NE 334 Week 8, October 29 and 31 2024

Learning objectives for the week:

• Monatomic solids: the Harmonic oscillator and the Einstein and Debye models
• Partition function for molecules
• Born Oppenheimer approximation
• Molecular vibrations
• Molecular rotations
• Symmetry e↵ects: identical particles, Bosons and fermions

5.5 Monatomic Solids

5.5.1 Simple Harmonic Oscillator (SHO) Ensembles
Energy levels:
✏v = (v + 12 )h⌫osc , v = 0, 1, 2, · · ·
The canonical partition function:
1
X 1
X
✏r /kB T (v+ 12 )h⌫osc /kB T
zvib = e = e
r=0 v=0

h⌫osc /kB T
change variables by defining y ⌘ e , so that
1
X
1 1
zvib = y 2 y v = y 2 {1 + y + y 2 + · · · }, y<1
v=0
1
y2
=
1 y

Thus, we see that by using the formula for a geometric progression, we may obtain a closed–form
expression for the partition function for a simple harmonic oscillator in equilibrium with a thermal
bath: we obtain
e h⌫osc /(2kB T )
zvib (T ) = .
1 e h⌫osc /(kB T )
Now, if we define a characteristic temperature ⇥ through the dimensional relation kB ⇥ =
‘characteristic energy’, or explicitly in the present case, as
Energy h⌫osc
⇥⌘ = in practice use:
kB kB
⌫ osc
⇥vib =
kB
then zvib (T ) can be written as
e ⇥/(2T )
zvib (T ) = .
1 e ⇥/T
For a solid:

63
 • crystal with atoms at lattice points: distinguishable
• N atoms – 3N coordinates needed:
overall translational motion: 3
overall rotational motion: 3
remainder of coordinates associated with collective vibrations of N crystal atoms:
3N 6

5.5.2 The EINSTEIN MODEL (1907)

Now define cohesion energy, with symbol W , of solid as
W ⌘ 12 N '(0) ,
so that canonical partition function for N –atom crystal given as
W/kB T
ZN = e z1 z2 · · · z3N .
Einstein proposed that each vibrational mode has same fundamental oscillator frequency ⌫osc : Ein-
stein model has partition function z for each of 3N vibrational modes of monatomic crystal that
for a SHO with characteristic temperature ⇥E to give
W/kB T
ZN = e z 3N .
From the Einstein model expression for ZN , we may now calculate all thermodynamic properties
using the formulae that we have developed earlier. 1)
Helmholtz Free Energy: A = kB T ln ZN , or
W/kB T
A= kB T ln e z 3N

=W 3N kB T ln z
⇢
e ⇥E /2T
=W 3N kB T ln .
1 e ⇥E /T
We can therefore write as a final form for the Helmholtz energy associated with a monatomic
crystal the expression
3 ⇥E /T
A = W + 2
N kB ⇥E + 3N kB T ln(1 e ).
✓ ◆
2 @ ln ZN
Internal Energy: U = kB T , or
@T N,V
 ⇢
2 @ W 3 ⇥E
U = kB T N 3N ln 1 e ⇥E /T
@T kB T 2 T N,V

 ✓ ◆
2 W 3 ⇥E 1 ⇥E ⇥E /T
= kB T 2
+ N 2 3N e
kB T 2 T 1 e ⇥E /T T2
The final form for the internal energy thus becomes
e ⇥E /T
U = W + 32 N kB ⇥E + 3N kB ⇥E ⇥E /T
.
| 1
{z e }
due to excited states

64
 ✓ ◆
@U
Heat Capacity at Constant Volume: CV = , or
@T N,V
✓ ◆2 ⇥E /T
⇥E e
CV = 3N kB ⇥E /T )2
,
T (1 e
or ✓ ◆2
⇥E /2T
CV = 3N kB .
sinh(⇥E /2T )
✓ ◆2
⇥E ⇥E /T
For T large, we see that CV ⇠ 3N kB , and for T small, we see that CV ⇠ 3N kB e .
T
✓ ◆ ✓ ◆
@U @ e ⇥E /T
= 3N kB ⇥E
@T V @T 1 e ⇥E /T

⇥E e ⇥E /T e ⇥E /T
(⇥E /T 2 )e ⇥E /T
= 3N kB ⇥E 2 ⇥ /T
+
T 1 e E (1 e ⇥E /T )2

✓ ◆2 ⇥E /T
 ⇥E /T
⇥E e e
= 3N kB ⇥E /T
1+ ⇥E /T
T 1 e 1 e
Asymptotic behaviour:
T large ) ⇥TE small
✓ ◆2
⇥E /(2T )
CV = 3N kB ' 3N kB
sinh(⇥E /(2T )
⇥E
T small ) T
large

✓
◆2
⇥E /(2T )
CV ' 3N kB 1 ⇥ /(2T )
2
e E
✓ ◆2
⇥E
= 3N kB e ⇥E /T
T
Einstein’s model explained WHY the heat capacity of a monatomic crystal fell below
the classical value 3NkB given by Dulong and Petit.

Our result for CV obtained using the Einstein model is of the form
✓ ◆
CV ⇥E
=f ,
N kB T
so that two di↵erent monatomic crystals, with Einstein temperatures ⇥Ea , ⇥Eb , will be such
that whenever the temperatures at which CV for the two crystals are to be determined are
such that
⇥E,A ⇥E,B
= ,
TA TB
the heat capacities for the a and b crystals are the same.

65
 6 4.5

4
5
3.5
CV / cal mol-1 K-1

CV / cal mol-1K-1
4 3

2.5
C
3
Si C
2
Cu Si
2 Pb 1.5
Cu
1 Pb
1
Einstein model heat capacity 0.5
Einstein heat capacity
0 0
0 1 2 3 4 5 0 0.1 0.2 0.3 0.4 0.5
T/ E T/ E

Comparison between Einstein model prediction of the heat capacity of monatomic solids and
experiment.

4) Entropy: S = (U A)/T . In this case, because we have already obtained expressions for
both U and A, we can write immediately

⇥E /T
S = 3N kB ⇥ /T ln(1 e ⇥E /T ) .
e E 1
✓ ◆ ✓ ◆
@A @ ln ZN
5) Pressure: P = = kB T
@V T,N @V T,N

This expression is true in principle, BUT we cannot obtain an expression for P or an equation
of state for the monatomic crystal in this direct manner, because W and ⇥E are functions of
the particle density N/V : these are as yet unknown functions of V !

6) Chemical Potential: G = N µ = A + P V

The vapour pressure for crystals is usually extremely small, so that P V ⌧ A, U , and so on.
In such a case, we can approximate G by A, H by U . If we make this approximation, then
A W 3 ⇥E /T
µ' = + kB ⇥E + 3kB ⇥E ln(1 e ).
N N 2
• solid state physics: often write µ = F/N, with F called the ‘free energy’. They
mean the Helmholtz energy A.

Note: we can obtain an expression for the pressure P0 of a solid by employing

the thermodynamic criterion for phase equilibrium between solid and vapour phases:
namely, that the chemical potentials for the two phases are equal, i.e., µgas = µsolid .

66
 New Objective: develop a better model for solids (to fix the low T behaviour)

5.5.3 The DEBYE MODEL (1913)

If one atom in a crystal is vibrated, it will a↵ect some of the nearby atoms, so that we should not
assume that all normal modes of a crystal have exactly the same frequency. ZN will in general have
the form
3N
Y
W/kB T
ZN = e zi (⌫i )
i=1
so that
X 3N
W
ln ZN = + ln zi (⌫i ) .
kB T i=1

There are many normal modes for a typical N of interest (1020 or so), and they will lie very
nearly in some sort of continuous distribution
• typical phonon frequencies are of order 6 ⇥ 1012 s 1 , and not many orders of
magnitude greater (or the crystal would melt), and there are of order 1020 fundamental
frequencies of vibration available (i.e., distinct normal modes of the crystal lattice).
We shall designate by g(⌫) the function that gives the number of vibrations with frequency ⌫,
so that g(⌫)d⌫ represents the number of vibrations with frequencies in the interval (⌫, ⌫ + d⌫):
Z 1
W
ln ZN = + g(⌫) ln z(⌫) d⌫
kB T 0
Z 1 
W h⌫
= + g(⌫) ln(1 e h⌫/kB T ) d⌫
kB T 0 2k B T
The number of oscillators is N and the number of modes of vibrational motion is 3N : this
information gives us the normalization for g(⌫) as
Z 1
g(⌫) d⌫ = 3N .
0

Frequencies of crystal vibrations are low ) long wavelengths: this is the origin of the Debye
model
treat the crystal as an elastic continuum
the frequency distribution will be similar to that for electromagnetic radiation under the classical
Rayleigh–Jeans ‘law’, i.e.,
8⇡kB T 2
⇢(⌫, T ) = ⌫ = kB T n(⌫)
c3
but modified accordingly to take into account that we are dealing with sound waves travelling
through the elastic medium: the appropriate expression is

1 2 12⇡V 2
g(⌫) = 4⇡V 3 + 3 ⌫ 2 ⌘ ⌫ , (⇤)
cl ct c3
in which cl , ct are phase velocities for longitudinal and transverse sound waves.

3 1 2
c is defined via ⌘ +
c3 c3l c3t
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 assume that g(⌫) can be applied for all crystal frequencies:
⌫ ! 1 ) infinite value for N , so that a condition
Z ⌫D
12⇡V ⌫D3
g(⌫) d⌫ = ⌘ 3N , (⇤⇤)
0 c3 3
that limits the number of modes of vibration to 3N must be introduced.

12⇡V 9N
(**) ) 3
= 3 ; substitution into (*) gives g(⌫) as:
c ⌫D
⇢
9N ⌫ 2 /⌫D3 , 0  ⌫  ⌫D
g(⌫) =
0 , ⌫ > ⌫D

We are now set to calculate all thermodynamic properties of a Debye crystal. Let us, however,
simply focus upon the internal energy U and the heat capacity at constant volume CV :
Objective: develop a better model
✓ for ◆ solids (to fix the low T behaviour)
@ ln Z
Internal Energy: U = kB T 2
@T N,V
Z 1 
h⌫ 1
U =W+ + h⌫ g(⌫) d⌫
0 eh⌫/kB T 1 2
Z ⌫D
9N h⌫D 9N h⌫ 3
=W+ + 3 d⌫
8 ⌫D 0 eh⌫/kB T 1

Another way to represent this result is to set

h⌫ h⌫D
x⌘ , ⇥D ⌘
kB T kB
to give

✓ ◆
9 ⇥D
U = W + N kB ⇥D + 3N kB T D ,
8 T
in which D(u) is the integral
Z u
3 x3 ⇥D
D(u) = 3 dx ; u= .
u 0 ex 1 T
Heat Capacity at Constant Volume:
⇢
3u
CV = 3N kB 4D(u) .
eu 1

68
From this expression, we obtain the results

T large : CV ⇠ 3N kB

Dulong and Petit

✓ ◆3
12N kB ⇡ 4 T
T small : CV ⇠ .
5 ⇥D
Debye T 3 law

See Figure for an example of the behaviour of CV calculated from the Debye model together
with a comparison to experiment.

69
6 Polyatomic Systems
• Polyatomic species: rotational, vibrational, in addition to translational and electronic states
✏ = ✏int +✏trans , independent (uncoupled)

Molecular partition function z is product of partition functions for translational and internal
motions, ztrans , zint :
z = ztrans zint ) Z = Ztrans Zint ,
with Ztrans and Zint given by
N
ztrans N
Ztrans ⌘ ; Zint ⌘ zint .
N!
Note: division by N! occurs only once!
• Consequences:
A⌘ kB T ln Z = kB T ln Ztrans kB T ln Zint (T )

= Atrans + Aint (T )

• Generally true also for other thermodynamic state functions, e.g.,

G ⌘ A + P V = Atrans + P V + Aint (T )
| {z }

= Gtrans + Gint (T ) .

In dealing with internal state contributions to thermodynamic state functions, deal firstly with
diatomics, then generalize to polyatomics.

6.1 Diatomic Molecules

Concept of potential energy (PE) curve arises from an approximation in which electrons in
the molecule are treated as moving in a potential field supplied by ‘clamped nuclei’.

70
Begin with Schrödinger equation:

H (R, r)= E (R, r) ; E = Enuclei + Eelectrons

H= Tbnuclei + Helectronic

‘clamped nuclei0 ) fixed R : (R, r) = (R) el (R; r)

The Schrödinger equation reduces to:

Hel el (R; r) = Eel (R) el (R; r)

Eel (R) / Eel (AB) Eel (A) Eel (B): zero for energy
Procedure known as the Born–Oppenheimer (BO) approximation.
Eel (R) ⌘ V (R), e.g., V (R) for a diatomic molecule
V (R) used to solve nuclear motion problem: two nuclei, six coordinates
Transform into CM and relative coordinates:
– CM coordinates ! overall translational motion of diatomic
– relative coordinates ! concerned with relative motion of nuclei; more difficult to solve
because energies not simply additive
coupled in principle
Introduce two further approximations:
1) Replace V (R) by parabola fitted to minimum
2) Separation of vibrational and rotational motions: assume that diatomic has fixed inter-
nuclear distance re for rotational motion:

71
 rigid–rotor approximation
These two approximations taken together referred to as
the SHO–rigid rotor approximation.
✏ = ✏trans + ✏rot + ✏vib + ✏el ,
gives
zN
Z= ; z ⌘ z(V, T ) = ztrans (V, T )zint (T ) ,
N!
for the partition function, with
✓ ◆ 32
2⇡M kB T
ztrans (V, T ) = V ; M = m1 + m2 .
h2

zint (T ) represents total internal–state contribution for diatomic molecule (i.e., rotational, vibra-
tional, electronic)

6.2 Vibrations
Within SHO approximation for vibration of diatomics, potential energy given by

V (R) = 12 k(R Re ) 2 .

Choose an axis system in which z–axis lies along line joining the two nuclei: atoms of mass m1
at position z1 , and m2 at position z2 (z1 < z2 ).
Coordinate system for description of vibrational motion of a diatomic molecule.

With this coordinate system, R ⌘ z2 z1 , and

V (R) = 12 k(z2 z1 Re ) 2 .

72
 d 2 Ri
Newton’s 2nd Law: F i = m i ai = m i
✓ ◆ dt2
@V
We also have: Fi =
@Ri Rj 6=Ri
Apply these equations to diatomic to get

d2 z1 @V
m1 = = k(z2 z1 Re ) ,
dt2 @z1

d2 z2 @V
m2 = = k(z2 z1 Re ) ,
dt2 @z2

and deduce therefrom equation for relative motion as

✓ 2 ◆
d z2 d2 z1
m1 m2 = (m1 + m2 )k(z2 z1 Re )
dt2 dt2
or
d2 (z2 z1 Re )
m1 m2 = (m1 + m2 )k(z2 z1 Re )
dt2
from which
m1 m2 d 2 ⇠
= k⇠ (⇠ ⌘ z2 z1 Re ) .
m1 + m2 dt2
or
d2 ⇠ k
= ⇠⌘ !2⇠ DE for SHM
dt2 µ
as equation of motion for relative (vibrational) motion of two nuclei.
Fundamental oscillator frequency ⌫osc = !osc /(2⇡) is
s
1 k
⌫osc = ,
2⇡ µ

and SHO energies are ✏v = (v + 12 )h⌫osc , so that molecular vibrational partition function becomes
simply
e ⇥vib /2T
zvib = ,
1 e ⇥vib /T
with ⇥vib ⌘ h⌫osc /kB : Zvib (T ) = [zvib (T )]N . Vibrational contributions Uvib , CV,vib , Svib to U , CV , S
are those of N 1–D SHO’s all with the same fundamental frequency ⌫osc :
✓ ◆
2 d ln zvib ⇥vib ⇥vib
Uvib (T ) = N kB T = N kB + ⇥ /T ,
dT 2 e vib 1
✓ ◆2
dUvib ⇥vib e⇥vib /T
CV,vib (T ) = = N kB
dT T (e✓vib /T 1)2
✓ ◆
⇥vib 1
Svib (T ) = N kB ln(1 e ⇥vib /T ) .
T e⇥vib /T 1

73
 ⇥vib – characteristic vibrational temperature

T ⌧ ⇥vib ! few vibrational states are occupied

T ⇥vib ! many vibrational states are occupied
Consider carefully how to describe origin for various energy states of diatomic molecules. Ex-
amine cartoon showing potential energy curve for ground electronic state of a diatomic molecule:
with the separated atoms as the zero of energy, energy levels in SHO approximation for vibra-
tional motion given as:

De + 12 h⌫osc , De + 32 h⌫osc , etc., i.e., De + ✏ v , v = 0, 1, 2, · · ·

and partition function is

X
( De +✏v )/kB T
zel zvib = !e1 e
v
X
= !e1 eDe /kB T e ✏v /kB T
| {z }
|v {z }

zel (T ) zvib (T ) SHO zvib (T )

These approximations give simple additivity for most thermodynamic state functions: assum-
ing that ✏vib,rot ' ✏vib + ✏rot
A= kB T ln ZN = Atrans + Arot + Avib + Ael

 ✓ N ◆
z
kBT ln ZN = kBT ln trans + ln zrot
N N
+ ln zvib + ln zelN
N!
N.B. only ztrans depends upon V

with ⇣z ⌘
trans e
Atrans = N kB T ln ; Arot = N kB T ln zrot ;
N
Avib = N kB T ln zvib ; Ael = N kB T ln zel .
zint(T ) = zvib(T )zrot(T )zel(T )
V
Recall: z(V, T ) ⌘ ztrans (V, T )zint (T ); ztrans (V, T ) =
⇤3 (T )

74
 Note that due to forms taken by ztrans , zrot , zvib and zel , equation of state for diatomic gas, which
is given by
✓ ◆
@ ln Z
P = kB T
@V N,T
✓ ◆
@ ln ztrans N kB T
= = N kB T = ideal gas law
@V N,T V
does not depend upon zrot , zvib or zel .
(because they all depend only upon T )

6.3 Rotations
 ✓ ◆
c2 = 1 @ @ 1 @2
J sin ✓ + (✓, ) ⌘ jmj (✓, );
sin ✓ @✓ @✓ sin ✓ @ 2
c2 jm (✓, ) = j(j + 1) jm (✓, ) , Jbz
J jmj (✓, ) = mj jmj (✓, )
j j

Recall: { jmj (✓,

c2 , Jbz .
)} are simultaneous eigenfunctions of J

Upon setting µRe2 = I (the moment of inertia of the rotor), we obtain

~2
Erot = j(j + 1) = ✏j , j = 0, 1, 2, · · ·
2I

N.B. energies independent of mj

The j,mj (✓, ) = Yj,mj (✓, ) are the spherical harmonics: for each value of j, there will be 2j + 1
values of mj and, as the energy depends only upon j, each level will be (2j + 1)–fold degenerate!

X X ✏j,mj
Estate
zrot (T ) ⌘ e = e
states j,mj

X 1
X
✏level ✏j
⌘ ⌦level e = (2j + 1)e
levels j=0

double sum over all states reduces to a single sum over all levels, with level weightings
⌦j = 2j + 1
Note:
~2 ⇥rot
✏j = j(j + 1) ⌘ j(j + 1)
2IkB T T

characteristic rotational temperature ⇥rot defined as

~2
⇥rot ⌘
2IkB

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 (i) For temperatures T such that T ⌧ ⇥rot , zrot (T ) can be written as
2⇥rot /T 6⇥rot /T
zrot (T ) ' 1 + 3e + 5e + ···

(not quite true for homonuclear diatomics)

(ii) For temperatures T such that T ⇥rot , we have

1
X
j(j+1)⇥rot /T
zrot (T ) = (2j + 1)e (quantum mechanical)
j=0
Z 1
j(j+1)⇥rot /T
' (2j + 1)e dj . (classical approximation)
0

Z 1 Z 1
j(j+1)⇥rot /T j(j+1)⇥rot /T
(2j + 1)e dj = e d[j(j + 1)]
0 0

1
j(j+1)⇥rot /T
e
=
⇥rot
T 0

T
=
⇥rot
(Again, not quite true for homonuclear diatomics)
If rotational states can be treated classically, we obtain
2IkB T T
zrot (T ) ' = .
~ 2 ⇥rot

What we have done so far is rigorously correct for heteronuclear diatomics, such as
HD, HF, HCl, CO, etc., in which all orientational configurations are distinguishable, but not for
homonuclear diatomic molecules, in which configurations separated by 180 are indistinguishable.
Note: generally speaking, rotational degrees of freedom
can be treated classically in non-spectrscopic applications
at room temperature and above.
More generally, we write in the classical limit that
T
zrot (T ) = ; Zrot (T ) = [zrot (T )]N , Note absence of N !
⇥rot
in which , called the symmetry number, has value 1 for unsymmetrical diatomic (heteronuclear)
molecules, and value 2 for symmetrical diatomics (homonuclear), respectively.
=1 heteronuclear diatomic molecules
=2 homonuclear diatomic molecules

76
 In classical limit, rotational contributions to the thermodynamic state functions A, U and S
are: ✓ ◆
T
Arot (T ) = kB T ln Zrot (T ) = N kB T ln ,
⇥rot
d ln Zrot
Urot (T ) = kB T 2 = N kB T ,
dT
dUrot
CV rot = N kB , CV,rot =
dT
✓ ◆
Urot Arot Te
Srot (T ) = = N kB ln .
T ⇥rot

6.4 Symmetry Requirements for Homonuclear Diatomics

In the same way that total (1, 2) for a He atom must be antisymmetric under the exchange of the
two He 1s electrons (because electrons are spin– 12 particles, fermions), the total wavefunction of
a homonuclear diatomic molecule (which includes electronic, vibrational, rotational, translational,
nuclear spin contributions) must be EITHER symmetric OR antisymmetric under the exchange of
the two identical nuclei.

total (1, 2)

SYMMETRIC ) nuclei have INTEGER (or ZERO) NUCLEAR SPIN;

called BOSONS
ANTISYMMETRIC ) nuclei have HALF–ODD–INTEGER NUCLEAR SPIN;
called FERMIONS
Treat interchange of two identical nuclei as a 2–step process:
i) ROTATE molecule by ⇡ about an axis perpendicular to bond
ii) RETURN electrons to their original positions
We shall see why we do it this way shortly.
We can write the molecular wavefunction as a product of wavefunctions for the various inde-
pendent motions (in the approximations that we are employing here), so that

0 0
total = trans rot vib el total (1, 2) = total (1, 2) spin (1, 2)
0
total : total wavefunction ignoring nuclear spin
X2 molecule: point symmetry group D1h
Let us examine how each of these components behaves with respect to the symmetry operations
associated with a homonuclear diatomic molecule:

77
 trans – depends upon coordinates of CM: not a↵ected by inversion

vib – depends upon |R Re |: una↵ected by inversion

el – most molecules found mainly in ground electronic state

at normal temperatures: ground electronic state for
vast majority of molecules is symmetric under
operations i) and ii).

Homonuclear diatomics often have term symbol ⌃+

g
E↵ect of particle exchange on rigid rotor wave function:
|m|
Yjm (⇡ ✓, + ⇡) = ( 1)j+|m| Nj Pj (cos ✓)eim ( 1)m

= ( 1)j Yjm (cos ✓, ) .

Even j corresponds to SYMMETRIC, odd j to ANTISYMMETRIC rotational states

Beginning of derivation (aside)
i) Rotation by ⇡ about the x–axis permutes the nuclei and changes the electron coordinates:
c2 (x)
(xi , yi , zi ) ! (xi , yi , zi )

ii) Return the electrons to their original coordinates via following two transformations (leaving
the nuclei unchanged): first inversion,
i
(xi , yi , zi ) ! ( x i , yi , z i )

followed by reflection in the yz–plane

v (yz)
( x i , yi , z i ) ! (xi , yi , zi )

( ) ⇢
i v
fu ! fu f+ ! +f+
i v
fg ! +fg f ! f

Let’s consider the behaviour of a typical spherical harmonic function, Yjm (✓, ) under inversion
of coordinates:
(x, y, z) ! (x0 , y 0 , z 0 ) = ( x, y, z)
(⇢, ✓, ) ! (⇢0 , ✓0 , 0 )
For spherical polar coordinates, we know that the domains on which these variables reside are:

0⇢1; 0✓⇡; 0  2⇡

We now wish to determine how ⇢0 , ✓0 , 0 are related to ⇢, ✓, . We will proceed in the following
way. The relation between ⇢0 and ⇢ is relatively straightforward, namely,
1 1
⇢0 = [x02 + y 02 + z 02 ] 2 = [( x)2 + ( y)2 + ( z)2 ] 2 = ⇢ ,

78
 To see how ✓0 and 0 are related to ✓ and , we need to take a closer look at the Cartesian
defining relations for the inversion process, making use of the relation ⇢0 = ⇢.

z ! z, or cos ✓0 = cos ✓ ) ✓0 = ⇡ ✓;
0 0
x ! x, or cos = cos ) = ±⇡ ;
0 0
y ! y, or sin = sin ) = +⇡ ;

Thus, we see that the operation of inversion through the center (origin) can be expressed in spherical
polar coordinates as
(⇢, ✓, ) ! (⇢, ⇡ ✓, ⇡ + )
Express the spherical harmonic Yjm (✓, ) in the form
|m|
Yjm (✓, ) = Nj Pj (cos ✓)eim ,
|m|
with associated Legendre function Pj (cos ✓) represented as

|m| |m| d|m| Pj (cos ✓)

Pj (cos ✓) = (1 cos2 ✓) 2 ,
d cos ✓|m|
Pj (cos ✓) a Legendre polynomial, given by

dj
Pj (cos ✓) = const. (cos2 ✓ 1)j .
d cos ✓j
Inversion of the coordinate system results in Yjm (✓, ) becoming
|m|
Yjm (⇡ ✓, ⇡ + ) = Nj Pj ( cos ✓)eim eim⇡

dj
Pj ( cos ✓) = const. j
[( cos ✓)2 1]j = ( 1)j Pj (cos ✓) ,
d( cos ✓)
so that

|m| i |m| |m| d|m| Pj ( cos ✓)

Pj (cos ✓) ! Pj ( cos ✓) = (1 cos2 ✓) 2
d( cos ✓)|m|
|m|
= ( 1)j+|m| Pj (cos ✓)

i
eim ! eim( +⇡)
= eim eim⇡
=
eim (ei⇡ )m = ( 1)m eim

End of derivation (aside)

We say that the parity of Yjm (✓, ) is ( 1)j .
0
Hence, we see that total is:

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 • unchanged by inversion of coordinates when j is even,

• changes sign upon inversion of coordinates when j is odd

Role Played by Nuclear Spin States for Homonuclear Diatomics:
– the H atom has 1 proton, spin– 12 , for which the corresponding spin states can be referred to
as ‘spin–up’ and ‘spin–down’; we commonly represent these two spin states via the symbols
", #
1
– the H2 molecule has 2 protons: nuclear spins Ia = Ib = 2

– the total nuclear spin for an H2 molecule is thus:

I = I a + I b , Ia + I b 1, · · · , |Ia Ib |
= 1, 0

""
p1 ("# + #") : symmetric to nuclear interchange (spin triplet)
2
##
p1 ("# #") : antisymmetric to nuclear interchange (spin singlet)
2
We refer to the triplet nuclear spin states of H2 as ortho-hydrogen (oH2 ) and the singlet nuclear
spin state of H2 as para-hydrogen (pH2 ). Ortho means ”high spin”.
Pauli showed that the wavefunction for a collection of equivalent fermions must be an-
tisymmetric to the exchange of any two of them, while the wavefunction for a collection of
equivalent bosons must be symmetric to the exchange of any two of them.
wavefunction $ ‘total’ wavefunction
Symmetry version of the Pauli Principle!
Application to H2 : 2 equivalent electrons and 2 equivalent protons requires that the overall
(or total) wavefunction, which we can write in the form
0
total = total nuc.spin

must be ANTISYMMETRIC under the exchange of the two protons, i.e.,

H2 ( 1 ⌃+
g) ! el even, ( vib even, trans even)
rot (j) ! ( 1)j rot (j)

0 0
total ! ( 1)j total

Now, because total (2, 1) = total (1, 2) for fermions, we may deduce that

– H2 molecules in states with j odd must combine with the symmetric triplet of nuclear spin
states

– H2 molecules in states with j even must combine with the antisymmetric singlet nuclear spin
state

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 In the absence of an externally applied magnetic field, the nuclear spin states are strictly degen-
erate, so that the j = odd rotational states of H2 have a nuclear spin statistical weighting of 3, while
the j = even rotational states have a weighting of 1. This nuclear spin statistical weighting
has a profound e↵ect both on the spectroscopy and low temperature thermodynamics
of bulk hydrogen gas.
Hydrogen: Comparison between Theory and Experiment.

• Bohnö↵er and Hartek (1926) – experiment vs. calculation for the equilibrium mixture

• Dennison (1927) – realized that the ortho–para equilibration process could be quite slow: in
the absence of a suitable catalyst, this process has a half–life of about 3 yrs at NTP

• Bonhö↵er and Harteck (1929): used activated carbon as a catalyst, and obtained experimental
confirmation of the calculations for an equilibrium mixture of ortho and para H2 .

Temperature dependence of the percentage of p-H2 in an equilibrium mixture of o-H2 and p-H2 .

6.5 Nuclear spin contribution to properties

More generally, for a homonuclear diatomic molecule made up of atoms with nuclear spin Ia :
Ia  MIa  +Ia
pair of nuclei ! (2Ia + 1)2 nuclear spin pair–states
Consider antisymmetric pair combinations i (1) j (2) i (2) j (1): there are (2Ia + 1) choices
for the MI value for the first spin and 2Ia choices for the MI value for the second spin; as these
spins are indistinguishable, we must divide by 2, which gives

(2Ia + 1)(2Ia )
= Ia (2Ia + 1)
2
for the number of antisymmetric pair combinations.
the remainder of the (2Ia + 1)2 spin pair states must then be symmetric: i.e.,

(2Ia + 1)2 Ia (2Ia + 1) = (Ia + 1)(2Ia + 1) .

Let us return now to the H2 molecule:

Ia = 12 ! 2Ia + 1 = 2, giving 4 pair–states (as seen earlier)

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 The combined rotational–nuclear spin contribution to the canonical partition function is

zrot,nuc = zortho + zpara ,

with X
j(j+1)⇥rot /T
zortho = 3 (2j + 1)e
j=1,3,5,···

and X
j(j+1)⇥rot /T
zpara = 1 (2j + 1)e
j=0,2,4,···

X 2 ( 1 ⌃+ 1 +
g ): homonuclear molecule in ground ⌃g electronic state

⇢
2 Ia (2Ia + 1) antisymmetric
(2Ia + 1) nuclear spin pair states in total
(Ia + 1)(2Ia + 1) symmetric

bosons: nuclear spin Ia is an integer, and so (2, 1) = (1, 2), and

X X
zrot,nuc (T ) = (Ia + 1)(2Ia + 1) (2j + 1)e ⇥rot j(j+1)/T + Ia (2Ia + 1) (2j + 1)e ⇥rot j(j+1)/T

j even j odd

12 16
C, O, 4 He have Ia =0; 14
N, 2 H have Ia =1.
16
examples: D2 , O2

fermions: nuclear spin Ia is an (odd-integer)/2, and so (2, 1) = (1, 2), and

X X
zrot,nuc (T ) = Ia (2Ia + 1) (2j + 1)e ⇥rot j(j+1)/T + (Ia + 1)(2Ia + 1) (2j + 1)e ⇥rot j(j+1)/T

j even j odd

1 13 15
H, C, N, 3 H,3 He,have Ia =1/2; 35
Cl, 37
Cl have Ia =3/2; 17
O has Ia =5/2.
examples: H2 , T2
These restrictions are imposed by NUCLEAR SPIN SYMMETRY: note that zrot,nuc (T ) does
not factor in general into a product zrot (T )znuc (T ).
However, for T ⇥rot , the quantum sum can be replaced by an integral: we then have
X X
(2j + 1)e j(j+1)⇥rot /T ⇡ (2j + 1)e j(j+1)⇥rot /T
j even j odd

1
1X j(j+1)⇥rot /T
⇡ (2j + 1)e
2 j=0
Z 1
1 j(j+1)⇥rot /T
⇡ (2j + 1)e dj
2 0

T
= .
2⇥rot

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From this ‘high temperature’ result in our expression for zrot,nuc (T ), we obtain

(2Ia + 1)2 T
zrot,nuc (T ) ' = zrot (T )znuc (T ) ,
2⇥rot
in which we have
T
zrot (T ) = , znuc = (2Ia + 1)2 .
2⇥rot

83