e t seq

. . . . .

106 E Ma de l u ng, N a c h r ( 1 k g ] G e s d Wi ss zu
. .ott i n ge n , m a the m
. . . . . G .

h
p y s i k al K l a s se.1 9 0 9 , p 1 0 0, a n d 1 9 1 0, p 1 . . .

107 W S u ther la nd , Ph i l M a g
. 20, 6 57 . .

108 If n a n d x a r e the c oe ffi c i e n t s o f r e f r a ct i on a n d ext i n c t i o n o f a

s u b st a n ce re s p e c t i v e l y , t h e n , a cco r d i n g to M a x we l l s Th e o ry , i t s r e fle c t
’

i n g p ow e r i s
2

R ( n x
.
2
(n K

If w e r eq u i re th e p oi n t of m axi m u m r e fl e c t i o n w e h a ve , to f orm t he
aR 0, whi ch g ives a ft er red u ct i on th e f ol l owi n g r el a t i o n
e qu a t i on =

'
s an f
2m i € = a
K +
V

F ro m t h i s w e se e h a t t h e p o si t i o n
t of m axi m u m fl e c t i on d o e s
re n ot

Q5
c oi n c i de e xac tly w i t h t h e p os i t i o n o f
b u t t h a t i t l i es t h e n ea rer t o i t , t h e l e s s t h e c oe ffi c i e n t of re r a cti o n
m a x im u m a b sor p t i o n
(f av

v a r i e s w i t h t h e f re qu e n cy O n t h e o t h e r h an d , t h e p oi n t o f m axi m u m
.

a b sorp ti on li e s, a cc or di n g to t h e d i sp e rs i on t h eory , i n t h e i m m edi a t e

n e i gh b o u rh o o d o f th e n a t u ra l f r eq u e n cy v, “

109 H R u ben s an d E E N i c ho ls , W i e d em A n n 60, 4 1 8

. . . A l so . .
 N O TES A N D RE FERE N CE S 1 49
H . Ru ben s H Hol lna gel Be r
a nd .
, . d kgl p r e u ss A ka d d W i ss
. . . . . . 1 9 10,
p 45 ;
. H H ol l na ge l D i ss e rt Be rl i n 1 9 1 0 ; H
.
, . . R u ben s , Be r d k gl . . .

p re u ss . A k a d d W i ss 1 9 1 3 p 5 1 3 ; H Ru ben s
. . .
, . . and H v Wa r ten ber g,
. .

i bi d 19 14 , p . 1 69 .

As a n e xa m pl e w e gi v e e re th e h fol l o w i n g sm a l l t abl e i n whi ch A

d e n otes t h e w a ve -
gh
l en t of t h e r e si d u al ray s as gi ve n b y t h e a b ov e ,

i nv e st i g a to rs .

52 TIC]
K B )?
A gBl '

98 8u '

,
. Tl Bl ‘

1 10 Cf .
, h o w ev e r , n ot e 1 08 .

111 W
N er ns t a n d F A L i ndema n n , S i t zu n gsb er d k gl p re u ss
. . . . . . .

A a d d W i ss 1 9 1 1 , p 4 9 4
k . . W N er ns t, A n n d Phy s 36 , 4 26
. . . . . .

112 Th e fo l l o w i n g s h or t t a b l e gi v e s t h e v a l u e s for y wh i c h a r e c a l c u l a t e d
from E i ns te in s f orm ul a
’
L i n d ema n n s f o r m u l a
’
f r om t h e
re s i d u a l ra y s a n d fro m t h e ob s e rve d a t o m i c h e a t
”
(see n o t e
“

a c c or di n g t o a n e m pi ri ca l f or m u l a ( 40) p rop o s e d b y N er ns t an d
Li nd ema n n F or m ore d e t a i l e d d a ta wi t h , i n p ar t , corr e ct e d n u m e ri c a l
.

f a ct ors se e 0 E . . B lom , An n . d Phy s

. .
42 1 39 7
,

”
S b 8 t a nce V a t omi c h ea t
ra y s
( N ern s t Di nd erna nn ) -

Al
Cu
Zn

113 W
N er ns t, E Kor ej , F A L i nd e ma n n , U n t e rs u c h u n g e n fibe r d i e
.
'

. . .

s p e zifi sc h e W ar m e b e i t i e f e n T e m pe ra t u r e n I 11 II S i t zu n gsb e r d . . . . . .

k gl p re u ss A a d d W i ss 1 9 10, 3 Ma rc h — W N er n s t, i d em III , ibid ,

. . k . . . . . . .

1 9 1 1 , 9 M a rc h — F A L i nd ema n n , id e m IV , i bi d 1 9 1 1 , 9 M a rc h — W
. . . . .

N er ns t a n d E A Li nde m a n n , id em V , i bi d , 1 9 1 1 , 2 7 A p ri l — W N er ns t
. . . . . .

and A L i n de m a n n , id e m V I , i bid , 1 9 12 , 1 2 D ec — W N er n s t, id em
F . . . . . .

V II , ibi d , 1 9 1 2 , 1 2 D ec —W N er n s t a n d E S chw er s , i d em VIII , loc

. . . . . .

ci t , 1 9 1 4
. W Ner nst, D e r E n e rgi e i nh al t f es te r S t o fi e An n d Ph ys
.
-
. . . . .

36 3 9 5
,

1 14 W N er nst D i e t h e ore t i sc h e n u n d ex pe ri m e n te ll e n G ru n dl a g e n d es
.
,

n e u e n W ar m e sa t ze s
( W Kn a pp Hal l e . .
,

118 Th e Fi rst La w sta t e s If d Q i s t h e h e a t s u p p lie d t o a sy st e m d A

’ ’
,
1 50 T HE Q UA NTU M T HEORY
th e work d on e on th e sy st e m fro m o u t si de then , th e i n c r e a se o f e ner gy
U of t h e sys t em i s gi ve n b y
' '
dU d Q dA .

Th e Se con d L a w sta t e s i f d Q i s su ppl i e d r ev e rsi b l y a t th e t e m p e ra tu r e

’

i
T, t h en i i s th e com pl et e d iff ere n t i al o f t h e e n t r o py S , h e nc e
T
d Q
dS __ .

Let us fol l ow He lm holtz a n d i n t rod u c e t h e “

f re e e n erg y E d efin e d by

F U T S .

Th e n i t f ol l ow s t h at
dF = d U T . dS T dS
. S . dT

dF = d A S dT
’
i . e. .

for ev e i y r e ve rsi b l e proc ess .

If t h e proc ess i s i sother m a l ( d T 0) th e n i t f ol l ow s t h a t d E d A

’

a fi n i t e c h a n g e o f sta t e E2 PI A If we s et A
’
o r, f or , . A, so

t hat A ’
i s t h e w or k ga i ne d w e ge t ,

Th at i s , t h e w or k g a i n e d i n th e i sotherma l r ever si ble p roce ss— whi c h i s ,

as m ay be sh o w n th e m a x i m u m ob t a i n a b l e— i s e qu a l t o th e d e c r e a se o f
,

f re e e n e r gy .

F u r t h er , i t fol l ows si n c e a t c o n sta n t v ol u m e V t h e w o rk d A

’
, 0,
t hat
OF F
( ) 57 7
V
s or T .

V
TS F U .

Th ere fore , form u l a ti n g t h es e ex p re ssi on s for t w o s ta t es , we ge t

{W } F
( . F .) U
( .
-

or , fi n al l y , i f we w r i t e for s hort UI U2 U
’

1 A
( )
!

U
’ ’
A T
8T V

a n e qu a t i on m u ch u se d
phy si c a l c h em i st ry
in .

a ccord i n g t o N er ns t s h ea t t h e o re m
’
Si n c e , n ow , ,

a
— i
A
( ) 8T l i m r =o

(A
’
U
’
) va n i s h e s for T 0, b e i n g a b ov e th e firs t or d er .

'
3 ( A U )
r

H e n ce lim O
T =O OT
an d h en c e a l so
Thi s i s eq u a ti on ( 39 ) of t h e t ext .

l i z—
E
F r om S , it fol l ows fu r th er t ha t
afl S? S,, or

82 -
31

a nd h en ce N er ns t s Th eor e m m ay b e
’
form u l a t e d th u s

T =O

t ha t i s , i n the ne i ghbou r hood o “

f t he a bs ol u te zer o a l l p r ocesses p r ow ed
w i thou t cha n ge o f en tr op y .

Cf , for ex a m pl e , M P l a n c k , Lect u res on Th erm o dyn a m i cs

1 18 . . P l a nc k .

goe s furt her t han N er n st i n asm u c h a s he postu l a te s t h a t no t on ly the

di fferen c e o f t h e e n tr o pi es S 2 S 1 i s zero a t a b sol u t e ze ro (se e pre vi ou s
n o te ) b u t a l so t h a t t h e i n d i vi du a l va l u es t h e m se l ve s b ec o m e zero He n c e , .

a c c ordi n g to P l a n c k , a t t h e a b so l u t e ze ro of t e m pera t u re t he en tr op y of

ever y chem i ca ll y homogen eou s bod y i s e qu a l to zer o From t h i s the c on .

cl us i o n gi ve n i n t h e t ext ,

as
8T

m ay b e dedu c ed i mm e di a t e ly . It fol l ows from the rel a t oni ( oc cu rri n g

i n t h e l as t n ot e )

an d from P la n c ks ’
ve rsi on of N er ns t s Th e ore m , t h a t F
’
U va n i s hes for
T 0, b ein g of hi gher or e r d t h an t h e fi rst .

He n c e
8 (F U) BU
l
12
1
1
) UT
0 or h
(
3T
S 0

or , fin al ly ,

11 7 F or l ow t e m p era tu re s , t h a t i s , for hi gh v alu es of x =

k
h,
7 " E i n s te i n
’
s

—x
fo rm u l a ( 34 ) t a ke s th e foll owi n g form : 01, 3Rx 2e
. Th e falli n g -
off a t

l ow t em pe ra t u res t he re f ore follows a n ex pon enti a l l a w ; m ore e x a c t ly , it

v a ri es as

00118 5
1

1 18 W . F A Li nde ma n n , Si t zu n gsb e r d k gl
N er n s t an d . . . . . preu ss . A ka d .

d . W is s 1 9 1 1 , p 4 9 4 ; Z ei tsc hr f E le t roc hem i e , 17 , 8 1 7

. . . . k
119 A E i n s te i n , A n n d Ph ys 35 , 6 7 9
. . . .

degre e s of freedom ; t he whol e bo dy ha s t here fore 3 N degree s of free dom .

As is pro ved in m ech a ni c s h owe ver (of R H Weber an d R Ga ns , . . . .

,
152 T HE Q U A NTU M T H EORY
Re pert ori u m d e r Physi E d 1 pp 1 7 5 e t a m ec h a n i c a l syste m o f
k . . .

3 N de grees o f free d o m h as 3 N n a t u ra l fre qu en c i es , a n d the m ost gener a l

sm a l l m o ti on of ea c h a tom con s i sts i n a su p erp os i ti on o the se 3 N n a tu r a l
f
fr equ en ci es .

121 P D ebye , A nn (1 Phy s

. 7 89 . . .

1 22 M . B
or n a n d Th v Kar m d n , Ph y s Z e i tsc h r 13 , 29 7
. .
14 , . .

15, 65 Cf a ls o M or n , A nn d Phy s 44 , 605 ( 1 9 1 4 )

. . B M or n , . . . . B
Dyn a m i d er Kr ist a ll gi tt e r ( Te u b n er , L e i p zi g a n d erli n
k B
123 Cf , for e x a m pl e , R Or tva y , I
. Jb er di e A b zii h l u n g d er E i ge nsch wi n
.

gu n gen f ester KOrp e r A n n d Phys 42, 7 4 5 . . . .

Or tva y co ns i d ers t h e n a t u ra l fre qu e n c i es of an e l a sti c c u b e , e ac h si de

o f whi c h h a s t h e l en g t h L Th ere are f ou n d t o b e t h ree grou ps o f n a tu ra l
.

fr equ en ci es The first two grou ps a re th e tr a n sver sa l frequ en ci es th e

.
,

t h ir d grou p i s t h e grou p of th e l on gi t u di n al frequ e n c i e s Tha t the t ra ns .

ve rsa l fre qu en c i e s f orm t wo grou p s ( m ore over i d e n t i c al ) i s e asi l y see n .

F or i n t h e c ase of a t ran sve rsa l vi b ra ti on whi c h is pro p a g a t e d i n say t he , , ,

di re ct i on of the x axi s two e qu a l a l te rn a ti ves are prob a b l e n am ely t h a t

-

, , ,

t h e p ar ti c l e s vi b ra t e p ar all el to t h e y o r to t h e z a xis In t h e c a se o f t h e -
.

l on g it u di n a l osc i ll at i on s h owe ver t h e re i s n a tu ra ll y on l y one gro u p ; for

, ,

i n t h e c ase of pro p a g a ti on a l on g th e x ax is t here i s o n l y one po ssi b il i ty -

n am e ly t h a t t h e p art i c l e s vi b ra t e p aral l e l t o t h e x a x i s
,
Th e fre qu e n c i e s -
.

o f t h e firs t t w o g rou ps a r e c h ara ct e ri se d b y t h e v a lu es

h d
th e t i r grou p b y
JW

He re c an d 0 ar e
,
th e ve l oc i t i e s of prop a ga ti on of tra ns ve rsa l and l on gi tu
,
di n a l wa ve s i n t h e bo y , d whe re a s posi tive whol e
a, b, c a re ar b i t rary

n u m be rs .
h f If t e re ore w e c a ll poss i b l egi ve a b
v a l u e s i n a ll,p o ssi b l e c om
,

b i n a ti on s ,
p o s si
w e ge t a ll t h eb l e t ra n s v e rs a l a n d l on g i t u d i n a l n a t u r a l fr e
e n c i e s wh i c h to g e t h e r f orm t h e e l ast i c s pe c tru m o f t h e c u b e If n o w
q u .
,

we i n q u i r e h o w m a n y t r a n sv e rs a l n a tu ra l f r e q u e n c i e s o f t h e fi rs t gro u p

fa ll b e low t his m e ans n ot hi n g el se t han i nqu i ri n g h ow m any t ri os o f

if ,

val u es ( a b c ) fu l fil t h e c on di t i o n
, ,

m+
/a
'

;
e a +
t
L

Im a gi n e a , b, c as c o or -
di na tes of a poi n t i n sp ac e . Th e n a ll poss ib le tri os
a re re prese n te d b y t h e t ot a l
p ”
of va lu e s l tt i in t of t h e “
(a , b , c) a c e o s -

posi ti ve Sp ace oc t an t , an d the ab ove qu esti on is ans wered b y c ou nti n g h ow -

21 ”
m an y l a tt i c e poi n ts are a t a d i st an c e l ess t h a n —1 from t he o rigi n ( 0, 0,
-

C
t
 N O TE S A ND R E FERE N CE S 15 8

ra di u s i s 2 5
. Si n c e n o w on e l a tt i c e -
poi n t i s ass i gn ed to e ve ry vo l u m e of
c
t
m agn i t u d e l — n a m el y , e very e le m en t ary cu b e — t he re q u i re d
n u m be r o f
l a tti c e -
poi nts provi d e d t ha t i t i s su ffi ci en tly la rg
,
e , i s e q u a l t o t h e vo l u m e

é
) c
”
of the posi ti ve spheric a l oc ta n t of rad i us i a i s e qu a l t o , . .

4 11 2 L V 3 y “

(
il
1 °
4 1r L
s 3 ct 3 c f
If V ’
L i s t he vol u m e o f th e g i ve n c u b i c al b o d y , t h e n th e n u m b e r
of th e t r a n sve rs e n at u ral fr eq u e n c i es be l o w if b e l on gi n g t o t h e fi r s t
grou p i s

Th e nu m b er b e l on gi ng to t h e s e c on d g ro u p i s th e sa m e , t ha t i s

2 2
2 2 1

F in a l l y , t he nu m b e r o f t h e l o n gi t u i n a l d . f re q u e n c i e s co rr e s pond i n g to
t h es e is

W e th u s ge t for t h e t ota l o f a l l n a t u ra l fr e q u e n c i e s b e l ow if

é
( )
1r
Z = ZI + Z2 + Z3 — 3
.

--
V 3
'
V 0

3 0
,
c
l

Th e t ota l of n a t u ra l f re q u e n c i e s i n t h e i n t e rva l y u

d i ffe r en ti a t i on with re sp ec t t o v

zet a 4 1r V
< a
0
,
'

t
C ‘

a nd h
t i s is j u st f orm u l a (4 3 ) of th e t e x t .

124 In form u l a ( 4 3 ) for Z ( y)d y l e t u s re pl a c e , ac cor ding to fo rm u l a ( 44 )

t ext t h e fac t or
'

of t he ,

1 2

Th e n i t f o l l o ws t h a t
154 T HE Q U A NT UM T H EORY

If w e n ow se t Km , w e ge t

4 w
x e dx

125 A t a bl e h owi ng h ow th e D ebye fu n ct i on C d ep e n d s on am is gi ven

s u ,

b y N er n s t ( D i e t h eor e t i sc h e n u n d ex p e ri m en t el l e n G ru n dl a g e n d es n e u e n
W arm e sa t zes W K n a pp Hal l e 1 9 1 8 p
. . In i t t h e sim pl e
, , .

E i nste i n f u n c ti on [ f orm ul a ( 3 4 ) o f t h e t ex t] i s a l so t ab u l a t e d .

1 26 If T i s g r ea t t h e n x i s sm a l l c om p a r e d w i t h 1 ; t h e n w e m a y
m ,

r ep l ac e i n th e i n t e r a l o f 4 5 c n t h e n u m era t or a n d e
‘v
1 by x x
g ( ) b y 1 i ,

i n t h e d e n om i n a t or It t h en f ol l ows t h a t
.

127 If T i s sm a ll , t hen xm i s l a r ge , and w e m ay re p l ac e th e u pp e r

l im it of t h e i n te gra l as a first a pproxi m ati on b y 00 Th e i n te gra l wi ll
t hu s b e c om e a nu m e ri c a l con sta n t i n d e p en d e n t o f mm , a n d i t f ol l o ws t h a t

9R c o n st
3
9
6 ”m
.

c o n st . T3 c o ns t . T3
ar
3 h k3 3
m
128 F rom t h e t heory o f e l a sti c i ty it f ol l o w s t h a t

wh ere x i s the c om pre ssi b i l i ty , p t h e d en si ty , an d 0

°
t he ra t i o

t ra n sve rse con t ra c ti on

g
l on i tu i n a l d dil ata ti o n
If we i n se rt t h ese va l u es i n ( 44 ) a n d no t e fu rt h er t ha t V f orm u l a
(4 6) of t h e t ext fol l ows .

1 29 As t he f requ e n c i es bel ow i i s proporti ona l to 3 we get

n u m b er o f f V , ,

for exa m pl e t h e f ol l o wi n g p i c t u re : i f we di vi d e t h e i n t e rval from O to

,

u
m i n t o 1 0 p a rt s a n d i f o n,l y on e n a t u ra l f r e qu e n c y l i e s i n t h e fi rst

d i vi sion t he n i n t h e fol l owi n g di vi si on s t here wil l b e 7 19 3 7 6 1 9 1

, , , , , ,

1 2 7 16 9 2 1 7 2 7 1 n a tu ra l f re qu en c i e s ; i e t h e n a tu ra l f re qu en c i es c rowd
, , , . .

c o n t i n u a l l y c l o se r t o g e t h er .

1 30 P D ebye A n n (1 Phy s 39 7 8 9
.
, . . W N er n st a n d F A
.
, . . .

L i n dema n n Si tzu n gsbe r d Be rl A ka d d W i ss 1 9 1 2 p 1 1 60

, . . . . . .
, . .

1 81 A E u c ke n a n d E S c hwer e V erh a n d l d d eu t sc h p h y sik a l G e s

. .
, . . . . .

15 5 7 8
, W N er ns t a n d F S chwer s Si t zu n gsbe r d Be rl A kad d
. .
,
. . . . .

W i ss 1 9 1 4 p 3 5 5 ; P Gr i l n ther A n n d Phys 51 8 2 8
.
, . .
W H
, . . .
,
. .
 N O TE S A N D R E FERE N CE S 1 55
Keesom Ka me r li ngh On n e s , Am sterda m Proc 17 , 89 4
and -
. Cf .

a l so t he gra phi c ta b l es b E S c hr od i n er Ph s Z ei tsc hr 20 4 9 8

y g , y . . . .

188 If we i n tro du ce i n to e u a t ion 44 o f t he text ,

q ( )
4 1r V 1
33 V ": 3N

a m ea n ac ou sti c v el oc i t y 0, b y th e o b vi ous defini ti on

3
l 2
3
E O
i O
i
t h en for th e or d er o f m a gni tu de of th e s m a l l e st wa ve -
l engt h Am in t h ere ,

fol l ows

If n ow th e a to m s i n t he c u bi c a l s pac e l a tti c e
-

, for e xa m pl e , a re a rra n ge d
so a s to b e a di sta n ce a a part t hen , Na 3 = V, an d h enc e

f
1 38 F o r re e ren c e s see n o te 1 2 2 .

134 Cf B or n , Dyn a m i k d er K ri sta l l gi tt e r , 1 9

. .

188 F Ha be r V e rb d d eu t sc h ph s G e s 13 , 1 1 1 7
.
, .
y . . . .

F or i f t h e a t o m i c re si du e ( m a ss m ) a n d t h e el ec t ron ( m as s 14 ) a re h e l d
t o t h ei r ze ro p o si ti on s b y f orc es o f t h e sa m e o rd er o f m a gni tu d e , a n d i f
t h ey vi b ra te i n d e pen d e n tl y o f o n e a n ot h e r ( a si m p l i fy in g su ppo si ti on ) t h e
eq u a ti on o f vi b ra ti o n o f t he a t o m 13 mx a x
2
0, t h e sol u ti on o f whi c h i s
x A sin
( Th e i n f ra -
red frequ enc y of t he a t om i s , t h ere f ore ,

a n d c o rre s o n di n p gl y , the u l tra vi o l et

-
f requ en cy of th e e l ec t r on

Hen c e Ha ber ’
s La w f ol l ows : if , m, rs /Z: Jfi . Th e

gen e ra l s pac e l a tti c e t heory

-
of M . B or n c on firm s t h i s l a w an d s h ows t ha t
in t h e l a tt i c e , t oo , a to m i c re si u e s a n d e l ec t r on s a d
ea r u o n a n eq u a l pp p
f g
oo ti n , a n d a re ac te d p
u on b y o rc es o f the s a m e or der of m a gn i tu d e f .

186 Cf M . . B
or n a n d T hos v Har m an , P y s Z e i t s c h r 13 , 29 7. . h . .

W e ma y trea t t i s rob l e m , h
wh hp d
i c i s of c ourse on e i m en si ona l , m os t -

s i m p l y t h u s : If w e i m a gi n e
a n e n dl e ss c h a i n o f po in ts o f eq u a l m a ss m
di spo se d a l o n g t h e x a xi s a t a di sta n c e a pa rt a a n d i f w e su pp o se fo r
-

s i m pl i c i t
y t h a t eac h m a ss p oin t onl y a c ts u po n i ts tw o n ei gh b ou rs t h e n
-
,

th e eq u a ti o n o f m o ti o n o f t h e n t h po in t i s

mx ,, x" ) (
a x ,, at“ ,

Here a is a c o n s ta n t , an d n c a n a ss u m e al l va l u es be t ween co a n d co

As a sol u t i on l et us se t for tr ia l
15 6 T HE Q U A NT U M T H EORY
Thi s repre sen ts a proc e ss whi c h i s peri odi c i n spac e an d t i m e tha t i s a , ,

wa ve whi c h i s propa ga te d a l on g t he c ha i n i n t h e di rec ti on o f in c re a si n g

x . Th e f re qu en c y o f thi s wave i s i t s l en g t h i s A Th e n i f a f t e r p
if , .
,

p oi n ts t h e sa m e d i sp l a c e m en t i s t o rec ur p a m u st A a n d h en c e i t , ,

a c t u a l l y fo l l o w s t h a t

A S 11] Wil t (n
g
A sin ra
A

In or erd t o fin d t h e re l a t i on b e t wee n y a nd A (th at i s, the “

l aw of di s
l et us i n s er t t h e a b ov e f orm u l a i n t he eq u a t i o n o f m o t i on .

Th e n i t f o ll o ws t h a t

(
3
m ( 2 1ry ) A 2
sin 21 t 71

2
a A
{ Sm 2 7t ( 77
. 8 111 w t (n

(
'

Qa A si n 2 7t n 1 CO S

Th a t i s ,

( ) f
1r
( 21ry ) m
’
2' 2
4a si n
A
1 a 1
y = 3L = ym s m a t
, 1f we se t
1r m A A 1r m

187 Cf . B or n , Dyn a m i k d e r Kri sta l l gi t te r , p . 51 .

F rom t h e s pec i al c a se t rea t e d

previ ou s n ote w e a l so rec ogni se
in t h e ,

t h e t ru t h of l a w f or if A i s m u c h g rea t er t h a n a t h e di sp e rsi on l a w ,

ta ke s t h e f orm y
a q 17
wh ere q a re p re sen t s t h e ve l oc i ty of
_
"m _ '

i A a ’ ,

propa ga ti on o f th e wave a n d t hi s i s i n de pe n d en t of th e wa ve l en gt h
,
-
.

1 38 Th e sta te m en t t h a t a g iven di re c ti on l i e s i n t h e e l e m en t o f sol i d

a n gl e d o i s i n te n d e d to c onvey t h e f ol l owi n g se n s e : a b o u t a n a r b i t ra ry

o ri gi n 0 d esc ri b e a u ni t s ph ere i e a sphere of ra di u s 1

”
, N ow l e t a c on e
. . .

o f i n fin i t el y sm a l l a n gl e b e c on st ru c te d o f ra y s pa ssi n g t h rou gh 0 t h e p oi n t ,

o f t h e c on e l yi n g a t 0 L et t h i s c on e cu t ou t o f t h e su rfa c e of t h e u ni t
.

s ph ere a sm a l l e l em en t o f su rf ac e d o N ow l et t h e pa ra l l e l ra y t o t h e
.

gi ven di rec t i on b e dra wn t h rou gh 0 ( h ere f or exa m pl e t h e wa ve , ,

n orm a l s) If t hi s ra y l i e s in th e c on e j u st c on st ru c te d t h en we sa y t h a t
.
,

th e gi ve n di rec ti on l i e s in th e el em en ta ry sol i d a n gl e d o .

189 Th e c a pa c i ty fo r h ea t o f a c erta i n fin i te b o dy i s t h a t a m ou n t o f h e a t
whi c h m u st b e i m pa rte d to the w hole bod y i n order t ha t i ts t em pera tu re
b e ra i sed b y 1 C If M i s t h e m a ss o f t h e b o dy a nd c i t s spec i fic h ea t
°
.
, ,

t h en i t s ca pa c i t y fo r h ea t i s
 N O T ES A N D REFERE N CES 1 57

F rom t h e m ea n e n e r gy c on ten t E o f the w ho l e bod y , 1 “

f ol l o w s by
difi e ren ti a t i on wi t h re s pec t t o t h e te m p e ra t ure

dE

140T i sh so m e wh a t co m p li ca ted ca l c u l a ti o n ru n s a s f ol l ows : we

l1)
F kV
”

an d firs t repl ac e A by hu s w e
T ge t

3
Q A”)

a nd th e i n te gra l wi th respec t t o A i s tra n s fo rm e d i n to on e wi th p

re s ec t to
vi . Th e l i m i t s of t h i s in t egra l a re

y; 0 ( co rres p on din g t o A 00

3 4n

i =1 0

In pl ac e o f t he qu a n ti ti e s qi (n ) a n d Aa (n ) wh i c h st i l l d e pen d e sse n t i
a ll y o n t he di re c ti o n , l e t c e rta i n mea n va l u e s b e i n t rod u c e d Fi rst l y , l e t
.

u s se t

In t h i s wa y t hre e m ea n a cou s ti c ve l oc i ti es 2 1 , q, , q, , in de pe n den t o f th e

dir ec ti on , a re d efin ed W e f u rt her i n trod u c e i n pl a c e o f A m (n ) a m ea n
.

va l u e i n d e pen d e n t o f t he di rec ti o n , i n t h e f o l l o win g m an ne r In d ed u c .

in g f o rm u l a ( 5 5 ) w e sa w t ha t
1 58 T HE Q UA N T U M T HEORY
If w e c a rry ou t th e i n te g ra ti on wi t h respec t to A, we ge t

N ow , i n a wa y a n al o g ou s to t ha t u se d f or t h e ac ou sti c ve l oc i t i e s q,
se t

1 l dn 3N
'

a s 41 j
0
A i m) 1m V
'

Hen c e

In t o mamm 1
-
we i ntro du ce i n
p l ac e of qi (n ) a n d Am (u ) t h e m e an
v al u es qi a n d A m whi c h a re i n de p en den t o f di rec t i on ; t h ereb y x i ( n ) al so
,

b ec om es i n dep e n de n t of d i r ectio n a n d i s tran s f orm e d i n t o

,

It f ol l ows t ha t
3

m “W
m 4 x

f
I

5t 3
o

3 xi

x e xd x
4
1
?
an
O

14 1 A t t h e l o west t em pe ra tu re s
 N O T ES A ND REFERE N CES 1 59

N ow t he val u e of t h e in te gra l s If we fu rt her se t R N k, an d

fo r x th e va l u e we get
i

If we in tr o du c e i n pl ac e of t he t h ree a c ou stic ve l oc i ti e s q“ q 2, q3 a m ea n
_
acou sti c ve l oc i ty q b y m ea ns o f t h e d e fi n i ti on

25 2 :

i =1
1
4” rm
G
i ( see n ote 1 40)

it f oll ows tha t

1 6n5 k 4 p T 3

we ca n wri te VA ( m ea n a to m ic vol um e ) a nd t h u s get t h e

142 H . Thi rr i n g, Phy s . Z e i t s c h r 14 , 8 6 7

. 15, 12 7 , 1 80 ( 19 1 4 )
143 M . Bor n and Th . v. Kar m d n , Phy s . Z ei t sc h r 14 , 1 5
.

144 Of n ote 1 3 2 . .

145 Cf n ot e 1 2 8 . .

146 A E u c ke n , V e rh a n dl d d e u t sc h ph y si k a l G e s 15 , 5 7 1
. . . Cf. . . .

a l so A E u c ke n , Di e Th e o ri e d er S t ra h l u n g u n d d er
. u a n t en W Kn a pp ,
( Q .

Ha l l e pp 3 8 6 et seq , A pp en di x
. . .

14 7 Of A E u c ke n , D i e Th eo ri e d er S tra h l u n g u n d d e r
. . u a n te n ( W Q .

Kna pp , Ha l l e p 387 . .

148 To ca l cul a te t h e m ea n a c ou sti c ve l oc i ty q, th e re l a ti on gi ve n in n ot e

1 4 1 i s u se d
3
3

We have t here f ore to di spe rsi o n e qu a ti on of the

o b ta in fr om t he “

c ry sta l in qu e sti on o r l on g wa ve s h
( f ) t h e v a l u e s o f t h e t ree a c ou st i c
_
v el oc i ti e s q n ) q ( n
1( 2 ) q3 (n ) a s fu n c ti o n s o f t h e wa ve di rec ti on ; q i s t hen
, ,

ob ta i n e d fr o m t h e a b ove f orm u l a b i n t t i n l l d i r ti n s a nd
y e gra o o ve r a e c o
fin a l l y su m m a ti o n .

149 L Hop an d
f . L echn er , V e rh a n dl G .
. d deu tsc h
. .
p hys i ka l Ges 16 ,
. .

64 3 e
180Th e f o l l owi n g sh o rt ta b l e i s ta ke n fr o m t he pa per of Hopf an d
Le c h ner ci te d i n n ote 1 4 9
1 60 T HE Q UA NT U M T HE ORY

q cal c f rom
”

e la s t i c
Cr y s tal 5 ca l c . from 60 .

1 51 W N erns t, V ortr a ge u b er d i e ki n e ti sc h e Th eori e d er Ma te ri a u n d d e r

.

E l e kt ri zi tat Wol fskeh l Kon gre ss 1 9 1 3 i n Getti ngen ( Teu b n er , Lei pzi g
.
-

a n d Be rli n pp 6 8 e t seq . .

152 W N ern s t, i bid , pp 8 1 e t seq

. . . .

163 E S c hr od i n ger , Phy s Z ei ts c hr 20

.
, 50 3 S chr od i nger c orr ec tl y
. .

poi n ts ou t t ha t— a pa rt from th e su b sti t u ti on of one si ngle m ean a: f or

t he t h r e e qu a n t i t i e s Debye t e r m s— a p p rom m a t i on a bove a ll
'

th e th e in
th e s ec on d pa rt o f C, ( i . e . th e re p l a c em e n t of t h e 3 (s 1) fr eq u en ci es
v4 b y v th e c ons ta n ts V ) m a y n ot b e pe rm i s si b l e i n m a n y
3 3 .

c a ses : n a m e l y , i n t h os e c a se s i n wh i c h t h e m a sse s o f t h e va ri ou s in ds k
o f a t om s a r e n o t v e ry di ff e r e n t from o n e a n ot h e r If w e were t o a l l ow .

— so h e arg u e s — th e m a sses o f t h e d i fier en t i n ds of a to m s a n d t h e for c es k

a c ti n g u po n t h e m g ra d u a l l t o b e co m e eq u al t o on e a n o t h e r , a si m pl e
y
a t om i c l a t ti c e wou l d re su l t , a n d d u ri n g t h i s pro c e ss t h e 3 ( s 1 ) b ra n c h e s
o f t h e s p e c t ru m , whi c h c orr e s pon d to t h e s e co n d t y p e o f m ot i o n , wo u l d ,

m erg e i n t o t h e t h r e e fi rs t b ran c h e s “
Th ey c a nn o t t he re fo r e e en b e . v
a pproxi m at el y m on oc h r om a ti c i f the ma sses di fie r o n l y sli g h tly .
”

1 84 H Th i rr i n g, Phys Z e i t s c h r 15, 1 2 7 , 1 8 0
. . .

1 88 114 B or n , A n n d Phy s 44, 6 05

. . . .

156 E Gr i me i se n A n n d Ph y s 39 2 5 7
.
, . . .
,

1 57 S R a tn ows ki , V erh an d l d d e u tsc h p h y si ka l G e s 15, 7 5

. . . . . .

158 Vort r ag e fi b e r d i e ki n eti sc h e Th e or i e d e r Ma t eri e u n d d er E l e k

t ri zi t at . Wol fsk ehl Kon gr e sz zu ot t i n g en , 1 9 1 3 (Te u b n er , L ei p zi g
-
G .

a n d Be rli n V or tra g P D ebye . .

159 If U i s t h e en erg y , a n d S t h e e n t ro p y o f th e s ste m , t h en t h e f ree

y
en e rg y i s d e fin e d acc or d in g t o He lm ho l tz b y th e rel a ti on

F U S T.

It t h e n f ol l ows f rom n o te 1 1 5 t h at

dF dA S
’
dT

wh ere d A ’
i s th ewor k d on e from wi t ho u t If we . se t i n t he u su a l wa y

d A
’
pdV (p p r es su re V , vo l u m e )
M pdV Sd T .

From thi s w e get i mm e d i a tel y t h e eq u a ti on ( 66 ) i n t h e te x t

 N O T E S A N D R E FE RE N CE S 1 61

a nd h e nc e

160P . D ebye , loc . cit .

, not e 1 58 .

16 1 E . Gr ane i s en , Ann . (1 . Phy s .

26 2 1 1
, 33 , 65 ( 1 9 1 0) 39 2 8 5
,

1 62 P D eby e
.
, loo . ci t ,
n o te 1 58 .

163 A . E uc ken , An n . d Phy s

. .
34 1 8 5 , V e r h a n dl . d d e u t sc h
. .

h
p y s i ka l G e s . .
13 , 8 2 9
1 64 P Dr u d e , A n n d Ph s 1 , 5 6 6
.
y . . .

165 E R i ec e , Wi e d e m A n n 66 , 3 5 3 , 54 5
. k . .

166 Cf , for e xa m pl e , H A L or e n tz, Th e T h e o r o f E l e c t ro n s Te u b n e r ,

.
y . .
(
Le i p zi g , a n d erl in B
167 Le t
q b e t h e a ve ra g e ve l oc i ty o f the el e c t ron s a l o n g t h e fr e e pa t h I .

1
Th en t he e l ec t ron ta ke sp a ss ove r th i s free p a t h
t h e ti m e 1
—
to .

9
D ur i n g t hi s t i m e i t i s e x p o se d t o t h e e l e c tr i c a l forc e E o f t h e e x t e rn a l
fi e l d Its i n cr e a se i n ve l oc i ty d u e t o t hi s fo rc e i s a t t he c o m m e n c e m e n t
.

ff:
e
of the f ree p a t h O, at t he end of it W h e re e and m a re th e

c h a r ge a nd m a ss of the e l ec t ro n res p ec t i ve l y . In t h e m e a n , t h e r e f ore ,

6 3? e El
t he ma l l ddi tiona l v e l oc i ty gen era te d by t he fi el d i s
M
s a Aq
2m
Th e wi t h t hi s v e l o ci ty a g a i n s t th e fie l d
e l e c t ro n s s t rea m u n i d i r ec ti on a l l y .

If N i s t he n u m b e r of e l ec t ron s p e r u ni t vol u m e , t h e n t h r o u gh u ni t
a rea o f t h e su r f a c e t h e re st r e a m s r s e co n d a q u a n t i t y o f e l e c t ri c i t y
p e
2
N e lE
N qe A T h i s i s h o w ev er t h e
“
cu r re n t d e n s i t y
”
I wh i c h i s
m
, ,
2
k n ow n to b e conn ec t e d wi t h th e fie l d E b y t h e r e l a ti on I « E . Th e
ex p r essi on ( 6 7 for t h e co n d u c t i vi ty 0 t h e re f o re f ol l o ws
)
'
.

A m ore t h oro u gh t re a t m e n t i s d u e to H . A . L or e n tz ( see note

He does no t gi ve t he el e c t ro n s a si n g l e vel oc i ty q b u t i n t ro d u c es M a cr ,

w e l l s su ppos i ti o n kn o wn fro m t h e ki n e t i c t h eo ry o f ga se s t h a t a l l
’

, ,

possi b l e ve l oc i ti e s occ ur whi c h a re d i s tri b u te d a m o n g t h e el ec t ro n s

,

acc o r di n g to a fix e d l a w t h e so c a ll e d Ma x we l l L a w o f Di s t ri b u t i on
,
-
.

H e t h u s o b ta i n e d a form u l a o f t h e f o l l o w i n g f o rm

whi c h t here for e onl y di ffers b y a n u m e ri c a l fa c tor f ro m D r u d e s f o rm u l a ’

he re q Jef t h e r oo t m ea n sq u a re o f t h e vel oc i ty
f
,
.

168 Le t a te m pe ra tu re gra di en t al o n g t h e a
n axi s b e p re se n t i n t h e p i ec e

o f m e ta l Le t a s ec ti on b e ta k en ( see F i g 1 2 ) a t r i gh t a n g l es to t he
. .

11
1 62 T HE Q U A NT U M T H E O RY
x a xi s ; w e sh a l l c a l c u l a te t h e e n e r gy t ra n s po rt a c ross t hi s sec ti on
p er
Se c o n d . If w e su ppo se t h a t i o f a ll el ec t ron s wa n d er i n ea c h o f t h e t hree
dir ec ti o n s i n spa c e t he n 1 m ov e i n t h e positi v e a: d i rec tion ; a n d f u r th er
, ,

t h e n u m be r o f e l ec t rons w hi c h
pa ss t hro u gh t h e u n i t o f su r
fac e i n o n e se c on d wi l l be a l l _ ,

t h ose wh i c h a re c on ta i n e d i n
t h e sm a l l s ha d e d c y l i n d er wi t h
t h e b a se su rf a c e a rea 1 a n d t h e
h e i ght q (vel oc i ty ) n a m el y , ,

F IG 1 2 . .
iq W e a l so m a ke th e su p .

posi ti o n u su a l i n t h e t h eory o f ,

g a se s (a l t hou gh n ot stri c tl y t ru e ) t h a t t h e en ergy whi c h ea c h e l ec tron

, ,

t ra n sp orts t hrou gh t h e cross sec ti o n ha s t h e va l u e c orres pon di ng to t h a t

-

wh i c h i t h a d a t t h e p oi n t wh ere i t l a st c ol l i d e d .

N ow t h e e ne rgy i n t h e se c t i on i t sel f a t t e m pe ra tu re T i s e qua l to sk T ,

a n d h e n c e t h e e n er g 3k T i l a t t h e po i n ts wh i c h l i e a t a
y
”

di sta n c e Ii n front o f a n d be h i n d t he sec ti on Here o n th e a vera ge th e .

, ,

e l e c t ro ns c om i n g f ro m t h e ri gh t a n d t h e l e f t m ee t wi t h t h ei r l a st c ol l i si on s .

Th e e n ergy t ra ns po rt p er sec on d t hrou gh u n i t o f c ro ss sec t i on i s -

t h e r e f ore

fl m n9
(
2

( fi )
T — k
t k s z Nq -

tk 1 t

He n c e 7 tn k i s t h e c o e ffi ci e n t o f t h e r m a l c o n d u c t i vi t y .

Here a l so H A L or e ntz ha s dee pe n e d t h e theo ry b y t a ki n g

. . t h e di stri
b u t i on o f ve l oci ty i nto ac c ou n t , a n d fin ds t ha t

“
F i fi ? N MC
3 11 L '

wh ere a g a i n q q
169 G
Wi edem a n n a n d R F r a n z Pogge n d A nn 89 4 9 7
. . L , . .
, .

L or en z W i e d e m A n n 13 4 2 2 5 8 2 Cf a l so G Ki r chhofi a n d
'

. .
, . .
, ,

G Ha n sem a n n W i e d em A n n 13 4 1 7
. ,
W Jae ger a n d H
. .
, . .

D ie sse l hor s t, A b h d phy s t ec h n R ei c h sa ns ta l t 3 , 2 6 9

. . . .

Th e f ol l owi n g sh ort ta b l e i s ta e n f ro m t h e pa p e r k of t h e t wo i n ves ti

ga tors l a st n a m ed ; i t gi ve s t h e ra t i o Z for v a ri ou s m eta l s at a t em pera t ure

a
°
of 18 C .
 N O T ES A N D RE FERE N CE S 1 63

1 70It fol l ows fro m ( 6 7 ) b y se tti n g } q 1

shT ,
t ha t is , q

N ow , l e t N be t h e n u m b e r o f a to m s pe r u n i t vol u m e , N
o f a to m s i n a gra m m e a to m (A voga d r o s n u m b er) If , fu rt h er , A i s t h e
’
-
.

a to m i c we i gh t , M t h e m a ss o f a n a tom , a n d p t h e d e n si ty , t h en

N = N 31 * .

We next a ssu m e t ha t N , t he n u m b e r o f e l ec tron s pe r u ni t o f vol u m e , is

If we i nsert t h is va l u e , t hen we get for t h e free pa t h

We s ha l l m ake a rou gh cal cu l a ti on for co pper a t 0 °

C . W e h a ve

A
.

k
T 27 3
m
"
N 61 1 023

10
e 10
-
1 64 T HE QU A NTUM T H EORY
S in c e t h e a to m i c dis ta n c e i s d er m a g ni t u d e 2 —8
of the or of . 10 , the
e l ec trons wo u l d t h ere f ore o nl y ff er c oll i si on a f ter pa ssi n g m an y t hou
su

s a n d s o f a t om s Th i s i s u n ac c e p ta b l e si n c e t h e ra d i u s o f m ol e cu l a r
“
.
,

a c t i on o f t h e a to m s i tse l f h a s di m e n si on s whi c h fa l l wi t h i n t h e or d e r o f

m a gni tu de o f a bou t 1 0 —8
.

1 71 H A L or en tz, loc c i t , n ote 4 3

. . . .

1 72 J J Thom son , Th e Corp u sc u l ar Th eory of Ma tt er

. . . .

1 78 H Ka m mer li n gh O n nes , Le i d en Co m m u ni ca t 1 9 1 3 , 1 3 3
.
-
. .

1 74 C H L ee s, Phil Tra n s ( A ) 20
. . 8, 3 8 1 —
.44 3 .

175 W Me i ssner , A n n d Phy s 47 , 1 001

. . . .

1 76 W N er ns t, e rl B e r 1 9 1 1 , p 3 1 0
. B . . . .

1 77 H Ka m mer l i ngh On n es
. L e i de n Co m m u n i c a t 119 , 22
-

, .

1 78 F A L i n d e ma n n ,
. . e rl Be r 1 9 1 1 , p 3 1 6 B . . . .

1 79 W Wi en , . erl B er 1 9 1 3 , p 1 8 4
B . Cf a l so Vo rl e su n g e n
. . . . u ber

n eu ere Pro b l e m s d er t h e ore t i sc he n Ph y si p g k Berl i n

( Te u b n er , L e i zi an d .

V orl e su n g
3 . .

1 80If s i s t h e ra di u s o f a t om i c ac t i on , N t h e n u m b er o f s ta ti on a ry a t om s

p e r u n i t of vol u m e , t h e n , a c c or di n g t o a we l l kn own re su l t o f t h e ki n e ti c -

t h eo ry o f ga se s , t h e m ea n f re e pa t h s o f t h e e l e c t ron s

1 _

1r N8 2

Le t u s se t

3 a
0

W here so i s t he ra diu s of a tom i c a cti on for T 0 t ha t i s wh en the a t om s , ,

a re a t re st ; l e t a b e t h e a m pl i t u d e o f a t om i c vi b ra t i on N ow t h e m ea n .

l
e n ergy E o f t hi s vi b ra t i on ( f re qu en c y ) o n t h e on e h a n d i v , ,
2
( M i s the a t om i c m a ss) ; on th e ot he r h a n d , i t i s, a cc or di n g to P la nc k
E i ns tei n,

From t hi s i t f ol l ows t ha t

N ow , ac c o r din g to f orm u l a ( 6 7 ) of t h e t ex t , t h e re si st a n c e

1 2m q
W ”

Ivar

If w e here set f or q the va l u e ( cf . n ote a nd fo r N , ac c or di n g

t o J J Thom son
. .
’
s su pp osi ti on , a N/ ,
T a nd fo r } the va l u e
l
2
ar Ns wN ( a
2
+ 2 a s0 3 3)
 N O TE S A N D REFERE N CE S 1 65

it f o l l o ws tha t

21 N J3 k m 22 m . m 2
-

2 {1 Ihv
6 a 1
ak T 1 1

a n ex pres si on whi c h c on ta in s on l y
,
a and so a s u n kn own c on s ta n t s . If
we se t

t hen W a ssu m es th e f orm gi ve n i n t h e f orm u l a

181 F A L i nd em a n n , P hil Ma g 29 , 1 2 7
. . . .

18m F Ha ber , B e rl Ak a d Be r 1 9 1 9 , pp 5 06 a n d 9 9 0
. . . . . .

182 J S ta r k , Ja h rb d R a di oa kt u E l e kt r oni k 9 , 1 8 8
. . . . .

163 G
B or e l tu s , A n n (1 Phy s ; 57 . 2 7 8
. . .

184 K Her zfe ld , A n n ( 1 Ph ys 41 , 2 7

. . . .

»
185 If w e se t 5 q E , t h e re for e q t he first of t h e t wo f o r
m
fol l ows f rom
m u l ae ( 7 2 ) If we fu rt he r ta ke in to ac c ou n t t ha t in Dr u de s ’

2 dE
Theo ry E 3k T t ha t , i s , t ha t k t h en f ro m ( 6 8) t h e sec on d f or
_ ,

3 dT
m ul a ( 7 2 ) f oll o w s .

186 F . v . Ha u er , A nn . (1 . Phy s .
51 , 1 8 9
18 7 W . Ber 1 9 1 1 , p 6 5
N er n s t, B e rl . . . .

188 A E u c en , . Be r 1 9 1 2 , p 1 4 1
k B erl . . . .

I89 K S c hee l a n d W H eu se , A n n ( 1 Ph y s 40
. .
, 473 Cf a l so . . . .

L Hol bor n , K S c hee l a n d F Henn i n g, W arm eta b e l l e n d er p hys i ka l

. . . .

t ec hn R e i c hs a n sta l t ( Vi e we g
.

190A E i n ste i n a n d O S ter n , A nn ( 1 Ph y s 40, 5 5 1

. . . . .

19 1 Th e qu a n t u m f o rm u l ae 7 6 ) a n d p p rl y c orr e s p on d t o t h e
( ( )
7 7 ro e

P l a nc o scil l a t or, t ha t i s , t o a sy ste m o f one d e gree o f free d o m , whi l e

k
h ere , i n t he c a se of r ota ti on , w e ha ve t o d o wi t h tw o de gree s o f fre e d om .

Bu t t h e e n e r gy o f t h e P l a nc o s c i l l a t or i s c o m p o se d o f t w o equ a l p a rt s , a
k
k i n e ti c an d a p o te n ti a l p art , whi l e i n t h e c a se o f r ota ti o n on l y i n e ti c k
en e r gy c o m e s i n t o q u e s t i on Th i s i s o f te n e x p res se d t hu s : t h e P l a nc
. k
o sc il l a t or p o sse sse s o n e p o te n t i a l a n d o n e i ne ti c d e gree o f f ree d om , wh il e k
t he ro ta t in g m ol ec u l e p ossesse s t w o i n e t i c d e gr ee s o f fr e e d om k .

192 P E hr e n e s t, V e rha n d l d d e u tsc h

.
f p h y si k a l G e s 15 , 4 5 1
. . . . .

193 A c c o r d i n g t o n o te 4 8 , t h e u a n t u m c a n o n i c a l di s tri b u t i on f u n c ti o n i s
q
1 66 T HE Q U A NT U M T H E ORY
an d t h e m ea n ener gy is

If w e h ere set a l l p s 1 a n d i f for E w e

n
’
, n su b st i tu t e th e va l u e E l
?
)
from t h ere f ol l o w s f or t h e m ea n ro ta ti on a l en e r gy of a m ol ec u l e

0
00
where a

26
O

a nd f or t h e hea t of rota ti on of hy drogen w e ge t t h e ex pre ssi on

dE r
Cr : 2N
dT

194 The t u r n in g i m pul se ( m o me n t o f m o m en t u m ) of a sy st e m , t h e

m a ss poi n t s o f wh i c h po s se ss t h e m a ss m i , t h e v e l oc i t i e s m, a n d t h e d i s
-

t a n c e s r i f ro m a fix e d poi n t (sa y t he or i gin o f c o ordi n a t e s) , 18 a vec to r of

t h e va l u e

[U ] Em i v m si n (c m ) .

In t h e p re sen t c a se , the sy ste m c on si s ts on l y o f t h e tw o a t om s ( m M

a ss)
whi c h ro ta t e ar o u n d a c i rc l e of ra di u s r wi t h th e c o n sta n t l t
v e oc 1 y
v 7 2 1m
He nc e h ere
J 2 1rv,
.

wh e re J = 2M r ? i s t h e m o m en t o f i n e r ti a .

195 Th e i m p u l se o r m o m en t u m p i c orr e s pon di n g to r a l i se d

( ) a ge n e cc

8L
or d in a t e q; i s , a c c or i nd g to n o te 48, d efi n e d by the re l a ti o n pi :

agi
'
,

dqfi
wh qte re :
_
’ a n d L i s th e
k
i n e t i c e n e r gy o f t h e sy st e m N ow h ere .

dt
t h e a n gl e o f r o t a t i o n i s c h o sen a s a g e n e ra l i se d c c or d in a te B u t t he -
.

k i n e t i c e ne rg y of a b ody ro ta t i n g a b o u t a fi x e d a xi s i s n own to b e k
Q ( m o m e n t o f i n e rt i a ) (
x a n g u l a r h e n ce

He n c e
”
(
i
t 2 6

a t J an y .
 N O T E S A ND REFEREN CE S 1 67
196 F . Re i c he , A n n d Ph ys 58 , 6 5 7 . . .

1 97 Th e b es t c u rv e w a s o b t a i n e d b y a s s i g n i n g t h e w e i gh t 2 n t o th e
n t h q u a n t u m s t a t e o f ro t a t i o n T he r ota ti on le ss s ta te ( n 0) t h u s .

r e c e i v e s t h e we i gh t ze ro , i s i t d o e s n o t e xi s t T h i s a m ou nt s t o t h e . . .

s am e t h i n g a s t h e i n t ro d u c t i o n o f a ze r o p o i n t r ot a t i o n -
.

1 98 E Holm , A n n (1 Ph s 42 , 1 3 1 1 ‘

.
y . . .

199 J v We y sse n hofl, A n n (1 Ph s 51 , 2 8 5

'

. .
y . . .

200 M P l a nc k , B e r d d e u t s c h p h y s i k a l G e s 17 , 4 07
. . . . . .

201 S Rots za yn , A n n ( 1 Ph y s 57 , 8 1
. . . .

202 Th e c u rv e i s n o t d ra wn b
y P l a n c k , b u t i s d i sc u s se d i n t h e a u t h or s
’

p a p er c i t e d i n n ote 1 9 6 .

208 S e e l i k e wi s e t h e a u t h o r s p a p er u ot e d i n n o t e 19 6
’

q .

204 P S Ep s te i/n , B er d d e u t sc h h si k al G es 18 , 3 9 8 Cf
. .
p y . . . . . .

a l so Ph y s Z e i t s c h r 20 .
, 2 89 .

205 N B ohr , Ph i l M a
.
g 1 9 1 3 , p 8 57 . . . .

206 D u ri n g “ r e gu l ar p r ec e ss i on t h e t op t u r n s u n i f o r m l y a b o u t i t s
a xi s o f sy m m e t ry ( a x i s o f i t s fig u r e , wh i l e a t t h e s a m e t i m e t h i s a x i s
)
d e scrib e s a c on e o f c i rcu l a r sec ti o n a b ou t a n a xi s fi x e d i n sp a c e .

207 A c o m p i l a t i o n o f t h e m om e n t s of i n e r t i a o f t h e h d r oge n m o l e c u l e
y
u se d b y t h e v a ri o u s i n vest i g a tor s i s a s f ol l o w s

J . 1 04 1 .

2 2 14
2 2 93 d i ffer ent c u rve s .

md
Rots za yn
E p s te i n ( B ohr 3
’
o el
)
208 N . Bj er rum , N er n st F e s t sc h ri f t 1 9 1 2 , p . 90 . Bj er r u m di d n ot ,
b y t h e wa y , sta rt f r om f orm u l a bu t c a l cu l a te d wi th t h e va l u e s
nh
V =
n +
25
si n c e , f ol l o wi n g a prop osa l of H . A . L or e n tz, h e se t the ro ta

E W) m t o E hr e nfest f orm u l a ti o n
’
t i on a l e n e rgy e qu a l to n hy , c o n tra st s
n
r

whi c h rests on a sou n d er b a si s .

209 8 P L a ngle y Ann a l s o f t he A strophy si ca l

. . ,
Ob se rva t ory of th e
S m i t h son i a n In s ti t u t i o n V ol I p 1 2 7 Pl a te X X , .
, .
,

21 0 F P a schen W i ed e m A n n 51 1
. 52 209 53
, . .
, , , 335
21 1 H R u bens B er l B e r 1 9 1 3 p 5 1 3
.
, . .
, . .

21 2H . R u ben s and E A sc hk i n a ss , . Wi ed e m . An n .
64 5 8 4 ,

213 H . R u ben s and He i tner , G . B erl . B er . 19 16 , p . 1 67 . S ee a l so

G .B e ttne r , A nn . ( 1 Ph y s 55, 4 7 6
. .

21 4 W u r mei s ter , B e r
. B . d d e u tsc h
. . h
p y s i k a l G e s 15, 5 89 . .

21 5 E v a v a hr , B e r . B . d deu t sc h
. . h
p y s i k a l G 68 1 5 , 7 1 0, 7
. 3 1 , 1 1 50 .

C
19 13
21 6 f L or d R a y le i gh, Phi l Ma g 34 , 4 10
. . .
Le t an H Cl m o l e
cu l e, for e xa m pl e , be c on si de re d , whi c h c o n si st s of a posi ti ve ly c ha rged
 1 68 T HE Q U A NT U M T H E O RY
hydrogen a tom H + a n d a n e ga tively c hl ori n e a t om 01 (see F i g L et .

i ts c e n t re o f gr a vi ty b e S a n d l e t a b e t h e di sta n c e o f t h e H + a to m f ro m
,

Le t t h e l i n e j oi ni n g t h e t wo a to m s be t h e a xi s o f w a n d l e t t h i s a xi s
'
S .
,

tu rn i n t h e posi t i ve di re c ti on a bou t S a t t h e ra te o f re v ol u t i on s p e r

se co n d wi t h re sp ec t t o t h e fi xe d a y sy ste m If n ow t h e t wo a to m s
- -
.
, ,

V i b ra t e re l a t i ve l y t o o n e a n ot h e r wi t h t h e f req u e n cy ” a n d t h e a m pl i tu d e
0
A t h e n th e w c c or di n a t e o f t h e H + a to m s m a y b e re pre se n t ed t h u s
’
-

'
A si n ( o )
x a 2 1rv t .

If we proj ec t t hi s v i b ra t i on u pon the fix e d c c or -

di na te sys te m , it follows
t ha t
’

( Ql w r t) ( r ) ( 27r y t) ( r)
{
x a c os ‘
a c os 2 1ry t A si n cos 2 1rv t
o
'
y y Si n ( QM / T l ) a Si n
( 21ry 7 t)
- A 8 111
( o)
2 1rv t Si n
( 2 1rwr t
)

fo r whi c h we m ay a l so wri te
a c os
( 2 r )
1rv t si n 2 m m ,
s
1
£
5
si n any
, m t

A
a si n c os 2 1r( uo y
r)
t 4 c os 2 ( 1r u
r)
v t
5 o .

F ro m t h e poi n t of vie w of t he syst e m at re st we h a v e t hu s

o sc i l l a t i o ns

( )
a f
th e l e t -
c i rc u l a r o sc il l a ti o n

}
in a 008
W1 t h t h e f requ e ncy y, .

(0 a si n 2 7 W? t)

( ) e l e ft
b t h -
c i rc u l a r o sc i ll a t i o n

a:
2
‘
V
7
.
”
wi t h t h e fre qu enc y ”0 ”1
4 008 2 ( vo 1r V
o
.
) t
5
 N O T E S A ND RE FERE NCE S 1 69

( )
c t he ri gh t c ircu l a r osc il la ti on
-

a: 4 2 1r( y o V
7
.
)
2 wi t h t he freq u en cy yo y .
r
1
; cos 2 1r( y o y, )
21 7 S Imes , As trop h J ou rn 50, 2 5 1
E . . . .

21 8 A E u c en , Be r d d e u tsc h phys G es 1 5, 1 1 5 9
. k . . . . . E uc ke n has
here , o n ac c ou n t o f t h e asym m et ri ca l form of th e hyd rogen m o l ec u l e ,
a ssu m ed t w o d i ffe ren t m o me n ts o f i n ert i a

a n d J2 = 2 2 1
40
Ji -
10
-

a nd he nce ob tai ned t w o di fferen t seri es o f n u m bers gi vi n g t he re volu tions

p e r s e co n d o f t h e t a b l,e g i ve n t.h e re S ee a ls o t h e ta b l e i n R u ben s a n d .

B e ttner , loc . ci t .
, n o te 21 3 .

2 19 M . P l a nc k , A nn . d Phys
.
52 4 9 1 ; 53 24 1.
, ,

n o 0 S ac ku r , A nn
. . ( 1 Phys
.
36 9 5 8 40 6 7
.
, ,

221 H Te tr ode,
. Phys . Z e i ts c h r 14 2 1 2 A nn .
, . d Phys
. .
38 , 4 3 4
( 1 9 1 2)
222 W H K ee som Ph s Z e i tsc h r 15 6 9 5
. .
y , . .
,

223 A S ommerfe l d Vort rag e ii b e r d i e ki n e t i s c h e Theori e

.
,
d e r Ma te ri e
u n d d e r E l e kt ri zi t at Wolf sk eh l Ko n gress i n t tin gen 1 9 1 3
.
-
.
( Teu b n er ,
Le i p zi g a n d e rli n p 125
B . .

224 P S c her r er , t
. ti n ge r N ac hr 8 J u l y , 1 9 1 6 . .

225 M P l a nc , . e r l Be r 1 9 1 6 , p 6 53
k B . . . .

w W N er n s t, D i e t h eore ti sc h e n u n d ex pe ri m e n te l l e n
. ru nd l a ge n d es G
n e u e n W arm esa t zes W K pp H ll pp 1 e t se q
( n a , a e . 5 4 . . .

227 O S a o a r , Ber d d eu t sc h c h e m G es 47 , 1 3 1 8
. k . . . . .

228 0 S te r n , Ph s Z e i tsc h r 14 . 6 29
.
y Z e i.t sc h r f E l e t roc h e m i e . . . k
25 , 66
229 F or wha t foll ws c f pa per b y O S te rn qu ote d i n th e l ast n o te
o . the . .

F u rt he r W N ern s t D i e t heo re ti sc h e n u n d e x pe ri m e n te ll e n G ru n dl a gen

, .
,

d es n eu en W arm e sa t ze s ( W K n a pp H al l e C h X III . .
, . .

230 A s re g a rds t hi s a n d t h e f oll o wi n g c h a p te r t h e rea d er is re f e rre d fo r ,

m ore e xa c t d e ta il s to t h e a rti c l e o f P S E p s te in i n t h e P l a nc k n u m b e r . .

of N a tu r wi sse n s c h a f te n ( 1 9 1 8 p , .

231 A s t h e s i m p l es t Thom son a to m w e a re to i m a gi n e a s phe re o f ra di u s ,

a fil l e d wi t h t h e u n i t c h a r g e e o f po si
,

t i v e e lec tri fi c a ti o n o f s pa c e d e n si t y i n
p
-

, ,

t h e m i dd l e o f wh i c h a n e lec t ro n wi t h
t h e c h a r g e — e re st s Th i s s t ru c tu r e i s .

e xt e rna ll y n eu tra l If w e d ra w t h e .

e l ec tr on o u t fro m t h e c e n t re to a di sta n c e

r
( see F i g 1 4 ) t h e ex te rna l ( s ha de d )
.

h ollo w s phere ex erts n o forc e on t h e

el ec t ro n ac co r di n g to t h e w e ll kn o wn
,
-

l a ws o f el ec t rost a ti cs Th e i nn e r so li d .

s ph ere o f ra di us r o n t h e o t h er ha n d , ,

ac ts o n t h e e l e c tro n j us t as if i ts to ta l
c ha r g e we re co n ce n tra te d a t t h e ce n tre F IG 1 4 °
.

Th e f orce whi c h dra ws th e el ec tron bac k i n to i ts posi ti on of rest is

170 T HE QUA NTU M T H E ORY
t here fo re ,

t ha t i s i t i s p ro po rt i o n a l to t h e di sta n c e
, of t he e l ec t ron from i ts posi tion
o f e qu i l i b ri u m .

Cf
232 P D r u de Le hrb u c h d er Op ti k 2 A u fi Ch s V a n d V II
. a l so .
, . . .
, .

( H irze l Th er e i s a n E n g l i sh e d i t i on o f t h i s w or k .

233 Cf W Vo i gt Ma g n e to u n d E l e kt ro o p t i k ( Te u b n e r
. .
,
-

234 M P l a n c k Be r d Be r l A ka d d Wi ss 1 9 02 p 4 7 0; 1 9 03 p 4 80;
.
, . . . . . .
, .
, .

1 9 04 p 7 40; 1 9 05 p 3 8 2
, .
, . .

235 H A L or e n tz Th e Th eo r o f E l e c tro n s Ch s III IV Teu b n er

.
y .
( , , .
,

236 Th e e l e c t r on o sc il l a te s wh e n b ou n d
qu a si el a st i ca l l y a cc ordi n g t o
-

, ,

d2
t he e qu a t i on o f m ot i on m —
ii t; f ee , i f we r e stri c t ou rsel ve s t o l i n ea r os

c il l a t i o n s . He re m
i s t h e m a s s o f th e e l e c tro n , a: i s i t s di sta n ce f rom t he
p osi ti on o f re st , a nd f i s a fa c t or o f pro port i on a l i ty Th e sol u ti on of thi s .

di ff e ren ti a l e qu a ti on i s re prese n t e d b y t h e p u re h a rm oni c m oti on

where t h e frequ en cy is

Th e frequ en c y n i s t he re f ore a s w e see i n dep en d en t of th e a m pl i tu de an d , ,

t h ere f ore o f t h e e n e r g y o f vi b ra ti on .

23 7 Th e f re u e n c i e s o f t h ose s p ec t ra l l i n e s o f l u m i n ou s h y d r og en
q V ,

wh ic h a re i n cl u de d u nd er t h e n a m e B a lmer seri e s m a y b e re p re sen te d ,

wi t h grea t a cc u ra cy b y th e f ol l o wi n g f orm u l a gi ven b y B a l me r .

v = N
<
L2
2 n 2
wh ere
N is h ere a c on s ta n t , the so c a l l e-
d R y dber g n u m b er . If we se t f or t h e
c u rr e n t n u m b er n t he va l u e s 3, 4, 5 w e ge t i n su c c e ss i on t h e i re

qu en c i e s o f t h e re d l i n e o f h y dr o g e n H
( a) , t h e re e n l i n e g ( HB) ’ and the
b l u e l i n e ( H ) a n d s o f ort h 7 .

238 J . S ta r k , An n
43 9 6 5 J S ta r k a n d Wen d t ibid ,
. (1 . Phy s .
, . G .
, .

43 9 8 3 , J S ta r k a n d H K 1r schba u m , i bi d , 43 , 99 1 ; 43 1 01 7
. . .
,

( 1 9 1 4 ) J S ta r k i bi d 48 1 9 3 21 0 ( 1 9 15 ) J S ta r k O H a r d tke a n d G
.
, .
, , , .
, . .

L i e be r t, i bid , 56 5 6 9 1 9 1 8 )
( J S ta r k , i bi d
.
56 5 7 7 ( 1 9 1 8)
, L ie ber t . .
, , G .
,

i bi d 56 5 8 9 6 1 0
.
, J S ta r k a n d O H a r d tke i bid 58 , 7 1 2 ( 19 1 9 )
, , . .
, .

J S ta r k , i bi d , 58 7 2 3
. .
,

239 Cf . H . A . L or e n tz, Th e T h eory of E l e c t r on s ( Te u b n e r , L e i p zi g and

Berl i n Ch 1 1 1 . .

24 0 H Ge i er a n d Ma r s d e n Ph il Ma
g .
, g A pri l , 1 9 1 8 . . .

241 E R u therf or d , Phi l M a g 21 , 6 6 9

. . .

24 2 A cc o rdi n g t o C D a r wi n [ Ph i l Ma g 27 , 506 . G . . . th e ra di u s
o f t h e n u c l eu s , ta e n a s a sph e re , i s i n t h e c a se o f k g ol d at t h e m ost
—
3 1 0 1 2 c m s , i n t h e c a se o f h y dro g en a t t h e m ost
-
. 2 10 13 cm s .
 N O T E S A ND REFERE N CE S 17 1
248 A . va n de n B r oe k Phy s , . Z e i t sc hr 14 , 3 2 .

244 Of n o te 2 4 7
. .

245 N . ohr , Ph il Ma g 26, 1 , 4 7 6 , 8 5 7

B . .

246 A E i n s te i n , Ph y s Z e i t sc h r 18 , 1 2 1
. . .

24 7 Th e i te l e m e n ta ry ca l c u l a t i on i s a s f o l l o ws : l e t a n e l ec tr on o f
q u e
c h a rg e e a n d m a ss m r o ta t e a r ou n d a n u c l eu s o f c h a r g e E ez i n a

c i rc ul a r o rb i t t h e n z i s t h e a t o m i c n u m b e r ( fo r h y d r o g e n , i n p a rt i c u l a r ,
3 If a i s t h e ra di u s o f t h e c i rc l e , 0 t h e ve l o c i ty , a n d w t h e a n gu l a r
v e l oc i t
y ( f re q u e n c y o f r o t a t i o n ) o f t h e e l e c t r o n i n t h e c i rc u l a r orb i t , t h e n

t he c on di ti on fo r e qu i l i b ri u m b e t we e n t h e a tt ra c ti on o f t h e n u c l eu s a n d
t h e c en tri f u g a l f orc e i s

m a cs 2
or ma 3
w 2
eE e2 z.

Acc ordin g t o B ohr d hyp ot hesi s th e m o m en t m om e n tu m

’
s se c o n of

is a m u l ti pl e of 11 hence
7
,
2 1r

( n = 1,

F rom t he se t w o equ a ti on s f or a a n d to w e ge t for t h e di sc re t e of t he

pe rm i ssi b l e qu a n tu m orb i ts
2
n h
2
an :

4 11 e e m
z 2 '
-

a nd the c orres p on di n g frequ en ci es o f r ota ti on

8 1r 3 6 4 z‘3 m

The e n e rgy
( ki n e ti c p oten ti a l ) i s
e

t h ere f ore the di sc rete qu an tu m va l u e s o f th e en er gy a re

If, i n t h i s ex p ressi on , we se t

an da
w
we re c ogni se , t h a t W i s a f u n c t i on o f w and he n ce o f V
5?
,
1

of the e l ec t ron i n th e R u therfor d m o de l t h er e f ore d e pe n d s , a s sta t e d in

t h e te x t , fr equ en cy o f r ot a ti on
on i ts v.

If t he e l ec tr on pa sse s f r o m t h e n th t o t h e st h qu a n tu m pa t h t h e n a c , ,

c o rdi n g t o B o hr s t h i r d h y po t h e si s a h o m o g e n eou s s pe c t ra l l i n e i s e m i t t e d
’
,

Wn Ws = 2 1r 6 2

(
2 4
1
( l2 l ix
1

) )
7 r22
y N2 2 -

2
h3
s
2
n s n
172 T HE Q U A NT U M T H E O RY
where

248 Of n ote 2 3 7 . .

249 It i s o f hi st ori c a l i n t e re st t o n o t e t h a t , b e f ore ohr , A E Haa s in B . .

1 9 10 ( S i t zu n gsb er d W i e n e r A a d 1 0 M arc h , 1 9 1 0) su cc ee de d i n r e p re
. . k .

se n t i n g R yd ber g s n u m b e r i n t e r m s o f t h e u n i versa l c on s ta n t s e , h , m ;
’

h i s re su l t d i ffe red f r o m t h a t o f B ohr o n l y b y a f a c t o r 8 H e d e du c e d h i s .

re su l t a s f o l l o w s S ta rt i n g f r o m J J Thoms on s a t om i c m o d el , wh i c h
’
. . .

wa s g e n era l l y a c c e p t e d a t t ha t t i m e , h e ca l c u l a t e d t h e m a x i m u m osc i l l a
t i o n f re qu e nc y ( n o o f r e vol u t i on s ) ma x o f t h e e l e c tr on i n t h e si m pl e st
-
. y
a t om ( hy d rog e n a t om )for t h e ca se wh e n t hi s a t om , p rovi de d wi t h on e
e n er gy qu a n tu m , w a s
-
c i rc l i n g j u s t o n t h e su r f a ce o f t h e p o si t i ve s ph ere .

He o b ta i n e d

”m a x

Thi s m a x i m u m f re qu e nc y w a s n e x t i d e n tifi e d b y Haa s wi t h the se ri e s

l i m i t ( n = cc i n B a l me r s f o rm u l a
’

(
1
y = N —
§2 n

Th e n i t fol l ows t ha t
N H aa s

whi c h is a va l u e 8 ti m es gre a ter t ha n d t h i s re l a t i o n t o

N B oh r ° Haa s u se

c a l cu l a te f rom t he t hree q u a n t i t i e s t h e R y dbe r g n u m b e r,

N P la n c k s ,
’

c o n sta n t h, and t he ra t i o f a l l of whi c h h e a ssum ed k n o wn t h e c h a rg e

, ,
m
e of t he e l ec t ron . In d th e va l u e
c o n se qu e n ce o f th e fa c t o r 8 h e o b ta i n e

e a va l u e t h a t i s t o o s m a l l ou r p r e se n t kn o w a c c ord i n g t o

l e dge b u t wh i c h a gr ee d w e l l wi t h t h e m ea su re m e n t s o f J J T hom son a n d

, . .

H A Wi lson wh i c h were a va i l a b l e a t t h a t t i m e
. .
, .

250 T h L yma n Phil Ma g 29 28 4

.
, .
,

25 1 F P a sc hen A nn d Ph y s 27 5 6 5
.
, . . .
,

25 2 A F ow ler M o n t h N o t R oy A st r o n S oc 7 3 D ec 1 9 1 2
.
, . . . . . , . .

255 F P a schen A nn ( 1 Phy s 27 5 6 5

.
, . . .
,

2B4 E 0 P i c ke r i n g A s t ro p h J ou m 4 3 6 9
. .
,5 92 . .
, ,

255 E J E va n s N a t u r e 93 2 4 1
. .
, , ,

256 W Kosse l A n n ( 1 Ph y s 49 2 29 ( 1 9 1 6 )
.
,
D i e N a t u rwi sse n sc h a f te n
. . .
,

7 33 9 , 3 60
,

257L Ve ga r d , V e rha n d l d d e u t sc h p h y si ka l G e s 19 , 3 4 4
. . . . . .

258 A S omme rfe ld , A t o m b a u u n d S pe t ra l l i n i e n

.
( A n E n g l i s h e di t i o n k .

t ra ns l a te d f rom t h e 3 rd e rm a n e di t i o n
( 19 2 2 ) i s b G
e i n g pre pa re d b y

M e ssrs M e t hu e n Cc , L td )
. . .

259 R L a de n b u r g, D i e N a tu r wi sse n sc h a fte n 8 , 5

.

260A . S ommerfe ld , A n n d . . Phys . 51 , 1

 N O T ES A N D RE FERE N CE S 173
261E x p re sse d i n te rm s o f po l a r c c or di n a t e s t h e ki n e t i c
-
e ner gy L as

su m es t h e w el l n o wn f orm -
k
1
7
L
2

In i t , m d en o tes th e m a ss of th e e l e c tro n , the d ots pre sen t di ffere n ti a

re

t i on wi t h re s pec t t o t h e t i m e Th e i m pu l se s p , a nd p are t h e n d e fin ed a s
o
.
,

f ol l ows ( see n ote 4 8 )

BL 6L
'

er as;
262 0nl y when eac h im pu l se
de pe n ds s ol el y on t h e c orresp ondi n g
q; ( o r wh e n i t i s a c o n s ta n t ) a n d wh e n i n a dd i t i o n t h e l i,m i t s o f t h e , ,

pha se in te n a re i n de pen de n t o f t h e qi s d oe s th e pha se i n te g ra l work

-
’
,
-

o u t t o a c o n s ta n t Th i s i s b y n o m ea n s t h e ca se f or a n y a rb i tra ry c h o i c e
.

o f t h e c c ord i na t e s s t e m
y
- -
.

263 P S E p s te i n An n ( 1 Ph y s 50 4 89
. .
, 51 1 6 8
. . .
, ,

264 K S c hwa r zsc hi l d

. Si t zu n gsb e r d Be rl A ka d d Wi s s 4 Ma p
, . . . . . . .

19 1 6 .

265 A . E i n s te i n , V e rha n d l d d e u t sc h p hy s ik a l G e s 19 , 8 2
. . . . .

266 M . P l a nc , V erha n d l d d eu tsc h p hy sik a l G6 8 17 , 4 07 , 4 3 8

k . . . . .

A nn . ( 1. Phy s .
50 3 8 5 ,

267 Th e se m i -
m a j or axi s o f th e el l i p se wh i c h
, is c ha ra cteri sed b y t he
va l u es 11. a n d n
’
, h ere ha s t h e va l u e

’
( )
2
h2 n n
a

The ra t i o o f t he a xi s is
b n
"
a n + n

We see t ha t n
0 c o rre sp o n d s t o t h e c a se o f
'
B ohr s c i rc u l a r orb i ts
’
.

268 Th e e n erg y o f t h e e l ec tron m o vi n g i n t h e Kep le r p se ( n h

'
el li , n ) e re

h a s t h e va l u e
2 1r e z m
2 4 2

Th e se ri e s f o rm u l a ( 102 ) of t h e te xt t hen f ol l ows from B ohr ’

s La w of

269 1f a c c ou n t i s ta ke n of t he in fl u en c e of re l at ivi ty t h e seri e s form u l a ,

for t h e s pec tra of th e h y dro g e n t y pe b ec om e t o a first a pproxi m a t i o n

V0 = N 2
3
174 T HE Q UA NTU M T H EORY
In t hese exp re ssi on s th e sym b ol s N and a h ave t h e f ol l owi n g m eani n g

mo i s th e m a ss of t h e e l ec tr on hi n gl y sm al l ve l oc i ti e s
a t va n i s .

He n c e where a s t h e fir st te rm ”0 gi ve s t h e o l d f or m ul a whi c h wa s ,

ob ta in e d b y n e g l e c t in g t h e i n fl u en c e o f re l a t i vi ty t h e sm a l l a ddi t i on a l ,

te r m ”1 re p resen t s t h e i n fl u e n ce o f re l a ti vi ty A s w e ob se rve y , d oe s n ot
. ,

onl
y d e pe n d o n t h e q u a n t u m s u m s s s a n d n n b u t a
'
l s o o n t h e
'
,

i n di vi du a l va l u e s 3 s n n Thi s m e m b er 1 i s t h u s re sp ons i b l e f or t h e
’ '
, , , .
, 11 ,

fin e -
stru c tu re .

27 0If we a ppl y t h e f orm u l a of the prec e di ng n ote t o H a , we have to set

W e t h en ge t

2
17 a

F IG . 15 .

Corresp on di ng t o t h e p ossib i l i ti e s of pa r ti ti on
cir le
1 1 e
c
ll 1 p se } 2 fin al orb i t s

c irc l e

2pse 3 i n i ti a l orb i ts
1 el l i

1 2 e l l i p se

or dy n a mi ca l rea son s t h e a zi m u t h a l m u m b er n ca nn ot u n d e r
( f q u a n t u n

n orm a l c on di ti on s a ssu m e a ze ro va l u e
) w e s h ou l d ex p ec t 2 3 6
,

p ossi b il i ti es o f produ c ti on a n d h en ce 6 c om p on en ts of the fin e str u cture -

of H e On e o f t h ese c om p on e n t s h owever na m el y t h e on e c orre s po n d

.
, , ,

in g t o th e t ra n s i ti on of t h e e l ec tron fro m t h e c i rc l e ( n 3 n 0) t o t h e ,
’

e l l i p se s ) d p f d m d
’
( 1 s ,1 oe s n ot r es e n t i t se l u n e r n or a l c on i t i o n s a s ,

fol l ows f rom the Princi pl e o f Se l ec ti on enu n c i a ted b y R u bi now i cz

“
 N O TE S A ND REFE RE N CE S 17 5
a nd S ommerf eld ( see Cha p te r V I, He n c e 5 c om p on en ts of t h e
fine str u c tu re re m ain t h ei r po si ti o n i s ex hi b i te d i n F i g 1 5
-
. .

As w e see t h e 5 c o m pon e n t s a rra n ge t h e m se l ve s i n to tw o m a i n gr ou ps ,

,

c on t ai n i n g 3 a n d 2 m e m b e rs , res pe c t i v el m i ss i n g ”
y T he “
li n e IIa i s . ,

d o tte d i n Th e di st an ce A y n b e twee n Ia an d II“, It a n d Il a, Is a n d IL; i s

.

c a ll e d h eore ti c a l hy dr og en d ou b l e t
the “
t .
”

Ac c ordin g to t h e a b ove f orm u l a t h e f requ en c y -

n u m b er of th e l i n e
Ia ( 3 , 0 0) i s

Th e frequ en c y -
n u m b er of t h e l i n e Il a. ( ,0
3 1) is

yl l a,
10 10

c orre spon di n g t o A A H
Th e hy dro g en d ou b l e t a c tu a ll y o b serve d i s m ea sure d fr om a b o u t t h e
-

m i ddl e o f I a n d It t o t h e m i ddl e of IL an d II o win g t o t h e a b se n ce of

a , c,

II“ . Thi s l ea d s t o t h e v al u e 0 8 A A H t h a t i s t o 01 2 6 3 °

, , 1 .

A c c ordi n g t o a p ri n c i p l e o f c orres p o n de n c e en u n c i a te d b y B ohr (see

Cha p ter V I as a re su l t o f whi c h t h e a zi m u t h al qu an t u m n u m b er c an
,

onl y vary b y i 1 t h e c om p on e n t s It an d IL a re al s o a b se n t
-

_ , ; .

27 1 F P a sc he n A nn d Ph s 50 9 01
.
y , . . .
,

2 72 F ro m form u l a 9 7 o f t h e te x t w e e t fo r t h e t w o R d ber
( ) g y g co n sta n ts

Na e

Moreover , ac co r di n g to n o te 2 6 9 , w e ge t t h e t i r h d form u la
va l u e o f th e c o n sta n t f or t h e fin e stru c tu re
-

2
2 11 6
-

he

Fro m t h e fir st two re la ti ons , by u si n g M He 4 51 3 , w e ge t

 17 6 T HE Q UA NT U M T H E ORY
a nd hen ce
e NH -

4N s e '

m oc Ma c Nae —Nn

Th e t wo R ydber g n u m b ers N H and N He h a ve b ee n m ea sure d b y P a sche n

wi t h grea t ac cu rac y :
NH ( 1 09 6 7 7 6 9 1 006 ) c

N He ( 1 09 7 2 2 1 4 4 1 0 .

6
Moreove r F is the e l ec t ro c hem i ca l eq u i va l e n t ( F a r ad a y
’
s nu m
MH
,
c
he r) , t ha t i s , the c ha rge whi c h ,
in e l ec t ro lysi s , a cc om pa n ies on e gra m m e
L
a to m
( i s N a tom s ) T is h nu m b er ha s t h e va l u e
MH
. . .

F 9 6 49 4 e l ec t ro m a g n e ti c u n i ts .

If we i ns e rt t h e t hree va l u e s o f N H, N a e and in th e re la t i on a b ov e

de d u c e d , w e ge t

10 7
el ec t ro m a gn eti c u n i ts ,

a val u e wh i c h a grees v ery well wi t h t hose v a l u es of t hi s qu a n t i ty wh i c h

were ob ta i n e d b y di rec t m e t ho ds ( d efle cti on of t h e ca t ho de a n d B ra y s i n . -

t h e el e c tri c a n d m a gn e ti c fi el d ) Le t u s n ow wri t e .

m
or nem t he va l u e o f g‘van a bo v e
MH
3 NH Na e

Th e ri gh t ha n d si de o f t hi s eq u a ti on is kn own
-

. If w e co m b i ne wi t h it

t h e va l u e for
7 00
7 5
— j us t fou n d a n d al so t h e va l u e ,

whi c h foll ows from P a sc hen s m ea sure m ents o f th e fi ne stru ct u re i n t h e

’
-

ca se o f h e li u m w e ha ve t hr ee e qu a ti ons i n t h re e u nk n o wns 6 m o h
, .
, ,

From t h e m we ge t
e i 008 8 ) 10
-
10

h 6
( 526 i 02 00) 10
“
27

A c c or di n g to S ommerfe ld i t i s m ore a d va n ta geou s to u se Mi lli ka n ’

s va l u e
fo r e . W e t h en ge t
 N O T E S A ND R E F ER E N CE S 17 7
278 K
G l i tscher , A n n d Phys 52 , 608
. . . .

27 4 A L a nd e , Phys Z ei tsc h r 20
'

.
,
2 28 ( 19 19 )
. 21 , 1 1 4 .

2 75 Of A S omm erf e l d , A to m ba u u n d S pe t ra l l i ni en
. . Ch IV , 6 k . . .

276 P S Ep s te i n , A nn ( 1 Ph y s 50, 4 8 9
. . . . .

277 P D ebye , t
. t i n ge r N ac h r 3 J u n e , 1 9 1 6 . .

S ommerf e ld , Phys Z e i tsc h r 17 , 4 9 1 Cf a lso A to m ba u

. . .

u n d S pe t ral li ni e n
k Oh VI, § 5 . . .

279 F P as c hen a n d E
. ac , A nn d Phy s 39 , 8 9 7 . B k 40, 9 60 . . .

280AR u bi now icz, Phy s Z e i ts c hr 19 , 4 4 1 , 4 6 5

. . .

281 N B ohr , O n t h e
. Q
u a n tu m Th eo ry o f Li n e s pe c tra Par ts I a n d II -
. .

D Kgl D a nske Vi d ensk Se lsk S kri fte r , N a tu rvi d e nsk o g Ma t he m Afd

. . . . . . .

8 , B a e kke IV , 1 Ko pe n ha g en 19 1 8 . .

282 Th e n u m b er o f r e v ol u t i o n s o f t h e el ec tr on e c on d i n t h e s t h
p r se

qua nt u m c irc l e of B ohr i s , i n t h e c as e of hy drog en , a c c ordi n g t o n ote 2 47 :

ws 41 2 4
3 7714
3
2 1r 8 h6

On t he o t h er h a n d , i t f ol l o ws f ro m f o rm ul a ( 9 3 ) of t h e te xt , if we t a ke 3
c on si d era b l y grea te r t ha n 1 ( h i gh q u a n t u m n u m b e rs) , a n d n s 1
( t ran sit i o n b e t wee n n ei ghb ou rin g c i rc l es ) , t ha t
m 2
‘
3 4
2 1r e ( s 3

2 1r e ‘m 2 3
m
yi s of the or de r 2s
“
4 11 e
4

h3 s h3 s b
S E p s tei n , A n n d Ph y s 58 , 5 5 3
283 P . . . . .

2B4 E A Kr a mer s , In te ns i ti e s of S pec tral Li n e s

. . D Kgl D a nsk e . . .

Vi d e n sk Se l sk Skrif te r , N a tu rvi d e n sk og Ma t h e m
. . A fd 8 , B ae kk e III, . . .

3 . K openh a ge n 19 19 .

285 A . S ommerf e ld a nd W Kosse l

.
, Be r . d d eu t sc h
. . h
p y s i k a l . Ge s 21 ,.

2 40
266 J F r an c k
. a nd G . Her tz Phys , Z e i t sc h r 20, 1 3 2
. i n whi c h .

f
re ere n c es a re a l s o Cf a l so gi ve n . . J F r a nc a n d P Kn ip p i ng, Phy s
. k . .

Z e i tsc hr 20, 4 8 1 ( 1 9 1 9 ) J F r a n c ,
. . k P Kn ip p i ng a n d The a Kr uger , Be r
. .

d d eu tsc h p hysika l G es 21 , 7 28
. . . .

287 J Ta te a n d F oote , Phi l M a J

.
g u l y , 19 1 8 . . .

288 R ef ere n c e s a r e gi ven in t h e re por t b

y J F r a n c a n d G H er tz, m e n . k .

ti on ed in n ote 286 .

289 A E in s tei n , Ph s Z e i t sc h r 18 1 2 1 L e t u s c on s i d e r t h e
.
y ,
. .

t w o qua n tu m s ta t es ( 1 ) a n d 2 ) o f t he a t o m , wi t h t h e e n ergi e s E 1 a n d E 2
(
Th e n u m b e r of tra n si t i ons 2 1 whi c h ta e pl ac e i n th e k
ti m e d l o wi n g to radi a ti o n i s t h e n , ac c o rdi n g t o E i n s te i n , N oA md t, in
whi c h N 2 i s th e n u m b er o f a to ms in t h e sta te 2 , a n d , t here fore , ac c ord
i ng to n o te 4 8

N b ei ng t he t o ta l n u m b er o f a t o m s . A 21 i s a fac to r of p ro port i onal i ty .

12
1 78 T HE Q UA NT U M T H E ORY

Th e i n tr o du c t i on of ex te rn a l m on oc h r o m a t i c ra di a t i on of f re qu e n c y v
a n d i n te n s i ty K ,, firs tl y b ri n gs a b ou t p o si t i ve a b sorp tio n , t h a t i s , t ra ns i

t i ons 1 2 Th e n u m b er o f t h e se i n t h e t i m e d t i s , ac c ordi n g t o
.

E i n s te i n , N l K o,
in wh i c h B 1 2 i s a fac t or o f p rop ort i on a l i ty , N 1 i s th e
n u m b er o f a t om s in t h e sta te 1 a n d h en c e ,

S ec on dl y , t h e e xt ern a l ra d i a ti on al so e ff e c t s tra n si ti ons 2 9 1 ( n e ga

t i ve a b sorp ti on ) Th e n u m b er o f t h e se t h a t occur i n t h e t i m e d t
.

N g Bol K v , wh ere B 2 1 i s a f ac t or o f p r op orti on a l i ty Wh e n t h e e n e r gy .

e xc han ge is in e qu i l i b ri u m the n u m b e r of t ra n s i t i on s 2 m us t b e
e qu a l t o t he n u m b er o f t ra n si ti o n s 1 4 2, h en c e
52 £1
, ,K
N Cp oe k TA d N op ,e kTB d N Cp l e k TB dt
ol t ,
t v
A 21
B 21

Wh en t h e te m p era tu re i n cre a se s i n de fi ni te l y , K m u st
y a l so i nc re a se t o
in fini te l y grea t va l u e s f rom t hi s i t f ol l o ws t h a t
291 3 12

172 3 21
A
Fi n a l l y , if w e s et
F ? )
A f or s h ort n ess , we ge t t h e rel a t i o n gi ve n i n t h e

3 kT

29 00f . the r é su m é by E . Wa gner Phy s , . Z e i t sc h r 18 , 4 05 , 4 3 2 , 4 6 1 ,

.

4 88
29 1 G . Mose le y , Phi l . Ma g 26 .
, 1 02 4 27 , 7 03
292 W Kos se l.
, V e rh a n d l . d deu t sc h
. . h
p ys i ka l G e s 1 6
.
, 89 8 ,
. 9 5 3 ( 9 14 )
1
18 , 33 9
293 A S ommerfe ld , A nn d Phy s 51 , 1 25
. Phy s Z ei tsch r 19 ,
. . . . .

29 7 Cf a l s o A t o m b au u n d S pe kt ra l l i ni e n Ch III, Ch IV
‘

. . . .

g 4 , Ch V 5 . .

294 L Ve ga r d , V erha n dl d d e u tsc h h s ik a l G s 19 17 pp 3 2 8 3 44 ;

.
p y e , .
, . . . . .

Phys Z ei t sc hr 20. 9 7 , 1 2 1
. .

295 P D ebye , Ph s Z e i t s c h r 18 , 2 7 6
.
y . .

296 J Kr oo, Phy s Z ei t sc h r 19 , 3 07

. . .

29 7 A S me ka l , Wi e n er Be r IIa 127 . 1 22 9
.
128 , 6 3 9 .

Verha n d l d d eu tsc h p h y si ka l G e s 21 , 1 4 9
. . . Cf a l so A S me ka l . . . .

a n d F Re ic he , Ann ( 1 Ph s 57 , 1 2 4
.
y . . .
 N O TE S A N D RE FERE N CE S 1 79
298 W Kosse l . Z eit sc h r f Phy si 1 , 1 1 9
, . . k
299 Si n c e t he L rin g c ons is t s o f sever a l e l ec tr on s , w e ta e t h e ex p re ssi on
-
k
e l l i p t i c m o t i on t o m ea n t h e f ol l o wi n g ty pe o f m o t i on e ac h e l ec t ro n
i n de pen d e n tl y d esc ri b e s a n e l l i p ti c pa t h a b ou t t h e n u c l eu s , wh ereb y t h e
e l ec tron s are a t eac h m om e n t s i tu a te d a t t h e c orn er s o f a re gu l a r p ol g o n
y
whi c h sh are s i n th e m o ti on o f t h e el ec t ro n s , al te rna te l y c on tra c tin g a n d
e x pa n d in g d u ri n g t h i s m o ti o n e l li p t ic a l cf S om me rfe ld . .

A to m ba u a n d S pe tr a l li ni e n k .

800A S me k a l , Wi e n er Be r IIa 1 28 . 6 3 9
. .

801 M . B
or n a n d A L a nd é , e r l A a d Be r 1 9 1 8 , p . 1 04 8 V erh a n dl , B . k . . .

d deu tsc h p hy si ka l Ge s 20, 202 , 2 10

. . M .or n , i bid , 20 , 2 30 . . B .

Ann d Ph y s 61 , 87 . . .

802 A L a n d e, Verha n dl d d eu t sc h p hys ik a l G e s 21 , 2 , 6 4 4 , 6 5 3 1 9 19 )

.
( . . . . .

Z ei ts c hr f Phy s 2 , 83 Cf a l so A L a nd e a n d E M a de l u n g,
'

. . . . . .

Z ei t sch r . f Phys
. . 2 230 ,

808 W . Kosse l , A nn ( 1 Phys 49 , 2 29 . . .

804 P . D eby e , Mii n c h A ka d B er 9 Ja n 1 9 1 5 . . . . .

805 P . S cher r er , D i e R ot a ti on sdi s pe rsi on d e s Wa s se rsto fi s . Di sserta t i on ,

G cttin gen , 1 9 16 .

806 G
L as k i , Phy s Z ei tsc h r 20, 2 6 9 , 5 50
. . .

807 Cf , for e xa m pl e , A S om merfe l d , A t om b au u n d Sp e kt ral l in i en , Oh

. . .

IV , 6 .

808 L a ngm u i/r , J o ur n A m er Ch e m S oc 34 , 86 0 Z e i t sc hr f

. . . . . .

E l ec t roc h em i e 23 , 2 1 7
309 Is na r d i , Z e i t sc hr f E l e kt roc h e m i e 21 , 4 05 . .

81 0J F r a nc k , P Kn ip p i n g a n d Thea Kr uger , Be r d d eu t sc h p hys i ka l

. . . . . .

Ge s 21 , 7 2 8
.

81 05 P l a nc k ha s m a d e a n a t te m p t t o a l ter B ohr s m od el i n su c h a w a y
’

t h a t t h e ri gh t hea t of di ss o c ia t i on re su l ts S ee M P l a nc k , B e rl A ka d . . . .

Be r 1 9 19 , p 9 1 4
. Of a l so H Ka llma n n , D i sse rta ti on , Berl i n 1 9 20
. . . . .

31 1 W L en z, Be r d d e u t sc h p h ysik a l G e s 21 , 6 3 2
. . . . . .

812 A S omme rfe ld , A nn d Ph y s 53 , 4 9 7

. . . .

81 8 F P a u er , A nn d Ph ys 56, 2 6 1
. . . .

814 GL as k i , se e n ote 3 1 4
. .

81 5 M P ie r , Z ei t sc h r f E l e kt roc h e m i e 16, 8 9 7
. . .

8 16 K S c hw ar zsc hi ld , Be rl A ka d Be r 1 9 1 6 , p 5 4 8
. . . . . .

81 7 H Des la n d res , Com pt Re n d 138 . 3 1 7

. . .

81 8 T H eu r l i n ger , Phys Z ei tsc h r 20, 1 8 8

. Z ei tsc hr f Ph y s i k . . . .

1 82
,

81 9 W . L en z, se e n o te 311 .

820A di fferen t vi ew i s u ph el d b y J B u r ger s ( V ersl K Ak va n We t . . . . .

A m ste rda m 26 1 1 5 i n whi c h a l so j u m pi n g e l ec tron s p rod u c e th e

, , , ,

mi ddl e li n e i n t he i n fra red of b an d In c on tra s t wi t h S c hw ar zsc hi ld a n d

-
.

Len s B u r ger assu m es t h at th e m oti on o f t h e e l ec t ro n s i s i nfl u en c ed b y

,

t h e rota ti on o f t h e m ol ecu l e Th e en e rgy of t h e sys te m i s t h e n n ot c om .

posed addi ti vel y o f th e e n ergy o f th e el ec tro n s a n d t h e rota ti ona l en ergy

o f th e m ol ec u l e b u t a t hir d te rm h a s t o b e a dded
,
w hi c h i s d u e to th e ,

Cori ol i s f orce of th e rota t i n g sy ste m .

1 80 T HE Q U A NT U M T H E ORY
82 1 T Heu r l i n ger , se e n ote 3 1 8
. .

822 F Re i c he , Z ei t sc hr f P h y si 1 , He f t 4 , 2 8 3
. . . k
M E S Ime s , A strop h ys J ou rn 50, 2 5 1
. . . .

824 A Kr a tzer , D i sserta ti on , M ii n c h e n 1 9 20

. .

825 In t h e c a se of t h e ga se s i n ves ti ga t ed b y Imes , n am ely H Cl , H Br , a n d

H F , t he f ol l owi n g m o m en t s o f i n ert i a were f ou n d

JH Cl JHBr 210
 IN DE X

Com pressi b ili ty , 3 3 .

p
A b sor ti on b a n , e e o f, 2 1 , 1 1 2 d dg . Con du c ti vi ty , t he rm a l , 60 .

c on ti n u ou s , 7 8 . Cou lomb , 1 2
Ac ou s ti c vi b ra t i on s , 1 57 .

A c ti on , qu a n t u m o f , 9 , 27 .

A to m i c ea t , 29 h .

n u m b e rs , 8 6 , 1 1 0 . D a vi s 1 06
, .

A voga d r o s c on sta n t , 1 2 , 2 9 , 1 6 3
’
. D eby e 3 8 3 9 5 8
, , , .

La w , 1 2 .
D eby e s f orm ul a 40
’
, .

D e ge n e ra ti on o f ga ses , 79 .

D es l a nd r es 1 2 2 , .

D es s a u er , 22 .

D i a m a n e t i sm , 2 5
g .

B ac k 2 2
, .
D i a m on , 3 3 d .

B a l mer 9 0 , .

B a r k l a 2 0 1 09
, , . Wi en ’
s,
B ec k 2 5
, . Di stri b u ti on n u m b ers , 1 14 .

of ve l oc i ti es , Ma xw e l l s La w
’
of ,
B er gen 1 06 , .
5 .

B er gma nn seri es 89 , . D i xon 1 00

, .

B i s hop 1 06 , . D op p ler 4 , .

Bj er ru m 7 5 1 23 , , . Dr u d e 6 1 8 4
, , , 17 .

B ohr 7 5
, . Du a ne 2 2 , .

B ohr s m odel o f th e a tom

’
, 86 , 1 1 9 . D u long a nd P e ti t s La w ’
, 29 , 30 .

princ i pl e of a na l o gy or c orre

se l ec ti on , 98 .

Bo ltzma n n 4 , , 13 .

B orn 3 8 4 2
, , . hrenfes t, 7 1 .

B r a gg W H , . . a nd W . L 1 09 . E i ns tei n , 1 , 1 5 , 1 6 , 30, 1 07 .

fu n cti ons , 3 1 , 3 2, 5 1
Bremss tr a hlu ng , 2 2 , 1 09 .

B r oc k , va n de n , 86 .

Br ogl ie , d e , 2 1 .

B u ns en , 1 09 . 20 .

E la st i c c ol l isi on s, 1 04 .

p
s ec tru m , 4 2 .

h
E l ec tr o n t eo ry of m e ta l s ,
E m i s si vi ty , 2 .

Cana l ra ys , 1 42 p . E nt ro y ,
Ca vi ty ra di a ti on , l a w of , 3 Ep s te in , .

Cha rac teri sti c Rb nt ge n radi a ti on , E qu i parti ti on , 1 3 .

1 09 . E u cken 56 , ,
18 2 THE Q UA N T U M T H EORY

F i n e struc tu re , S ommerfe l d s t h e ory Ka mmer l i ngh Onnes , 6 4

’
- -
.

of, 9 4 . Kar man , 3 8 .

of t h e R on t ge n r a y s , 1 1 3 . Kep l er e l l i pse s , 9 5 .

kk
F o er , 15 . Ki n e t i c ra d i a t i on , 23 .

F oo te , 1 05 .

k
F r a nc , 22 , 1 02 . K osse l , 9 1 , 1 02 , 1 05 .

F r i/ma n , 1 09 . Kr a mer s , 102 .

Kr a tzer , 1 2 4 .

K ri n gs , 1 1 1
-
.

Kr oc , 1 1 1 , 1 1 5 .

K se ri e s 2 1
-

G er , 85
ibb Ku r l ba u m , 9
.

G s , 1 3, 26
.

G l i tsc her , 9 7 .

G au c her , 1 06 .

G ram m e m o l ec u l e , 14 5
-
.
L a d en bwr g, 9 1
G r unei sen , 5 8
.

L a ngm u ir , 1 20
.

k
L a s i , 1 19 .

La tt i c e t h eo ry of a t om i c h e a ts ,
L a u e , 35 .

La w , A voga d r o s , 1 2
’

Ha a s d e 25 .

eq ui part i t i on , 1 8
.
,

Ha ber 4 6 6 6 15 5 .

o f ca vi t y ra d i a t i on , 3
.
, , ,

Ha mi lton 1 5 .

o f ra di a t i on , P l an c k
.
,
s, 10
’
Ha mi l ton s prin c i pl e 2 7’

, .
.

Ha u er von 6 7 R a y le i gh s , 1 0, 14
’
.

Wi en s , 5 , 7
.
, , ’

Hea t t he ore m N er n s t s ,
’
, 35 .
.

He l iu m 9 7 S tef a n a n d B ol tzm a nn , 5 .

L d ou b l e t s , 1 1 4
.
,

He l m ho l tz 1 60
-
.
.
,

Her tz, 2 2 1 02 .
L ec hn er , 56 .

,
L ee s , 6 4
Her zfe l d 6 6 , .
.

L en a r d , 1 9
H eu r li n ger , 1 22 .
.

H eu se , 6 9 L an e , 1 20, 1 2 2 .

Li gh t qu a n ta , E i ns te i n s , 1 6
.
’

H oo k e s La w , 59
’ -
.
.

Hopf 1 5 5 6 .
L i n d em a n n , 3 3 , 6 4 , 66 .

, ,

Hu ghes 1 06 .
L or en tz, 1 5 , 2 4 , 6 1 , 1 6 1 .

Hu l l 2 2 L or en z, 6 2 .

L ri n g s , 1 1 1
, .

Hu n t 2 2
-
.
.
,

Hydr og en t ype of seri e s , 88 .

L u mmer , 2 , 3 , 4 .

Ma d e l u n g 38 , .

Mar sd en , 8 5
Ime s , 1 2 3
.

.
Ma x w e l l , 5 , 1 3
Im pu l se or m om e n t u m , 2 6
.

Mea n a t om i c v ol u m e , 5 3
ra d ia t i o n , 2 2 , 1 0
.

9 .

Mei ssne r , 6 4
Inf ra red dis pers i on f req u e nc i es , 4 5
.

Me ta l s , e l ec tron t eory of , 6 1 h .

In te n si ty , 2 .
Mi che l son Mor le y , 1 -
.

Isn a r d i , 1 20 .
Mi l l i a n , 1 2 , 2 0
k .

M ol ec u l ar ea t , 5 3 h .

M om e n tu m , 2 6 , 1 66 .

m om e nt of , 7 2 , 1 66 .

Jean s, 1 5 . M ose le y , 1 1 0 .
 I ND E X
R u therfor d , 8 4 , 1 7 1 .

R yd ber g, 9 0, 1 1 0 .

N er ns t, 9 .

a n d L i n d e m a n n s f o rm u l a , 3 7
’
.

N er n s t s h ea t t h eore m , 3 5
’
.

N i c ho l s , 3 3 .

S a ck u r , 8 0 .

O S a d ler , 2 1 .

S chee l , 6 9 .

Orb i ts , a l l owa b l e , 8 7 . S c herr er , 7 9 , 1 19 .

Or tva y , 15 2 . S chr od i n ger , 5 7 .

S chwa r zsc hi ld , 9 3 , 1 2 1 .

P S el e c ti on , pri n c i pl e o f , 9 8 .

S om merfe ld , 2 7 9 1 , 9 4 , 1 02 ,
Pa ra m a gneti sm , 25 .
S ta r k , 2 3 , 66 .

P a rh e l i u m , 9 7 .
e fi ec t , 98
P a sche n , 6 , 9 , 8 9
.

.
S tefa n , 4
P au er , 1 20
.

.
S tef a n B ol tzm a n n , La w , 5
- .

Pha se i nte gra l , 9 2

-
.
S ter n , 2 5 , 7 0, 8 1
Pha se spac e ,
.

-
9 2 , 9 4 , 1 36 .
S to k es , 1 9
Pho to el ec trons , 2 0, 14 1
.

S u ther l a n d , 3 3
-
.

P i er , 1 2 1
.

P l a nc , 6 , 1 5 , 2 4 , 2 7 , 9 1 , 1 1 7
k .

P oi sson s ra t i o , 4 1
’
.

Pol a ri sa ti o n , 1 68 .

Pre ce ssi on , 1 6 7 .

P r i n gs he im , 2 , 4 .

Proba bil i ty , t herm o dyn a m i c , Thom son , J J . 1 9 , 6 3 , 84 .

Q u a n tu m o f ac t i o n , 9 .

R a tn ow s ki , 5 8 .

R a y le i gh, 1 0 .

R efl ec ti on , m e ta l l i c , 45 .
Wa gner 2 1 , 22 .
,
Rel a t i vi t y , 9 5 , 9 6 .
Wa r bu r g, 9 , 2 3 .

We ber , 3 0 .

Wey ssen hof v on , 74

P la nc k s
.
,
6
’
Reso na t ors , , .
Wi edema nn -
F r a n z, 6 2 .

Wi en 3 4
, , .

La w , 4 .

La w of

e fiw t , 9 8 , 1 20 0
IN G RE A T P RE ss , ABE RD E E N
 A S E LECT IO N FRO M

M ESS R S . MET HU EN S
’

P U B L ICA T IO N S
Thi Ca t a l o g u e co n t a i ns o nl y a s e l e c ti o n o f t he m or e i m p o r ta n t b o o ks

pu bli s h d by M
s
e es s r s M th e u en A c o m p l e te ca t a l o u e o f g t hi e r pu bli ca ti o ns
d
.

bt
.

may be o ai n e o n a p p li c a ti o n .

A r ms tr ong ( W T HE A RT OF Cl u tto n Brock W HA T IS T HE K IN G

h d
-

CR IC KE H A F
.

Cr T 800 63 net D OM OF E VEN i ft E i t i on

F
. . . . . .

Bal n ( F W ) ca p 8 vo 5 3 n et
DGT M N A Hi d L AY d
.

F
. . .
. .

A or TH E OO : n oo ove ES S S O N A RT S econd E i t io n cap

St y
I
D NT I
A
. . .
'

T S HE E S CE or THE UN : 8 vo 5 3 n et
f Bi t h D AWN AY d
or
AH F R
. . .

Cy l
.

c e o r EI E o r THE . E SS S ON B O O KS Thi rd E i ti o n
GR A T G D H A R A D R AUGH T
. . .

F ca 800 6 5 ne t
g
’
I N TH E E O S I
DU K Y
. .

F
. .

B LU N
.

o r TH E A E E. N SS E CE o r T H E S . MO R E S S A S O N B O O KS eat) 8 00
IN A R NA T N SN W AMN
. . .

A N C IO 0 1? T HE O I E 6 3 n et
P H M
. .

F AU LT T A H HA R F
.

or A G S HE S ES or OD . S KE S E A E S ’
A LE ca p 8170 T
B U BB L F AH A S YR U P
. . . .

H ES or T E O o n THE 5 8 ne t
J h M RR R
. .

L V RY
.

B EES T E T S HE I E OF VE HE UB Conr ad ( osep ) T HE I O OF .

T AN A DR A A ll F t 8 M
. .

CE o r 5 E N ee ) 00 5. T HE SE A : e m o ri es a n d Im p re ssi o ns
S
F h d
.

S PH R
.

E H
. .

net A H N Wd C O or T E E ES i e ou rt E i t ion F ca 89 0 6 5 net

J
.

y
. . . . .

D em 6d ne t 1 23 Dre ver ( a mes) T HE S Y CH O L O GY O F

R YD A Y
.

H R F
. . . .

Ba k e r (0 Coll i ns ) C O ME Ill u s E VE LI E Cr 800 65

PY H Y TRY
. . . .

O F IN D U S
. . . .

tr a t e d Q u a rto £ 5 5 3 ne t T HE S C O LO G
h F
. . . . .

Balf ou r ( Si r Gra a m) T H E LI E O F Cr 5 3 ne t
R TY
.

R RT AT
.

LO U IS S E V E N S ON T
. .

O BE Tw e n Ei ns tei n EL IV I THE
h d P A RA
.

l ie t E it i on I n one V ol u me S E CI L A ND T HE GEN E L
TH R Y T d by R B R
. .

B u c kr a m 7 s 6d net EO r a n sl a t e O E T W
h d
.

H A R AW N
. . . .
,

Bate ma n ( BOOK OF D A W L SO S eve nt E it io n 5 3 ne t

h d R AT TY
.

F y HT
. . . .

IN G S i ft E i ti o n Ro al 4 to S ID EL IG S ON EL IV I Tw o
by L B RT N T N
. . . .

1 03 6 d n et Le c t u r e s A E E I S EI Cr 800
SU BU BI R A
. . . . . .

D en y 4 to 63 net 3 3 6 d n et
A H RT H T R h T y
. . . . . .

IS O Y
.

Bell ( B e r I S O Ot er B oo ks on t he Ei nstei n he or
y CY gP A P A P A T M M TT R H RM A N N
. .

O F TH D ern So c 2 1 3 net S CE — I E— A E By E
W YL y
. . . . .

8 6 1106 ( E ) E D em 8 vo 2 1 s n et
PAR H LL A N D T AR H R RK
. . . .

IS , 8 s 6d net I S TH E S E A , 6 3 E IN S E IN T H E S E C E : H Is W O
T H NG AND ND R D W TH N T N
.

PLA N D
. . .

ne t ON NO I KI E SU B EX I E IN D IA LO G U E s I EI S E I
V RYTH NG y
. .

j E CTS , 65 net ON E E I 65 net By A LE x A N D E R M o s zx o w s m D em

M TH NG F R T AND A T
. .

L S , 6s
. . .

ON SO E I , 69 n et I S 800 1 28 6d net
TH A N D THA T AND TH R TR D T TH RY
. .

O U C IO N T O T H E
. . . . .

n et IS TH E O E , 63 A N IN EO
MA R ANT N TT R AT TY YN D N LT N
. .

ne t IE OI E E, 1 85 ne t OF EL IV I By L O BO O
P
. .

A
. .

T
.

Bl ac k more ( 8 owe ll ) L WN E N N IS Cf 8 00 55 ne t
D AT d y R T TY R
. . .

T T
. . .

U P TO E Ill us t ra t e D em 800 E LA IV I A N D G A VI A IO N By
d d by
- -

W
. . . .

1 2s 64 n et V ar i o us ri t e rs E i te J MA LCO L H
T T RA P R RD
. . . . ,

Car pe nte r 0 IN S E C NS O BI 73 6 d net

M AT N y R AT TY R
. . .

A N D T H E U N IVE S E
. .

IO D em 8 00 1 23 6d net EL IV I
d h D R H A RR Y H M D T d d
. . . .

Cha ndl e r ( A rt hu r) , D D , l a te Lo r Bi s o p o f . . By SC. I S ec on E i t i o n .

B l oe m fo n t ei n Cr 8 vo 5 3 net
y Th y D A T TH R Y
. . . .

A RA CmL I A n E ss a i n My s ti ca l T H E I E S O F E IN S E IN S EO
’
eo l o g ,
F A T H AND P R N J H
.

5 s ne t I E X E IE CE , 5 3 n et By T H IR RIN G Cr 8 m 5 5 net
UL T P A NG M M N T R AT TY H R RT
. . . . . . . . . . .
‘
rH E C o r TH E SSI O E és EL IVI F O R A LL By E BE
NGL H HU R H AND D NGL
. .
,

net TH E E IS C C RE I E F ea p 800 23 ne t
A L A MU N D J H J RY
. . . . . .

U N Io N , 5 s ne t SC . I, 4s 6d ne t . . . . Evans ( oa n) E N G L IS E WE LLE . .

Ches te rto n ( G K ) R oy a l 4 to £ 2 1 2 3 6d net

T H R FA R H M
. .

o r TH E W HI E
A LLAD
. . . .

TH E B O SE A LL Fy l e man ( B ose ) I IE S A N D C I
N D R D Y d
. .

T H TN G S CO S I E E T RE H E N D O U S NE S F e a p 800 T wel ft h E it i o n
TR FL AND UR N A
. . . . .

I ES A LA R H S D IS C S IO S 35 6d ne t
M LLAN Y FA R Y R d
.

T H E U SE S o r
. . . .

IS CE or ME N TH E I G E EN S i xth E i t ion
D R TY F
.
. .

IV E S I A ll Fe 800 63 ne t c a p 8 vo 3s 6d ne t
W N WAT R FA R Y F T
. . .

LU E
. . . . . .

I E, E , AN D ONG P a p 800 . . . THE I S ec ond Ed i t io n . .

Is 64 net
. . . P ee p 800 . 33 6d n et . . . .
z ME S S RS ME T H U EN .
’
S P UB LICA T IO N S

Gi bb i ns ( H de IN D U S T R Y IN T HE S E VE N SEAS 1 5 7 th T hou s a nd
E N G LA N D H IS T O R ICA L O U T LIN E S
. . .

Cr 8 vo B u c hr a rn , 7 s 6d n et A ls o
W th M p d Pl T th E d t i h h
. .

F
. . . .

i a s an a ns . en i on . ca p 8 vo Clo t , 6 s net
. le at er , 7 s 6 d
. . . .

D y S
en i 64 n t ea 1 25 e n et
IN D U S T R IA L H IS T O R Y O F d
. . . . .

T HE A l s o a Se r vi ce E i t i o n T we V ol u me s
E N GL A N D W th 5 M p Pl F h
. .

d i a s an a an. S qu a re ca p 8 11 0 E ac net
t h E d ti
3s
T w ty
.

h d
. . . .

en
Gi bb n ( Ed w d )
o
C 8
T H E D E CLIN E A N D
-

5
seve n
ar
i on . r . 00 . s .
THE F IV E N IO N SAT 1 2 6 th T ou s a n . .

FA LL O F T H E R O M A N E M P IR E Cr 8 00 B u ckr a rn , 7 s 6d net A l so
.

h h
.

F
. . . .

E d i t d wi t h N t Ap p d ca p 800 Clo t , 6 s net l e a t er , 7 s 6 d

d M p
.
. . . . .

e o es, en i c es an a s
t
by J B B U RY S y ne
, , ,

Al d
.

V l m D eve n o u es e rn
d h a Se r v i ce E i ti o n T we V ol u me s
. .
so
. .

F h
. .

8 00 Il l us t r a t e E ac 1 25 6d n et
d Sq u a r e ca p, 8 vo E ac 3 3 n et
.

U ni ll u s t r a te
. . . .

A l so i n S eve n V ol u me s
PA R TM TA
. . .

h
.

DE EN L DI IE S I o znd TT
Cr 800 E ac 7 s 6d ne t
h d
.
. . . . .

Gl over ( T B ) T ou s a n Cr 8 00 B u ckr a m, 7 s 6 d
F
. .

AR LY
. . .

N FL T R LG N
. .

T H E CO IC O F E I IO S IN T H E E
ne t A lso ca p
. 8 vo Cloth, 6 s n et ; . . .

R AN
OH B H P IR E , 1 03 6d ne t P O E Ts AND l e a ther , 7 s 6 d ne t
A
. . .

P U R T AN FR
. . .

l s o a Se r v i ce E di ti o n T w o V o l u m es
I S , 1 os 6d net O H P E R ICL E s
F h
.

PH L P
.

RG L
. . .

S qu ar e ca p 8 110 E ac 3 3 ne t
To I I , 1 o s 6d ne t VI I , 1 0s 6d
Y AR T h d
. . . .

H R T A N T R AD T N AND TH E S BE WE E N
. . . . .

n et THE C I IO IT s
E 9 5 th T ou s a n
IS I
F
. .

g
.

Cr 8 00 B u c hr a rn , 7 s 6 d net ca p
V E R IE ICA T IO N ( T he A n u s Le c t ur e f o r
h h
. . . . . .

8v o Cl ot , 6 s n et l e a t e r , 7 s 6 d net
6s net
A d
. .

h
. . .
. .

Gra a me THE W IN D l s o a Se r v i ce E i ti o n T w o V ol u mes

Ke n ne th) IN
F h
. .

T HE W I LO S T wel ft W .
.

h d E it i on .
‘

Cr .
Sq u a r e
H YM
c a p 8 vo
N BE O E
E ac 3 3
C IO N F R
Ill u mi n a te d
. .

A T
.

800 7 s 6d net
F
.

TH T Y
.

IS O R
. . . .

ca p 4 t o 1 3 6d net
Hal l ( H B T H E A N CIE N . . . . .

NE R E S RO THE A A T F M R E CE SS IO N A L F
. .

OF TH Ill u m i n a t e d ca p 4 to
E R LIES
A A TT
.

TTM
. . .

I E S T O T HE B LE 1s 6 d net
d F h TW T Y POE MS F R O M R U DY A R D
. .

A AM
.

OF S L IS Ill u s t r a t e i ft Edi EN
P h
. .

t ion D erny 8 00 2 1 s n et K I L IN G 3 1 3 th T o u s a nd F cap 8 vo

h h
.

T H E S CA R LE T
. . . . . . .

Hawt orne ( Na t a ni el ) 13 ne t
R W h h
. .

TT
.

LE E it 31 Il l u s t r a ti o n s in Kno x (E V P u nc ( Evoe
‘ ’
of
PA RO D R E G IN E D
A
. .

by H UGH TH M N y
.

Co l o u r , O SO Wi de Ro a l IE S Ill us t r a te
by RG M RR W
. .

8 vo 3 1 s 6 d n et GE O E O O F ca p 800 5s
h A H T R
. . .

IS O Y O F
. . . . .

Hol dswort W s) n et .
E N G L IS AW H
S eoen V ol u mes D e rn y La m b
( Char l es a nd Mary ) T H E CO M
h d d b
. .

P L E T E W O R KS
.

8 00 E a c 2 5 3 net E i te E
g H R T A MY T V
d d
.

M
. .

In e ( W
.

U A
. .

C IS I N S ICIS L C S A N ew a nd R ev ise
F h i t i on i n
h
. .
.

( T h e B a m p t o n Le c t u res o f
d
i ft S i x V ol u mes Wi t F r ont i s p ieces cap F
h
. . .

E i t i on Cr 7 3 6d ne t 8 00 E ac 6 5 n et
J A N O U LIN E O F E N G L IS T H
. . . .
. . .

e nk s The v o l u m e s a r e
LOC L G O V E N E N A i ft E i t i on , R M T . F h d 1 IS CE M
EO S OSE II E ILLAN U PR L A A ND
E SS Y or E I AT
.

A LA
. .

revi sed Cr 8 00 5 s ne t THE L S

A H RT H T R Y H III B o o x s
PLAY AN D
. . . . .

LA W P o u rs
H LD R N
. .

S O IS O O F E N G L IS POR C I E Iv S
FR M OARL T T M
THE E IE S I E S T o TH E E N D an d LE TT R
. . .

Y AR
o n TH E E 1911 S econ E i ti on , d d v
T H E E SS
.

AY
VI . E S
S O F E LI A Wi t h
.

In t r o
d d
an
.

by U A
.

revi s e D erny 8 00 12s 6 d ne t u c ti o n E V L C d 8 Ill us t ra

h GA R TH J N
S, an 2
. .

y R A
. . .

by A F
. .

Ju l i a n ( Lad oi Norwi c E VE L t i o ns
T d by
O ES. e e t) 800
.
. . .

IO N S O F IV IN E LO V E E d i te
RA h d 5 s net
.

CE W A R R A CE
. .

G S even t E i ti on Cr . . .

La nk este r Sir Ray ) SCIE N CE O AN FR M

8 00 53 net
.

Jh
.

P M .

d h E S A I Y HA
Il l u s t r a t e T i rtee n th R
.

d h
K ea ts ( o n)
‘
OE S E d i t e , wi t In
d
. .

by LN E i ti on Cr 8 00
.

7 3 6 d ne t
.

t r o d u c ti o n a n d N o t e s , E D E SE I
FR M Y H R
. . . . . .

U RT h F Ph S CIE N CE O AN
.

EAS C AI
CO Wi t a r o n t i s p i e ce i n o to
d d d d .

gr a v u re ou rt
.

E i t i on
.
D em F h d 800 . y .
S econ
ti o n
S er ie s
Cr 8 vo
Il l us t r a t e
7 s 6 d ne t
T hi r E i . .
o

6 d net
R A RA
.

NA U T T
. . . . .

d
12s
D IV E S IO N S OF LIS
. . .

Ki d ( Be nj a mi n)
P W R
O E
T HE S CIEN CE
N i n th E d i t i o n Cr 8 vo 7 s 6 d ne t
OF .
Il l u s t r a te T hi r E i t i on Cr d 8 00 . d d . .
.

A
. . .

S OCI L E V O L U IO N D e m y 8vo 8 s 6 d n et
T 7 3 6 d n et
. . . .

R T RT H
. . .

PH PH SE C E S O F E A A ND SEA
. . . .

Cr
R TH AT R
.

A IL O S O E WI N U E . .

d d
.

800 8 s 6d net
S eco n E i tion Cr 8 00 7 3 6 d ne t
. . . .

Ki li ng g y Ru dy ar d ) B CK OO
. .

A R RA
. . .

R
.

M Lod g Oli ver)

e ( Si r MA N AND THE
E h d U N IV E R S E : S N F LU N
.

A T UD Y
.

A L LA I 2 1 5 th T ou sa n Cr 8 00 or TH E I E CE
A DVAN NT F KN W
. .

B u c kr a m , 7 s 6d net A l so cap Bo o F or TH E CE IN S CIE I IC O

h h L DG UP N U ND R T AND NG
. . . . .

Cl ot , 6 s net ; le a t e r , 7 s 6 d net E E O OUR E S I or

A d
. .

CH R T AN T Y d
. .

ls o a Se rv i ce E i ti o n T mo V olu mes . . IS I I . N i nt h E it ion . Cr . 800 .

S quare cap 800 F

E ac h 3 s net . . 7 3 6d . . net .
 ME SS RS ME TH UE N P U B LICA TIO N S
’
. S 3
T H E S U R V IV A L O F M A N : A S T UD Y IN GU T ES 6s ne t PO E HS, 5s net THE
NR
U E CO IZE H U H A N GN D T RM F A UL TY S h WR A K
. .
, . .

C eve n t C or THE S O 6s net T HE

Ed t A N TH N Y A P y
.

M RA L
.
, .

C 8
i on 7 6d t 00. S 5. ne I C E OF O l a i n On e
M O D E R N P R O BLE MS C S 7 6 d t
i . r. . . T .

A t 3 6d t T B r. ea . 3 ne c ne HE U RG O H A S TE R
R A YMO N D AND D A T H
s
A Pl y i T h A t 5
or
L F
. . . . . . .
,

S OR M I E E T IL E ON DI : a n
t d Tw l ft h E d t i
re e c s,
B d
s.
D my 8
.

Il l t
u s ra e t eT H B TR T HAL ; iT h Bl on . e 00 ne E E O o r, e ue
Ch M UN T A N P A T H 6
. . . ir
1 05 6d t ne 6 t o o se s , s ne O I S,
L i ng ( F
8.
A T O M IC T H E O R IES T H S T RY T Y L TY L
. . . . .

or IL) n t e E O or 2 1 s.
D my 8 . .
. .
,

e 6d t 00 .
M i l ne ( A A )
1 23 . . ne .

T HA T MA TT R F p 8 6s
. .

Lu as ( E V )
c N OT IT E S ca oo
L F CHA R L I I MA Y F p 8
. . . . . .

T HE I E or L H l t ES A 6 t
B , 2 vo s 2 13 ne P ca vo . s. ne
A W AND R R H LLAND Ne i ll ( R l p h ) Y
. . . . . .
,

ne t 6d E E MIN A FA IR A N D M O N T
O 1 0s . v a
A W AND R R L ND N
.
.
,

A R T R E D my 8
.

ne t
L ND N R V
.

T D
6d
A M E E IN
5
On t O ,
1 0s . .
e vo . 1 s. e

d ( Gil b t) E U R IP ID E S
.

ne t O 6d O t E IS I E 1 0s ne
W AND R R P A R w AND
. . . .
,
or oo er
6d d 6
S HAW W T T R Y
.

ne t A W AND R R F L R N
E E t IN
6d E E
H
IS ,
IN
H 1 0s
E A .

O
C
E
. ne
CE , 1 05
an s .

: I O E SS S . r.
6d
A W AND R R V N
.

t
. .

t 6d t E
7 ICE , 1 0s ne
s . . ne .

ne E IN E
R A b T R T U R
.

P N AD
. . .

T HE O Li t t
E l B k f O sO
n ( E L I E A E AN D e oo or or
L IF E
.

W yf a 6 6d
a re rs , t TH FR NDL Y s. C 8 ne7 6d t E IE r. vo . s. ne

O nh m ( J oh n)
. . .

T WN A Li t tl B k f t h U b
. .

O : e oo or e r a ne , xe a
6 t F R D AND S U N H N
ne B I ESI AH ; A
E Li t t l B k f S I E, E ES IN BE R e oo o
T h gh t f l V
5
CHA R A T R AND C DY 6 t
. .

o s . net C E S m ll P tt ONE 800 s ne ou u e rse . a o

G NTL A Ch d A LL W L L ;
.
. . .
,

T HE TA E f L tt ES S t i ff B RT : t o i ce o e e rs oa r s 2s ne
’
S E
by E t t i i g H d 6 6 d t T H A C ll t P m TH K N G S
. . .

f W
’
n er a n n an s, s ne E o e c i on o ar oe s E I
ND P T 6 IN F N T W A Y T H V N S PL ND D
. . . .

S E CO t H OS H H s ne ER I I E IG E IS IO E I
A F m i P t i t G ll y
.

V A R TY F RY CR H GH A
. .
,

IE : TH e i n ne or ra Th a er E IE OSS I LT A R s z e
D C M PAN Y A R ll y f M R d f V i i t t t h B t tl fi l d f , .

6 s t ne G OO O : a o en, e co r o a s o e a e e s o
AND A N TH R 6 t F d Fl d H A RT C U R A
. .

6 5 t O
ne D NE AY O E s . ne r a n ce an an e rs E S O
LAM P L T R R CL A R ! A l l S m ll P tt
. . . .
,
'
O LD N w 6 t S POR E A s ne OI E E S GEOUS LL E a o
H A R V T 6 t CL UD AND S LV R 6 l th b d
. . .
,

ES s 8
ne P p 3d O t I E s. 00 a er , 1 s ne c o oa r s , as .
A B W LL B AGHDAD AND T H R W ND D AW N
. .
, , . . .

ne t OS E t OP H G H O E ne I S or T E E N TLE EN
AY 6 TW T E AGL AND K NG
.
, . .

E SS t S, s — TH
ne
’
t IX E E I 2s ne
D V 6 t T H P HAN T M J U RN AL Pet i ( W M Fl i nders) A H ISTO R Y O F
. . . .
,

O E s ne E O O
A N D TH R E A Y A N D D V R N 6 E G YPT t d
r e
. .
, , . . .

O E SS S Si V l m I C E S IO S, s
ALL Y S L T D A Ch i f 8 E h 9
Ill t us r a e x o u es . r.
.

SP
. .

ne t E CI E EC E : o ce o
y 7 6d t UR B AN T t 00 ac s ne
.
. . .

E ss a s, s Il l V I ne F M H 1 o H X VI H I IE S us O L. RO T E 31 T T E T
by G L S D Y NA TY N i t h E d ti
. . . .
.

t t d
ra e 7 6d t TA N P A 6d t ) s ne
( S n i on 1 0s ne
BR T H S H L A A d tl V
. . . . .
, .

N
. . .

A D
.

TH E I IS C TH OO : X V III H n ne c o a
G d t h B i ti h P i t d P i t
11 X V II O L. E TH T
D YN A T S i th E d it i
.

ui t e o e r s a n e rs a n a n
i g
S IE S on .
l G ll y 6
x
X X X H D Y N AS T S
.

n is th N ti n e t V a
III ona
X IX H a er 3. ne
OL T To T IE
R V NG E A T AND R V NG W T N t d E d it i
.
, . . .

O I S O I ES : o es
g t h d i I di J p
a e re d Am i n
V n
S
IV a,
E GYPT U N D R a an ,
H P an er c a . OL
eco n on .
E T E T O LE N A IC
E DW N A U T N ABB Y D YN T Y J P MAHA FFY S d E di ti
.

A
.

5 s t ne R A I S I E
V RM R D
. .
, . .
S . econ on .
E G Y P T U N D R R H A N R UL
. . .

2 lvo s £6 6 t s . ne
V V E EE OF E L PT ,
O L. E O E.

J G M LN S d HE d
. .
.

1 0s 6d . t . ne .
I E. ec o n
R E M B R A N D T S P A IN T V E G YP T M DDL A G
. .

l i d ru m ( D
’
e VI O L. IN T E I E E S.
IN G S Wi d R y l 8 £
.

t e S T ANL Y L AN
o a P L S d E d iEt iLL
oo . 2 2s ne
.

E E OO E. ec on on .

M th
e n ue A
.

N A T H O LO Y O F
N G S Y R I A A N D E G Y P T F R O M T H E T
. .

A M A R A TT R
,

M O D E R N V E RSE W t h I t d ti E L N L E E S i
C 8
n ro uc on
. r. 00.

by R B RT L YN D S t h E d i ti
.

5 t ne
YP
s
O E eve n on.
T T T
.

l th
.

F p 8 m th
.

E G I A N A LE S n l t d f ra s a e ro e
ca 6 t T hi p p
vo .
P
s . ne
y F n
h er, ea
.
. . a er ,
i i t S i t h t t rs e r es , Iv o E ri
D t d T h i d Ed t
p a r
7 6d t
s ne
y ty
.
. . .

ng all
Il l t n as us r a e r i i on .
Wil l ia m
. .

AN IN T R O D U C
T IO N T 6 S O C A L PS Y CH O LO G Y E G YP T IA N T A LE S T n l t d fr m t h
c o
C 8 t.
5 r. 00 . 3 . ne .

th E d t i
.
ra s a e o e
S t
eve n ee n C 8 8 6d t P py i S d S i
i on . r.
th t vo . th s. . ne
.

e r es , E V III o x xx
B O DY A N D M IN D A H T R Y AND A
e con
.

t d Ed t n
a r
Dy ty
.

Il l : t S nd IS O us r a e eco i io
F i ft h E d t i on
n as . .
.

D E P E N CE A OP C 8 N IN IS N
5 t i r. vo . s ne
D my 8
.

P oll i tt ( A rt h r T H E E N J O Y ME N T
. . .

e 6d t vo . 1 2 s. ne
u
. .

N A T IO N A L W E LFA R E AN D N A T IO N A L O F M U S IC S ond E d iti C 8 0 ec on r. 0

D E CA Y
. .
.

C S 6 n t . r. 5 t
ee . 3 . e . 3 . ne .

l ae te r l i n c k ( M a r i ce P ri
u c ( L L A S H O R T H I S T O R Y O F e
T H B LU B R DE F i ry Pl y i Si A t
E I P O LIT IC L E CO N O M Y IN E AN GLNAONLDD
a a n x c s
. .

6 t MA RY MAGDAL N A P l y i
ne F R O M A D A M S M IT H T O R E
TO Y N B E E E l e t h E d it i n C 8
s E : a n
Th A t 5 n t D A T H 3 6d t
. .

r ee c s, 3. e E s. ne ev n o r. vo.

E T R N IT Y 6
.

UN KN W N
. . .
, .

O UR n t TH E s n t , s. e . E O e. e .
 ME SSRS ME THUE N P U BLICA TION S
’

4 . S

Sol on: ( Ed mu nd)

'
Turner ( W L) . M U SIC A N D LIFE
.

TOH HY S H ITH S A N IH A LS TO H H Y Cr 8 vo 7s 6d t ne
TH R AN M A L TH M YS T ICIS M
. . . . . .

S H IT H S O
’
E I S TOHHY SN I Und erhi ll ( Evel y ) n
AT AGA N A dy i
.

T
. .

THE Zo o T O H H Y S H IT H I Stu t h e N a t u r e an d D e v e l o p m e n t 0
JA K N T
.
n
TH E Z O O E ac h 2 3 9 d
TH R
C
’
S I SE C S, Man s
’
S p i ri t u a l Co ns ci o u s n ess N i nt
N T d
. . .

y
.

as 6 d JA CE S O E
’
. . I SE C S , 3s 6d . .
E i t i on D em 8v o 1 ss n et . .

Y
. .

Shell s ( Pe cy Bysshe r P O E M S Wi th Var d on ( H arry) H O W T O P LA GO LF

by CLU TT N B R C d F
.
.

na nt d ti ro uc on O -
O E Ill u s t r a t e i ftee n th E di ti on Cr 8 1 m
and N t by C D L o es K Tw O CO C o
5 s 6 d n et
. . .

D my 8 0
. . .
. . .

V l m o u es £ t e 0 . 1 1 s. ne
W E A LT H O F N EW
.

Wad e
.

Smi t h ( A d a m) T HE (G TES T A ME N
E di t d by E DW N CA NN A N H IST O R Y y
.

N A T IO N S
.

e I D em 800 1 8s ne t
Thi d E d i t i
. . . . .

D my
.

Tw V l m o o u es . r on . e
b th) A LITT LE B O O
Wate rhous e ( Eli za e
£1 O F L IF E A N D D E A T H
net
.
1 o s. .

T yf w e nt i rs

E di i
Smi t h K ai nes) LO O K IN G A T
-

(S C
.

P T U RE S d Sm ll P d
. .
8
.

t on a ott 00. 2 s. 6 n et
IC Il u s t r a t e d S econ Edi
. . .

F p S H O R T H IS T O R Y O
. .

it on . ca 8 vo 6 s n et W ll A
(J
e s
A TH RA MA R O M E E igh h E di i
. . . .

Sp e na t) ane . E L IZ B E AN D .
Wi th tee n t t on .
M
.

Cr 8 00 65 n et . Cr 8 vo
ap s . 5s
E RS O F
.

TT
. .
. . .

Ste venson T H E LE (R
R O BE R L O U IS S E V E N S ON E di t e
T T d Wild e ( Oscar) T H E W O R KS O F O S CA
.

DE F h
.

by DN Y LV N W IL
.

Si r S I CO ca p 8 00 E ac 6 s 6d n e
A N ew Re
L R D ART HU R
. .

AN
. .
E I
.

d d F
.

S A V IL E S CE IH E
’
I O
a r r a n ge E i t i on i n fou r vol u mes ou rth
P RTR A T M R W H TH
.

d F h
.

TH E O I or 11.
E it i o n ca p 800 E ac 6 s n et
DU H P ADUA P M
. . .
. . . . .

C ESS OE III. OE S I'v

LAD Y W V AW A
. .

Snrt e es ( B S )
H A N DL Y CR F
’
. .
IN D E R H E R E S AN. OH
Mr
.

7
E 6d t OS S , s. ne
ID AL H
S P R T NG T U R 7
. . .
or N I O A H P O R T A N CE VI N E US
AND IM P RT AN B N
. .

S
’
P O N GE s 6d t O I O s ne
Th Ri h t C mm
B TH O CE or EI
A K MA MM A
V II E
. . .
,

E A RN T V A H U P H
. .

S or, e c es o o n er
E gl d 7 6d t J ES III O SE OE O E
G RANA T INT N T N
. .
'
i
n n an K s. ne ORRO C S S
D P E IO S x E RO
A N D J LL T MR
. .
,
E S. Ix
F UND AND P R N L TT R
. . .

£A Y R H
AUNIS
‘ ‘
6 t O I IE S , s. ne
E IS O E E S x1 s
H UND 7 6 d t IS
. .

AY A FL R NT N
. .

S AL
’
CE O EO R D S O S, s ne
S p ti g
ON E , O E
G R ANG ;
x 11 . I
.
S S.
. .

H W
Ad
A B U CE
f Th m
Th E or, e or n
T R AG D Y d L S A N T C U R T AN
E an A I E O IS E
tven ures S tt E q
P LA N R NGL T ? 7 6d n t
6 o o as co , s .
, s.
X III. A CR T P ALL MALL ,

I IC IN X IV
T D PR A R W LD
.

net I OR I E S s. e
S L EC E O OSE OP SC I
H L L NGD N H AL L 7 6d t
.
E
.
E
.

I I O , s. . ne .
xv A .A N D D RAT N RT E CO IO .

Tfld e n ( W T H E A RT O F LA W N
.

F d A H O USE O F P O ME G R A N A TES
‘
Ill us
éEn
t Ia t e d
L
T IS II u ou r th E i ti on
.

; t ra t e d Cr
. .
n et
.

6S
. . .

O
Til e st on ( Mar y D A ILY S R EN G T TH Yeats ( W A BO OK OF IR IS
A ILY D h VE RSE F
.

FO R D N EE S T wen ty s eve n t ou r th Ed i ti on Cr 7
d d
-
. . . .

E i t ion . Me i u m 1 6 mo 3 s 6 d n et . . . . net .

PA RT II .
— A SE LE CTIO N OF S E RIE S
The A nti qu ary
’
s Book s
D emy 8 11 0 . 1 03 . 6d . n e t e a ch vol u m e

W it h N u m e r o u s Il l u st r a t i o n s
A NC NTIE LA P A NT D
E NGLA N D I E G SS IN MA N R A ND M A N R A L R R D TH
O O I E CO S
AR H L G Y AND F AL ANT Q U T M D VAL H P T AL
. .

C E O O SE I I IE S E IE E OS I S OE N G LA N I:
B LL E NGLAND B RA E NGL H IN TR U M N T
.

TH E E T S OP HE SSE S O LD MU IS S E S OP SI
E NGLAND CA T L AND W ALL D E N GL H L BR A R
.

OP T HE S ES E O LD O S IS I IE S LD E R V IC
E N GLAND C LT E N GL H CHU R H PA R
.

T WN
.

O S OP A E IC RT IN B o o x s O P TH E IS C
CHU R H
IS
P AGAN AND CH R T A N T
.

M D VAL E NGLAND TH
.

IS I IE R S . C L IF E IN E IE
WA R D N A U NT T D PAR H R G T R E NGLAND
.

’
E S CCO S. HE OHESDA Y IS R E IS E S OP
T E N GL H CHU R H F U RN T U R
I
IN Q U ES IS C I E. H H PR H T R A
A IN s o r EN T E E IS O IC G E IN
.

E NGL H C T U M E N GL H M NA T LAND T R HAN E B R TA

.

IS OS E. IS O S IC HE O RA IN I I
L F E NGL H S AL F LK L R R AN B R T H B U LD NG A ND E
.

I E IS E S O O E As OR O I IS I I S AR T
W RK T R Y AL F R T
- -

A N H T R AL S N G LD AND
. .

IS T O IC CIE CE . HE I S O S E HE O O ES S OP N
C M P AN L ND N LAND T S H L M D VAL E
.

O TH
IE S H or O O E R R N IT S HE C OO S OE E IE N
A ND A N H R T E N G L A ND LA ND SH R N B R T H S A N TS
. .

C TH O I ES OP . E . I ES or I IS I .
 ME SS RS ME TH UE N P U B LICA T IO N S
’
. S 5

The A rd en Sha k esp ear e

G e n er a l E di t o r , R . H . CA SE
D emy 8 vo . Os . n e t e a ch vol u me

An e di ti on of S h ak e sp e ar e i n Sin g l e Pl a y s ; e a c h e di t e d wi t h a f u ll In t r o
d u ct i on , T e x t u al N ot e s , a n d a Co mm e n t a r y a t t h e f o o t o f t h e p a g e .

Cl assi cs oi A rt
E di t e d b y D R J H . . . W . LA IN G
Wi th n u mer ou s Il l u s tr a ti on s . Wi d e R oy a l 8 vo
“
BIS A R T O R THE G R R EE S, 2 1 s. ne t TH E n et . R A P HA E L 1 ss n et . R E M E RA N D T ’
S
R MAN HA R D N T H NG R E M B R AND T
. .
,

A R T O P TH E O S , 1 6 s net C I , E C I S, 31s 6d net

’
S
D NA T L L RG PA NT NG T NT R TT
. . . . .

1 ss n e t O E O , 1 6 s n et GE O E I I S, 42s n e t. I O E O, 1 6s net
H R LANDA T T AN 6 TU R N R S AND
. . . . . . .

'
R O M N E Y , 1 5 s n et G I IO , 1 5 s n et I I 1 s. n et E S E E T CH E S
AW R N M H LA N G L RAW NG
. . . .
.
,

L E CE , a 5 s n et IC E E O, 1 5s
. . . D I S, 1 5 s net . . V E LA S Q U E z, I ss . n et .

The Comp l ete Seri es

F u l ly Il l u s tr a ted . D e my 8 vo
TH E CO P E E A I
M L T R M A N 6 n t TH 1 s. e E 5s n et THE CO MPL LA w N E TE T NN S
E I
A AT U R B P LA Y R M PL T
. . .
,

CO H P LE T E M E 6d t O E E R, 1 os . ne E 1 zs . 6d n et T H E CO E E
M PL T A AT N F T M T R T M PL T
. .
. .
,

TH E CO E E S S O CI IO OO O O IS 1 os 6d n et T H E CO E E
B ALL R C MP L T M UN T A N R M PL T
. . .
,

E 6d t TH 1 03 ne E O E E O I EE 1 6s net T H E CO E E
AT HL T T R A N R O AR M A N MPL T
.
, . . .
, .

IC 6d n t T I E 1 0s
'

e HE 5 S 1 3 ne t TH E CO E E
B LL A R D P LA Y R
E
C M PL T
. . .
, .
, ,

O E 6d
I I E 1 os .
R UG BY F TB ALL R
E
C M PL T
.
,

ne t TH C E 6d
O t E E oox, 1 os . ne OO E ON TH E N EW ZEA
C M PL T F HUN T R 6 LAND S Y T M
.
. .
,

T HE O Et E OX E 1 s ne 6d S E 1 zs . n e t. T H E CO M
C M PL T SH T MPL T
. . .
, ,

T HE G O 6d t
E E O LP E R , 1 zs . ne P LE T E 6 t O 1 s ne TH E CO E E
C M PL T H K Y P LA Y R S W MM R MP L T
. . . .
,

T HE O E 6d E OC E -
E 1 0s 6d
I t E 1 03 ne TH E CO E E
C M PL T H R M AN 5 YA H T M A N 8
. . . .
, .
,

ne t TH E O E E O SE 1 3 C t S 1 s. ne .

TH C M P L T J J
.
. , ,

ne t . E C 8
O E E U ITS U A N . r . vo.

Th e Connoisseur Li brary
’
s
Wi th n u merou s Il l u s tr at i on s . Wi d e R oy a l 8 vo . £ 1 1 IS . 6d . n e t each vol u me

E N GL H C L U R D B O
IS ET H NG
O O E OES C I S. IV R J w
O IE S M E E LLE R Y E zzO T IN TS
EUR P AN E NA M L FN B K M N A TU R P R LA N A LS
. . . .

O E E S I E OO S I I ES. O CE I SE
G LD M T H A N D S LV R M T H W D S U LP T U R
. .

G LA
. .
’ ’
SS. O S I S I E S I S OO C E.
W RE O ILLU M N A T D
. MA N U R P T I E SC I S .

Handbook s of Theol ogy

D emy 8 vo
TH E D O CT RN I E or TH E N AR N A T N 5
I C IO 1 s. TH E C R D EE S, 1 2 s 6d net . T HE P H IL O S O P H Y
A H T RY E A R L Y CH R T AN R E LIG IO N NGLAND A N D A M R A
.
, .

ne t IS O or IS I OP IN E E IC
D TR N IN TR DU T N X X X IX A R T L
.
,
OC I6 t E, 1 s ne O C IO To 1 23 6d n et TH E IC E S o r
H T RY R HU R E N G L A ND
.

LG N H
. . . .

TH E IS O OP E I IO 6d t 1 zs ne TH E C C OP 5 n t 1 3. e
IN T R DU CT N To H TO Y R
. . .
, , .

AN O IO TH E IS or

Heal th Seri es
F ca p 8 vo . . 2s . 6d . n et
T HE B A T CA RR
RT . H B DY T HE OP T E O HE LO NG TH E P R V NT N E E IO O R TH E CO MM O N
AR T TH TH E Y LD YI TA N G P LAGU
. .

C E H OR T E EE E ES OP OUR CO S TH E E. h RO A Q
H LD R N H AL T H M DDL AND TR U B L TU B R UL
. .

C I E . E POR TH E I E EA R O ES E C O S IS .
A G D TH H AL TH A W M A N TH A LTH H LD
.

E . E E or O E TH E HE o r TH E C I 2s . net.
H A LTH S N L V
.
,
E H H w OR T E EI . o To I E
6 ME S S RS ME TH UEN P U BLICA T ION S
’
. S

The Li brary of D evoti on

Ha n d y d o f t h e g r e a t D e v o t i o n a l B o o k s w e ll e d i t e d
E i t i on s ,

W i t h In t r o d u c t i o n s a n d ( W h e r e n e c e s sar y ) N o t es
S m a ll P ott 8 vo cl oth 3 3 n e t a n d 3 s 6 d n et , , . . .

Li ttl e Book s on A rt
Wi th m a ny Il l u s tr a ti on s . D e my 1 6 mo .
5 3 . n e t e a ch vol u me

E ac h v ol u me p a g e s a n d c o n t a i n s fro m 3 0 t o 4 0
c o n s i st s of a b ou t 2 00 ,

Il l u st r a t i o n s i n cl u d i n g a F r o n t i s p i e c e i n Ph o t o gr a v u r e
,

A L BR HT DB EC TH A RT R E R. J APAN B U H R E H LB N S ILLU M NA T D
OP O C E O EI I E
B TT BURN MANU R P T J W LL R Y J HN H PP
.

LL
. .

B o o x P LA T E s O ICE I E SC I S E E E O O
J HUA R Y N LD M LL T
.

C LL N
. . .

J oN Es C E S I IM Si
H R IS T IA N Y H B O L IS N E R. r OS E O S. I E
CH R T CLAUD C N TA B L M N ATU R L AD Y
. . , .

ISA IN RT E O O A S E. I I ES UR IN RT
C R T E A R L Y E N GL H W A T R C L U R R APHA L R D N TU R N R V
. . .
.

O O IS E -
O O E O I E A N D Y CE .
FR D R L GH T N G R G W A TT
. . . . .

E N A H E LS . E E IC EI O EO E S
R MN Y GR KA AND
. .

O E . G EE RT . R E U zE

Th e Li tt l e Gu i d es
W i t h m any Ill u st r a t i on s b y E . H . NEW an d ot he r a r t i st s, a n d fr o m
ph o t o gr a phs
S m a ll P ott 8 vo .
45 . n et to 7 s . 6d . n et .

G idu es g h a n d W e l sh Co u n t i e s a n d s o m e w e ll k n o w n di s tri c t s
t o t h e E n li s ,
-

T h e m a i n f e a t u r e s o f t h e s e G u i d e s a r e ( I ) a h a n d y a n d c h ar mi n g f or m ;
( )
2 i l l u s t r a t i o n s f r o m ph o t o gr a ph s a n d b y w e l l k n o w n a r t i st s ( 3 ) g oo d -

p l a n s a n d m a p s ( 4 ) a n a d e q u a t e b u t c o m p a c t p r e s e n t a t i o n O f e v e ry t hi n g
t h a t i s i n t e r e s t i n g i n t h e n a t u r a l f e a t u r e s hi st o ry a r c h mo l o gy a n d ar c hi , , ,

t e c t u r e o f t h e t o w n o r d i s t r i c t t r e a t ed .

Th e Li ttl e Q u art o Shak esp eare

E di t e d b y W J CR A IG
. . . Wit h In t r o d u c t i o n s a nd N ot e s
P ott 1 6 713 0 .
40 Vol u m e s L e a the r p r i ce .
, 1s .
9 d ne t . e ac h vol u me
Cl oth, 1 5 6 d ne t . . .

Pl ays
F c ap . 8 vo .
3s . 6d . n et

MIL E S T O N E S A n ld B r o e nn e t t a n d E war d
d T Y PH N A Pl y i F A t M l hi OO a n ou r c s e c or
K bl k Te t h E d i ti L gy l E g h V by L
. . .

no oc n on i en e n li s e rs o n a u r e n ce
ID AL H U B A N D A Wi l d d
. . .

S O N. s c ar A Ie. S Edi ct r vi n ec o n tw n
i g Ed t g Pl y d ll
E
WAR
.
,
n i i on T G E A SE, HE eor e e e
E dw d K bl F th E d i G N R AL P T J E H l d T y
.

K M T
. .

IS ar no o ck . ou r E E OS aro e rr
d Ed i
E . . . . .

ti on S ec o n i t on .

T H G R A T A DV NT U R H N YM N A d B
.

E E E E. Ar no ld B T en ne t t . tt Tb i d HE O E OO r n ol e nn e r
F i fth E di ti Ed i
. .

on . i t on .
 ME SS R S MET H UE N P U B LICA T IO N S
’
. S

Sp orts Seri es
Il l u s tr a ted F ca p . . 8 vo
A LL A OB U T F L Y NG I A LP N
33 net I E P LA Y R AW N T NN 3 t
E S, 2 3 net L E IS , s . ne
AT H GH T AND A N AND D N T
. .

L AWN T NN
.
, . .

S E I IN G A LL EI S SE S O S, D t
E IS o s
’
O
’
S, 2s ne
Y UNG P LA Y
-

R UN TRY L AW N T NN
. .

5 3 net C O S S CO S E T IN G , 5 3 n et E IS P OR O E RS ,
AND D NT
-

LP
. .

L AWN T NN CLU
. .

’
GO Do s
’
O S, zs 6d net as 6d t ne E IS TOR E
UT D LF P LA Y R
. . .

L AWN T NN
. . .

Q C C S T o G OO G O 23 6 d n et 6d t E S , zs ne E IS P O E
U I R
N P R D LP DR V NG MA T H P LA Y R
. . .
,

H K Y
. . .

I S I E GO 2s 6d ne t I I C 6d t E S, OC E
A PP R A H NG P U TT NG
. as . ne
SW M
. . . .
, .
,

O C I I as ne t GO LF A s t H w ne t P o To I 23 ne UN D
'

LU B AND TH M S K A T NG
. .
, , . .
, . .

C S HO W To USE E as n et IN G , 3 6d t 3 s t ne I s. ne
R LP
.
, . .

A NAL WR T L NG
.
,

TH E S E C E T O P G O
. .

P O R O CC S IO t
ES I , as . ne .

The Westminster Commentari es

Ge n e r al E di t or W A L T E R L O CK ,

D e my 8 va
TH E A T C S or TH E A P TL OS ES, 1 23 6d net 1 6 s net 8 3 6d n et T HE JO B
S O P A T RA L
P H L P P AN
.

AM R N TH AN 8
. .

P TL
. . . . . .

OS, I CO I 83 6d . ne t . I S, 3. E IS E S, 8 s 6d ne t TH E I I I S,
JAM
. . . .

64 ne t E x o D U S , 1 53 n et E zE R IE L , 8 3 6d ne t ST ES, 83 6d ne t ST
H BR W
. .

N
.

MA TT H W
. . . . . . . . .

1 2 3 6 d net G E E S IS , 1 6 s net . . E E S, E S , 1 5 s net S T LU R E , 1 5 s net

A AH J R M AH
. . . . . . . .

8 3 64 net
. IS I .
,
1 63 net . . . E E I ,

Methu en s Tw o Shi lli ng Li brary ’

Ch e a p E di t i o n s o f m a n y P o p u l ar B o ok s
F cap . 8 00

P A RT 11 1 — A SE LE CT ION . OF W O R KS OF FICT IO N
d
Be nne t t ( A rnol ) m
Core lll ( Ha r
CLA Y HA N G R 8 E 3 net H LD A L I E SS W A Y S , A R M AN O CE o r TWO W O R LD S 7 3 6 d ne t
TWA N T CA R D
. .

T
,

V ND TT A y
. . .
,

83 6d net H E SE I HE E E or, T he S t or o f O n e Fo r
R G NT A Fi T w S t y f g t t 8 t TH L M A A g
. . . . .

T HE : ve o ns or o N o rw e i a n
Ad t i L d PR
E E o en, 3 ne E :
Pf AR DA T H y
. .

ven T n on on HE IC E or 8 6d t T h e S to r
BUR D AL V
ur e r i n ce s s , 3 ne
A MAN P R M D d S l f 7 6d t
.

L V UL
. . .

O E IE I E. O o a ea e s ne TH E SO or
N RT H MA T AD R FV D AD m
.

L L TH 7 6 d t W RM W
. .
, .

THE T O HE O o r TH E I E I I s ne O OO ra a
T WN WH M G HA T H J N D A f P
.

B A R A BB A AD m f
.
, . .

O S O OD OI E o 8 t
a n s, 5 ne S re a o
G R A T MA N A F li MR P th W ld T g d y 8
. .

S RR W
. .

E : ro c. . R O H A CE . e or t TH
’
s ra e s ne E O O S
S A T AN MA T R
. .
,
A ll 7 5 6 d n et or 7 6d t TH s ne E S E
T M P R AL P W R
. . .

CH R T A N 8 6 d
, . . .

Bu mi nghs m ( George A ) t
A R H P A R TY
IS I s ne E O O E :
P AN A St dy
.

H LD ,

G D
. . .

S IS GO T HE SE C Su m y 6 t
In u re ac 3 ne O
’
S
ALAG V R TM U
. .

D MA N A m p l L S t y 8 6d
. .
,

L E S LO E S
’
THE BA D I ES. P, G
T AW Y R A l l
OO i e ove or 3
R B L H LY O RD R Th T g dy f
.
. .
,

TH E E E S T H E LO S L . E . ne t O E S : e ra e o a
7 s 6 4 net IN IS H E E N Y , 8 3 6 d net .
Q t Li f 8 6d t T M GH TY AT M
gh g ui e e,
A S k t h 7 6d t
3 ne HE I O
. .

Ri ce )
. . .
. . .
,

Burr ou s ( Ed ar 7 s 6d t B ne OY : e c s. ne
AP CA M E V R LA T NG
. . . . .
.

T A R zA N or TH E E S, 63 net TH E 6 t
EO S, TH L 3 ne E IT E E S I
R E TU RN AT
. .

TH L V L NG A AN D
. .
,
or T A R zA N , 6 s net TH E B E S S 8 s 64 t ne E O E or O GO,
O TH R S T R
. .
.

N
. .

or T A RzA N , 6 S ne t T H E S O N o r T A R zA N , E 8 6d t INN
O IE S , s. ne O CE T,
UNGL TAL R T P W R: A
. .
. .

63 ne t J E E S o r T A R zA N , 6 3 6d t TH S
7 S ne E EC E O E
AND J W L O PA R
. .
.
. .

R o m an ce
.

net T
T
.

U N T A M D 7 6d t
A R zA N TH E E E S or , of t he Ti m e, 7 S 6d . . net .
6 t ne A RzA N T H E E S. ne
A PR N
S
MA R 6 t T G D
. .
. .
,

I CE SS O P S, 3 ne HE O S
MA R 6 WARL RD
. .

or t T S, 3 ne HE O OP
MA R 6 t T MA D M
. .

ne H UV I A , I or A RS,
S,
b
5
H T RR B L mehe ns
. .

6 t
s . ne T 6d t A R zA N T E E I E, 2S ne ( Ro e rt)
T NGU N N
.

W TH
. . .

T M
HE 6 t TH M U G RE R , 3 ne E AN I O ES 6d or CO S CIE CE , 73
Y
. .

T
.

A S UL 6 t
.

OUT O 3 ne F E LIx h r ee e ars i n a Li te , 7 3 6d

J
.

W M AN W T H
. . .

Conra d ( ose p h) TH E O I TH E F A N , 7 S 6d
R ARD N A LLAH
.

V IC O Y : A n T
.

A SET or 5 11 7 S 64 net TH E G E or 83 6d
d T
.

ALL L D
. . . .
, ,

Isl a n al e Cr 8 00 ne t TH E TH E C or TH E B OO , 8 3 6 d
R T AG NT A 93
D W LL R TH R H LD
. .

T
. . . . .

SE C E E : Si m p l e a le Cr 8 0m TH E E E O N THE ES O , 7
3 64 . .

W A Y AMB T N
.

U ND R T RN Y
.

net E WE S E E ES Cr ne t TH E or I IO 7 3 63 net
LD R
. . . . . .

C' m
AN IN TH E WI E N E SS , 7 3 6d net
.

O “a . CH CE “a . . . . . . .
8 ME SS RS ME THU E N P U B LICA TIO N S
’
.
,
S

Hope ( A nth y) on Oxenh am ( J ohn

A C A A MA N
HA N G E OF IR OP MAR E P R O P IT AND TE E S O o n HT
o ss. NG »
S M N D AL K NG M IRR O R h
.

NT
.

L
.

’
I OT E HE I S CI E a n d O t e r S t o ri es T H E CO I o r
D LL Y D AL GU
.

CA R N R OSE
U T
.

LD N
, .

T HE M O I O ES RS MA x O N E T H E Q E S O P T H E GO E
PR T T A Y UNG MA N Y AR
. . .

MA R Y AL N
.

’
O ES S O S E A LL O E -
A ll 7 3 64 net
H M F RO M W A RS
. . . . . .

BE A U MA R O Y O E THE .

A l l 7 3 6 d n et . . .
P ar k e r ( Gil b e rt )
b Y( W AWR G)
J MAN
a co s
MR S F AL H N TH TR A N LAT N C IO E S IO
A S AVAG WH N V M AM
. ,

U R CH IN S
. .

C SE A or E E AL ON D C E
OES, 55 n et
P N T A Th S t y f L t
.

A MA T R
. , ,

6d To O I C : e or o a os
55 net a n d 3s n et S E OP
.

CR A P T , 6 5
.

LI
.

GH T FR GH T 5
.

n et . N p la A A DV N T U R
o e on N E E OF TH E
Th L t A d
n et EI S, 3
K PP R W NG N RT H f P tty
.
. . .

THE S I
’
A T SU N
ne t O t e as ve n u r e s o re

W H P RT 5
IC D O
E S
5
O OI
n et
, 53 .

IA L S T O N E L E,
.

AN P T
i e rr e . S AT H
’
M GH TY TH HE E S OF T E I E
B A TT L S TR N G A R m
.

RA F T 5 AD Y
. .
,

ODD C n et THE L H E OF T E O : o a n ce
Ki gd m T RA L
5 5 . net. 3.
AR G
.
,

t B S A LT H A V E N , 5 8 of Tw To H n o s. HE I OF T E
S W RD N RT H R N L GH T S
or T H E E , 55 ne .

SA L R K N TS H RT
. .

n et . I O S
’
O , 5s ne t S O
. .
O . A ll 7 6d O E I . 3.

C RU IS E S , 65 . net . n et .

Lond on ( J ack ) W H IT E FA N G . N i nt h P hill p otts ( Ede n)

E d t tt on . Cr 800 . . 78 . 6d . n et .
C H LD R N
I E OR TH E M IS T TH E RI V R E
D M T R D AUGH T R H U MAN
. .

TH E
’
Lu cas ( E V E E E s E .

T N R UR b
. .

L IS E E s L E A n O l i q u e N a rr a t i o n ,
’
BOY A N D TH E WA R . A ll 7 3 6 d net . . .

V R y
.

A n E as
’
6 3 n et O E BE M E RT O N s :
g g h M R N GL D
.

oi n C r o ni c l e , 6 3 n et I ESI E ,
Roh mer ( Sax)
ND N AV ND R R T E G YP T T H O R HA R D
. . .

65 n et LO O L E E , 63 n et TAL S ES OP EC E E C
AND M A R K RM L N T A R TH G LD N S R P N A ll
. . . .
.

L S, 63 net THE V E I IO OF E S E O E CO IO
R NA MD T D VL D T R
. .
. .

B o x , 6 3 n et VE E IN T H E I S ,
7 6d
3 t T ne HE E I OC O
R AND R M Y T R Y D F MAN HU TH
. .
. . . .

8 s 6 d net OS E O S E , 6 3 n et T HE S E or R U C E
Y LL W CLA W A ll 3 6 4 t
. . . . . -
. .

McKe nna ( Ste p

NA
h en)
d
E O . 3 . . ne .

SO I : B e t w e e n T W O W o r l s , 8 3 ne t
H UR
.

—
N IN E T Y S Ix O S
’
LE E , 7s 6 d n et: AV S wi nnert on (E ) S H P S AND H O U S E S
O
TH N
.

M DA H A P P Y F A M IL Y O N
.

P T MB R
.

T H E S IX S E S E , 6s n et I S 8: S O N , . . SE E E TH E
. .

8 s ne t TH E STA R A I C SE CO Q E U TT E THE C H T AS E
WF M R Y
. . . .

A ll 7 s 6d n et TH E
M ale t I E E R
H A RT T A M NT Y UN G
. . . .

( Lu eas)
TH E H T R
IS O Y O F S IR R IC CA L M A D Y HA R D ID A
E
A ll 6
,
H E C SE E
net
, TH E O

A Ro m a nce AR MA E 5 . .

T H E C IS S I
.

I os net
AT L A RR R R ADHA M
. . . .

B
TH E
H AR D
G E E SS B
A l l 7 5 .Gd n et
IE
TH E ES OP
.

W AG Wells ( H . B E LE Y A . F ou rth E d it i on.

CO O E E N D E R B Y S W IP E , L N L
. . .

S IN 8 3 net
. .
’
.
Cr 8 vo . .
7s 6d n et . .

7 s Gd net
. . .

Will i amson ( C N an d A M)
M as on (A E CLE M E N T IN A GH T N NG C NDU T R Th S t g
. . . .

h T H E LI
.
O C O
.
I e r an
Ad t
e
Ill u s t r a t e d N i nt Ed t tt on Cr M t C LAD Y B TTY
’

800
. . . .
f
v e n u res o a o or ar E
A R W AT R H APP N D
.

7 3 6d net
. . .
C OS S I TH E E . T E E IN
E GY PT T S H P G RL T L GH T N N G HE O I HE I I
D A Y P LA
.

C NDU TR FR N D
.

TH E Y TH E O I Y R O ’
H L DA U ND M C E SS . Y IE TH E
S LV R
S O
N AW K
. .

O CE A ll Cr 800 7 3 64 net C S
H A U BP E U R T ET IN I E HE
P ARL S R T
EE
GR AT
.

L V
.
.

UNN Y
.

D
. . . .

THE S SI E Cr 8 vo 6 3 net E TH E EC E E O E
R P RAT
.
.

Y S TE Y M
. .

H U
. .

THE R E D Ct 800 I A ll 7 6d n t
E. C s. e R U CIP Ix
O SE
RN R
. .
. . .

6 3 net
. . CO E . 63 . net .

Methu en s Two Shi lli ng Novels ’

-

Ch e a p E d i t i ons of m a ny of t h e m ost P o p u l ar N ove l s o f t h e d ay

Wri te for Comp l ete Li st

F eap . 8 vo