= fv Gov eGndr ~ MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. It
(ii) Expectation value of momentum
‘The expectation value of momentum is given by
2 - .
= fv Hd pylatdr +3)
To solve the above integral, we have to find the value of p.on function of X but uncertainty principle
does not allow to find the value of p and x simultaneously,'$0 we try another method.
‘The wave function y for a particle having linear momentum p and energy E is given by
yoo) = Ae CEP)
av _ i a imeem
ax = APAC
or pye
— ;
Putting Eq. (4) in (3), we get
= fy «xo(~in Z}pcnae
cs
= -ih fv wn Zvcande
(iv) Expectation value of energy
The expectation value of energy E is given by
= f¥@DE Vand ao
‘The wave function of a particle havi : ;
is given by ' particle having energy E and linear momentum p moving along + X-direction
VD = Ae UME px)
= - Ey ume __E
m 2-7"
or Ep =
or 7
Putting Eq. (6) in (5), we get
ihe 5
* (6)
t a
= fy wo(in2) pana
ied
inf ¥ wo vende
6 : QUANTUM MECHANICS, 81
3.13. DEGENERACY
If there is more than one lineraly independent wave function belonging to the same energy eigen
value E, the energy level is said to be degenerate. If there are r linearly independent wave function (y,,
Poo Pn) belonging to the same energy state, then the energy level is said to be fold degenerate. It can
be easily shown that any linear combination of the degenerate wave functions of the form,
. = CWP) + C2 + + Vy
is also an eigen function belonging to the same energy eigen value.We will prove this for n = 2 the
generalization is straight forward. Since , and 2 are eigen functions belonging to same eigen value
E,, we have the relation
2
ey
In ge TVG = Ev @
and
wd vy
tn at +V@)¥2 = Ey, (2)
‘Multiplying the equation (1) by c, and the equation (2) by cy and adding, we get
wd
“Trae om F cph2) + V@) (q+ C22) = E, (cp + er2) +-(3)
which shows that the linear combination cy), + cs is also an eigen function belonging to the same
eigen value E,. So the case can be extended to any number of states.
EXACT STATEMENT AND PROOF OF UNCERTAINTY
/ PRINCIPLE FOR WAVE PACKETS
Precise definition of uncertainty .
Before making an exact statement of uncertainty principle let us give a precise definition of
uncertainty.
The uncertainty in measurement of an observable fis defined as
Of = [-7}!%, (3.11)
where. = fv Pur on(3.12)
Thus uncertainty in the measurement of an observable is the square root of difference between the
mean of the square and the square of the mean of fin the state w.
Exact statement of uncertainty principle
Uncertainty principle state that the exact position and momentum of a particle cannot be determined
simultaneously with aesired accuracy.
If Ax is the uncertainty in the measurement of position x of the particle and Ap is the uncertainty in
the corresponding momentum p, then
h
Ax. Ap = > eo)
Let — Ax and Ap be uncertainties in the measurement of position and momentum of a particle. We
define these uncertainties in x and p by the relations
Ax = [e2>-< ol? : (2)
and Ap = [- ?j!2 (3)
Consider two arbitrary well behaved functions f and g of space coordinates. Let us define three
integrals.
a=ffifdr b=ffigdr c=Sa'gdr 4) MODERN’S ATOMIC AND MOLECULAPPHYSICS (B.Sc. Il)
So SlrtePar = far re raftarar
= fa rrersas oe +f spars See “Pr
where 2 is a parameter which is assumed to take real values.
Using Eq. (4); we get
SlytePar = 2 atie' tbr (5)
Since the integral on the L.H.S. of Eq, (5) is positive,
so 22a+A(p" +b)+c = O forall values of A.
‘Thus for the above inequality to be satisfied, we must have
dac = (b" +b)?
or ac 2 fo+8 *? (6)
Putting Eq. (4) in Eq. (7), we get .
SP erfeedr = Lfre+ war] )
Let us consider the special cate of =Oand =0, and Ietus assume the following functions :
f= mpo-int
and g sixy. *
SP serfeaer = sl wt) oP esemvrurver
fs * .
= 0 SZ Rar fy ey dr
- 7 av" ay
® SfaraS F Marc?>
(<2 >= Sv'2y @r)
Sof f'rarf ged = 8 Sfoaly 1 -sy Btalee>
But ve = Oatx=t 0
Srrerfeeer = 1hv(-
or SPIO Seeds = p> <2> (8)
: ie ? ol
[s
. a ae 7 oy” .
And SU e+ fear = Ja wovscmBcwyle, s a
‘
or SUf'et fo) er= +) SExvarans #.v"|
‘92d
ay" . .
=A seers fy y Pr fy vars f Rave]
ay" . , .
A avers sy yartf 2% 2,)- Fy vel
-h [2 wp Pr-f vy #
Since p is normalized, so y*x y would vanish at x= + ©.
Suter feyar = -nfo-fy'yar]anfyyer
or Set fear = +h [fv vd'r=i]
Putting Eq. (8) and (9) in eq. (7), we get m
2
pr 2 5
or [xp?>]!2[cx?o]!2 z
or Ap.Ax 2 2
This is Heisenberg’s uncertainty relation.
3.15. ORTHOGONALITY OF ENERGY EIGEN FUNCTIONS
‘Any two normalized wave functions YY, 2) and Y_ (x ¥, 2) corresponding to two different eigen
values E,, and E, of energies are said to be orthogonal, ifthe integral of the product of one of them and
the complex conjugate of the other over the common domain of the functions is zero.
ie. S Ym¥ndt = JS Vivnde =0, if man wal)
Since the wave function are normalized, it mean that
+e inn aT Lif m=n (2)
where dr = dx dy dz is the volume element
Proof for One Dimensional Case
Let pq (x) and y, (2) be any two normalized non-degenerate eigen function of the one-dimensional
Schrodinfler time-independent equation for a Bound particle with corresponding eigen values E,, and
E, of energy.
‘The one-dimensional Schrodinger equations for y,, and Py ite given as
w dy,
om ad VYm = En Ym (3)
® dy,
mage +Vn = Eve (4) u MODERN'S. ATOMIC AND MOLECULAR PHYSICS: BS.) |
‘The Schrodinger equation for y?, which is the complex conjugate of is the Same as that for y,,
so longs the pote energy ira; o we have \
Ete ew, = EnV ao
Multiplying eq. (4) by y*, and eq. (5) by y,, we have
vr 7 Py, *:
— Fyn + Wn Ya = Evie J
Fy Swi, = EihVe O
Now subtracting eq. (6) from eq. (7),
=| = Em ~ En) ¥nPn
2m .
- or SA = En EnV
. d(d ay, d (dyn), Wn dy
«| sa} 4h {t}24
2m .
=FEn~ En) Yin¥n
h
+ d¥n)_d{ d¥mn) 2m .
a (va) Sf, = FE, E,)Vaie
d{. dv. dy 2m
or oly, eras vita} | een En Vins
inpuing bt tt nh ne bia to:
+o d{ dv, dm os
es on Yn Ge Yn aha. = SE,-E )f72 vin de
+ Wy ay," 2m oo
or [vests Tee oe -te,- Ey) f 72 Vinvn ae 8).
. dt
For a good wave function, y and spproach Zero as x > + 0; so the left hand side of eq. (8)
becomes zero at both end points.
2m +o 6
En ED) S72 Um Unde =0 (9) QUANTUM MECHANICS 8s
Ne ee
If the wave, function belong to two distinct energy levels to that E,, # E,, then we have
0
oe Pm Pade = 0 (form # n) +0(10)
For m= n, the factor E,,- E, = 0. In this case according to the physical interpretation of wave
function we must get
+0
ow Ym Yndt = 1 (form=n) (1)
So the wave function shows the orthogonality property.
‘When two or more linearly independent wave functions p,, 2, V3. -»- correspond to the same eigen
value of energy, E, then the energy is said to be degenerate. Such wave functions are not necesarily
orthogonal. But it is possible to find orthogonal linear combinations of degenerate wave functions in
many different ways. For example, a linear combination of , and p is the wave function given by the
relation ,
Pe = Cy + C2Y:
y-can be made orthogonal to , by choosing the constant coefficients c, and cp such that
Svivede = 0
or Sv avi tev)dr = 0
Sub vide-to, futvade = 0 4 Vivade
ore ¢. = =e
aa 2 J iba: oe Syivde
’s Equation for the Complex Conjugate Wave Function y* (x, y, 2, t)
We have the time-dependent Schrodinger equation of the wave function p (x, y, z #) is given by
wooo _ pd
-E Vet wy = ae I)
Since p is complex, s0 we may write
Y =o tidy =+(2)
where p and are real functions of x,y, 2,1. Putting this form for in eq. (1), we get
2 a a
-— V2(yy + iva) + Vr + iV) = Ps + a)
Equating real and imaginary pats on either side ofthis equation, we get the following two equation:
2
Avi +1
= nee
anh 3 (3)
2
HL viy eve = AGL ld)
Multiplying eq. (4) by — i and adding it to eq. (3), we obtain
» wy, 2 ih 2[y, +22
~ FV iv) + V 1 ~ ia) = br (» 7
a
= -ih>- (v1 - ya)
The complex conjugate p” of p is given by
ve = ve 5)
h . . oy
So vv eve = -int 6)
This is the equation for y* _— O_O _—— —_ OM
SIMPLE SOLUTIONS OF
“ SCHRODINGER EQUATION
4,1 PARTICLE IN A BOX
asi infinite potential well) -
inc pa ne inn eps a
ie. the particle moves only along a straight line say along x-axis. Let the alla of sh Pox be rigid,
elastic and non-penetrable. Let the particle can travel along x-axis between x = O and x = L.
Let the collision of the particle with the walls be
elastic so it does not loose energy. Let us represent
this by an infinite square well potential as shown in
Ppa TIEEE
figure 4.1. H
The potential V is defined as H . )
Va = 0 fordL H
Classical view <«———— |______+}
Classically, the particle can have any value of
energy. If E=0, the particle will be at rest inside the
box and if E > 0, the particle will move along x-axis
and at x = 0 and x = L, it will experience a force
= -& (Since V = 00, so F = e) in the direction
opposite to its motion and is reflected from the walls
and thus moves back and forth along x-axis.
Quantum view i:
‘The Schrodinger wave ‘equation for the wave
function of a particle moving along a straight line in
the presence of external field is given by
@y 2m
wen),
(6)
7)
sone(8)
‘where n i called quantum number. Since E depends on n so let us denote the energy of the particle
by Ey. Hence above equation gan, be written as
age
: nah
E, =
mi?
‘ 1
Thus E, « n?, ae E,* 7
Energy level diagram (or Eigen values of energy)
Forn~ 1, the value of E,, will be minimum and is given by
. er
ee DL
‘This is called ground level energy and the state is called
ground state. The energy corresponds to higher states is
called excited energy and the states are called excited states.
These are given by
Paw
Sar ne
32 2p2
Fe op
3 = me
we(9)
sxe 10) 104 MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.S. 1)
4
=> =16,
ea 1
and so on. : B,—-Heace
icle can have any value of energy given by Ey, 4, 9E,, 16E},...He
oop guniet Testioeas Values of energies ofthe patcle are called energy levels or eigen
values of energy, shown in fig 4.2, and are not equally spaced.
values of momentum
‘The linear momentum of any one of the allowed value E, is given by
Ph = 2mE,
Using Eq. (8), we get
or Pn = = (n=0, 1,2 en)
‘Thus momentum is also quantized into discrete allowed values. Hence the momentum of a particle
inside the box is
(directly proportional to the quantum number n ie. Py & n
1
Gi) inversely proportional to the length L of the box ie. py & L
(iii) independent of the mass of the Particle.
energy
Fe minimum possible energy possessed by the particle inside the box is called zero oint energy.
‘The energy of the particle inside will be minimum at n= 1
So zero point energy
we
1 oar (see Bq. 9)
Since E = Ois not allowed because if E=0, then y = O everywhere inside the box and th
density in the box | /? = O ie. the particle isnot inthe box. hence E
Hence, the panicle can not have zero total energy inside the bos, so ti cannot be at rest in the box
(quantum mechanically).
Wave function,
From Eq, (6, the wave function y (x) of the particle inside the box is given by
_ * yQ) =Csin ke wn(12)
Using Eq. (7), We get :
ien probability
¥@ =C sal
+ Probability y density °
P =¥"@) YQ) =¢ sa) cain
or yey =C2sin2 a
—— SIMPLE SOLUTIONS OF SCHRODINGER EQUATION 105
Since the probability density between x = 0 and x = L is 1, because the particle is somewhere within
this boundary.
‘i s
. * ) 2 Mn 2nn
ie fy vas 21) w-|2 =
L nx ;
or oo fsin’ Fax 2
0 L
or =1
or =l1
a, 2anx 529
or ail i foT =01 ©
2
255
or e =T_
ae ant Le (13)
‘The normalized wave functions 1, and 5 together with the probability densities jy, ly2/* and
vs? are plotted in fig. 4.3 (a & b). Although y, may be positive as well as negative but | Yq P is
Fig.4.3
always positive and since ,, is normalized, its value at a given x is equal to the probability density of
finding the particle there. In every case |, ? = 0 at x = 0 and x = L, the boundaries of the box. MODERN’S ATOMIC AND MOLECULAR PHYSICS (B. $0,
106.
The probability of the particle being present may be very different for different quantum number,
pek (maximum in the middle of the box)
a ea é the middle of the box)
=0 (in the middle o ; ;
tee a pt! in staat energy level of n = 1 is most likely to be in middle of the bor, white 4
particle in the next higher state of n = 2 is never there. Classical physics, of course, suggests the same
probabilit the particle being anywhere in the box. . .
Enamel, A vrtclels moving inone ‘dimensional potential box (of infinite height) of width 25 A,
Calculate the probability of finding the particle within an interval of SA at the centres of the box when
itis in its state of least energy. Sane ; ;
Sotution. We ow the the wave functions of a particle enclosed with an infinite potential well is
given by
2 max
v@) = yrsin
‘When the particle is in the least energy state n = 1, hence in this case
2 mx
vi) = fanz
At the centre of the box x = L/2, The probability of finding the particle in the unit interval at the
centre of box is given by
2. a(L/2) 2 a 2
p- | |—sin2 int 2
iveore| ce | cin ser
‘The probability P in the interval Ax is given by
P=|y@) Par = Zax
In this case L = 25 A = 25 x 10-! m and Ax= 5 A=5 x 10-10 m
x5x107!0
p22 x10
~ 25x10~'9
Example 2.4 proton or a neutron in a nucleus can roughly be regarded as a particle in a the
surface of the nucleus plays the role ofthe wall of the box and proton moves more or less freely fete
these walls. What is the energy released when a. ‘Proton makes a transition from the first excited state to
the ground state of a box of nuclear size i.e. 1-0 x 10-4 m ?
Solution. We have r= 1 x 10-!4 m,
and m= mp = 1-67 x 10-27 kg.
‘The energy of ground state is determined from relation
n tp? ;
2myr?*
ee ® x (105x107 Js)?
2 ~ =
mgr” 2X167X10-" kg x (10x 107 4m)?
=33x 10-13)
Energy of first excited state will be
2 A?
By = POG =4x33x 1035
-
= 13-2x 10-3 J ‘SIMPLE: ‘SOLUTIONS OF SCHRODINGER EQUATION
By -E = 13-2 10-3 3_3.3y 10-35
713,
=99x 1013s = 29x10"™
16x10-3
= 6-2 Mev,
Example 3. A particle is confined to a one-dimensional infinite ic ic is
; 0 potential well of width 0-2 nm. It is
given that where the energy of the particle is 230 eV, its eigen function has 5 ntoaden Find the mass
af the particle and show tha i can never have energy equal to 1 keV.
Solution. Since the eigen function correspondi i Particle isi
eee oe de eaen Rson cr ing to energy 230 eV has 5 antinodes, the particle is in
Es = S?E, =25 B, =230eV
so that E, = 92eV =92x16x 10-195
4-7 x 10-19 J
Also, L=02nm=02x 109 m=2x 10m
2p 2 2
Now E, = i= pase
2 mi? ‘
. 6625x1074)?
8VE, 8x4x10- x147x10-
= 93x 101 kg
For E,=1keV,n should be such that
ie,
Since n is not an integer, E,, = 1 keV is not a permitted value of energy.
Example. 4. Calculate the value of lowest energy of an electron moving in a one-demensional force
Sree region of length 4 A. . (HLP.U. 1997)
Solution. We have m = 9-1 x 10-7! kg, L=4 x 107! m
Since energy of electron in nth state is given by
222 nh
2mi? 8m?
Po (6625x107)?
Bm? 8x91x10 x (4x10?
Ey =0376x 10-8J
or
Example. 5. Calculate the value of momentum and energy of an electron in a box of wavelength 1A,
forn=2. [H.P.U. 2000 (S)]
Solution. We have L =A = 1A = 10"! m,n=2
, nth _ nh
Since thomentum, Py = “3- = 3p
Forn = 2
2% 6625x10-**
= 1
Py =~ aggro KBE
Py = 6625 10 kg ms“! MODERN'S ATOMIC AND MOLECULAR PHYSICS (8.5,
Pty? 2p?
n
And energy, Om? = aad
Forn=2
_ 4% (6625x1074)?
2 © 8x91x10-! x10"
Ey = 1508 eV.
Example. 6. A particle of mass 10 kg is moving with a speed of 104 m s! in a box of length 103 4,
Assuming this to be one dimensional square well problem, calculate the value of x /)
Solution.
We have m = 10 kg, v = 104 ms“!, L = 103 A= 10-7 m
Since energy of a particle in nth state is given by
nah?
B=
2 _2mUE, — 8ml7E,
n=
he
or n=
2mLv _ 2x10~6x1077 x107+
or ne zx 106,
h 662510"
Example. 7. Evaluate the expectation value for kinetic energy of a particle in one dimensional rigid
box in the nth quantum state. (H.P.U. 1998)
Solution. We know that the wave function of a particle enclosed in one dimensional box is given by
2. (nax €
vi « Ful
The expectation value of kinetic energy E is given by
oo o 2
P
= * = * —wdx
= f p*Epdx f vw
1 i
= Sy Lot in? yd
ra ay
spy kY,
am SY at
Ej fale Balt
=” fan( 2 we in ae
Sol ae i L ‘SIMPLE SOLUTIONS OF SCHRODINGER EQUATION 109
2 92p2 L,
wa
o = =) Sin? = ae (-ve sign is omitted)
Oo
L
ft ~cos288 ac
a = rer
mi 2m?
4.2. POTENTIAL STEP (Energy less than step height)
Potential barrier : If the force field acting on a particle is zero or nearly zero everywhere except in
a limited region, it is said to be a potential barrier.
A single step potential barrier is shown in fig. 4.4. At x =0, the force field acting on the particle is
Vo, where Vo is called the height of the potential barrier.
The step potential can be represented as
(0 for x <0 (region I)
VO@)= |v for x>0
fy for x >0 (region I)
In region x < 0, the particle moves like a free
particle and as it approaches the step potential in
region x > O, it faces the potential height V (x) = Vo
as shown in fig 4.4
ee INCIDENT WAVE)
Classically a particle in region I can move freely
as the force field is zero but at x = 0, discontinuity
occurs. Since energy of the particle is less than the
height of the potential barrier i.e. E < Vo and the VO=0 | EeVy
particle is in region I, so it will remain in region I
for ever. If sometimes the particle is moving towards
the positive x-direction, it will be completely
reflected back at x = 0. Fgaa
Quantum mechanical view
Since the potential Vo does not depend on time, so we apply time independent Schrodinger equation
to solve this problem. —
‘Schrodinger’ one dimensional (along x-axis) time independent wave equation is-given by
zy 2 Z
+ FFE-Vy=0 seu 1)
InregionI. V =0
So Eq (1) becomes
ay | 2mE
ae
da
orf athe =0 e2) MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. I)
110
where k= PE wo 2
In region II V = Vo
So Eq. (1) becomes
dy , 2m(E-Vo)
fy. =0
ae ”Y
; # co ke
we iy |
or be 14
= (4)
where ky aul)
‘The general solutions of Eq. (2) and (5) may be written as
° w-e(6)
v= Adht + Behe Lo
vu = Ceh* + De®”
where A, B, C and D are arbitrary constants and are to be evaluated.
In region i.e. x >0, the term De'?* increases rapidly as x increases ie. ¢4* ->© for x > 2
making yy ©, which violates the boundary conditions (i.e. yj has to be finite everywhere) hence the
term De'?* is rejected. .
Ym = cena . wD)
‘The values of A, B and C can be determined by using boundary conditions.
Boundary conditions
In the given situation, the boundary conditions are that the eigen function and its first derivative
should be finite, single valued and continuous, hence
(Ow must be finite and continuous at x = 0
ie. [vi].-0 =[¥u],—0
From Eqs. (6) and (7), we have
A+B =C ~@)
di
oy = must be finite and continuous at x = 0
: av) favo
ne [e)..-[1.,
From Eqs. (6) & (7), we get
ik, A-ik,B=-kC
or ik (A-B) =-kC
or ik, (A-B) =?kC SIMPLE SOLUTIONS OF SCHRODINGER Equation 7
14
or A-Bs Be
(9)
Adding and subtracting Eq, (8) and Eq, (9), we get
= fy 4 te z
A= (+2) t- (10)
= C{,_;% wa
and Bs 5 inet w(11)
Putting the values of A and B in Eq, (6), we get
Cf ke) yx . C(, ike
= [14s |eitix 4 Lf _ the) ine
WI 3! Bet Si Ps je (12)
Also from Eq. (7), we have
Vu = Ce“hx (13)
The first term of Eq. (12) represents the incident wave and second term represents the reflected
wave
. = £4 Hee) ike
= fy He) aye
and Pre = s( iE Je
Reflection coefficient (R)
jthe reflectance ot reflectivity or reflection coefficient at the potential discontinuity may be defined
as follows.
The reflection coefficient (i.e. the fraction of incident particle reflected) is equal to the ratio of
reflected probability density current 10 the incident probability density current.
Reflected probability density current
Incident probability density current
Density current of a free particle is the product of velocity ~ vy and probability density yy)
Cf, _ the) itis Cf the ) ity
( a2), S{i+H}e
Re
Re Weve 2
UVind
or R=1
Thus we find that the incident wave is totally
reflected and this is same as predicted by classical
consideration.
In region II (x > 0) the transmission coefficient
vanishes but the wave function is not zero. It means
that there is a finite probability of finding the particle
in classically forbidden region x > 0. The shape of
Wave function in the two regions is shown in
fig. 4.5. we MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. I
Peay 1
In order to observe the particle inthe region x > O, it must be localized within a distance Ax = b
‘and its momentum must be uncertain by
Ape pb = Im {Vo -E
4.3. POTENTIAL STEP (Energy more than the step height)
A single step potential barrier. is shown in
46.
fig “le i
"At x =0, the force field acting on the particle is
Vo, where Vo is called height ofthe potential barrier.
‘The step potential can be represented as
(0 for x<0 (region)
VG) = |v for x>0 (region)
Classical View
Classically a particle in region I can move freely
as the force field is zero but at x = 0, it experiences
a retarding force, F = = towards the left and its
velocity decreases and it would not be reflected at
x=0 because the particle has enough energy to enter
the region x > 0, thus classically, the particle is always transmitted. Fig. 46
Quantum mechanical view
Since the potential Vo does not depend on time so we use time independent Schrodinger equation to
find the motion of the particle in regiogs I and I.
Schrodinger time independent one dimensional wave equation (along x-axis) is given by
ay 2m
wie =0 nfl)
In region I v=0
So Eq. (1) becomes
@y | 2mE
ate =o
@
Si Satie =0, a
mE yy
where ee 3)
Inregion IT V = Vo
So Eq. (1) becomes
2, ~
LY , 2ME-Vy) 7
ae w 0) the term De~2* is rejected because there is nothing in region Il to cause a
relection of wave, and hence in region x > 0, there is only a transmitted wave.
o vun= Cet wT)
The value of A, B and C can be determined by using boundary conditions.
Boundary conditions
In the given situation, the boundary conditions are that the eigen function and its first derivative
should be finite, single valued and continuous.
(i w must be finite and continuous at x = 0
ie. [vileo = [¥uh-0
From Eq (6) & (7), we have
A+B =C (8)
a
(ii) 2 must be finite and continuous at x = 0
ie (= AL.
From Eqs. (6) and (7), we have
ik,A ~ iky B= ik,C
La
AoE wn)
or ky (9)
‘Adding and subtracting Eqs. (8) and (9), we get
c(,,%
sf +h) i (10)
k
and B= Simi) L— (LL)
ky
Putting the values of A and B in Eq. (6), we get
Cf, ko) piyx 4 Cf) 2) ite
w= Sli t2)e +5lI-Fle 02)
Also from Eq. (7), we have
vu = Cel MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. I)
4
‘The first term in Eq. (12) represents the incident wave, second term represents the reflected wave
and Eq. (13) describe the transmitted wave.
Cf, , ke) it
ie. Vin = Sst. ie
= £{;-22) nme
el st i}. ‘
Vir = Celt
ivi i ie it transmissivity or
‘The reflectance or reflectivity or reflection coefficient and the transmittance or
transmission coefficient at the potential discontinuity may be defined as follows :
Reflection coefficient (R) a. i aa
The reflection coefficient is equal to the ratio of reflected probability density current to the incident
probability density current.
s{i-Blm Sli lee
And R= Weve 2h 4 2\ kh :
Minin Lf ke) ita Cf be) mite
hy 27%, If
2
2 4
1-2 2
. & (: =e)
Re = 4 (14)
“ ph] “(nee
& ‘
From Eq. (14), we find that R < 1, but > 0, And R > O if ky = ky and R > 1 as ky > 0.
[2m(E=Vo) [2mE
Butky = cen ted by 2 pat
Sok, = kif Vo=0 and hence the reflection willbe zero only if Vg is equal to zero, Therefore, there must
be some reflection even when E> Vo, This is in contrast to classical mechanics where R = 0 for E3 Vo,
‘Transmission coefficient (T)
Zhe transmission coefficient is equal to the Fatio of transmitted probability density current to the
incident probability density current.
fe Te ei Py mC cet
ie k
Unit mt "st+B)eS[+B le
= Pu ae “
PL (ky +h)
Since Pi= VImE = kh coewen
Pu = J2m(E=V) = kyh [Using Eo (5)
2
Ts fh sat ~ Shik fe
Kh (ky +hy) (+h) a / .gmPLE SOLUTIONS OF SCHRODINGER EQUATION ee
From Eq. (15), we find that T < 1. This is in contrast to classical mechanics where T = 1 for E>Vo-
‘Thus we find that the behaviour of quantum particle is quite different from that of a classical particle.
‘According to definition the sum of reflection coefficient and transmission coefficient must be unity.
Thus
rete ch) mh) shaky
(4th) the?
= (4th «1
2
(ki +h)
Example 8. Show that the reflection coefficient for a step potential with E > Vo can be written as
v2
1-1-2
(-2)
1/2
14{1-%2)
E
NV
and find its approximate form when i <1.
Solution. The reflection coefficient for such a step potential is given by
fy _ [am(E-Vo)
k= w 2mE
Ng
For %o << 1, using Binomial theorem and neglecting the terms containing higher powers of ==
we get 6
MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc, i)
‘OTENTIAL BARRIER OF FINITE WIDTH AND HEIGHT (Tunnel Effect)
we consider a paricle incident on a barrier of the type shown in fig. having width ‘a’ a
with the
condition that the energy of particte E < Vo and the barrier potential is given by
0 for x<0 (region!)
V(x) =4Vo for 0Q, (region III)
+ Vo)
! Ve=Vy
INCIDENT WAVE
REFLECTED WAVE
E
ky *) 2
14+) sinh*(ka)
lz ky ;
2
b_k } sinh?
<7 (ka)
ly he a
Eq, (23) measure the probability that the particle is reflected from the barrier.
‘Transmission coefficient (T)
The transmission coefficient is equal to the ratio of transmitted probability density current to the
incident probability density curent. f
R=
R=
(23)
cosh? (kya) + (
Transmitted probability density current
ae T= “Ticident probability density current
Veer
or T= Suter
VVin Pint
Feltiagt ihe
or
te ae [ou=] 120 MODERN'S ATOMIC AND MOLECULAR PHYSICS (9, »
Peel
or Ts
AA
Using Eq, (18), we get
Te—_ FF
Ike YL
FF’ | cosh? (kya) +—| =2—4L] |einh’ (kya)
4k ky
cosh? = 1+ sinh?)
2
1+sinh?(k,a)] 1+ Baap
ky
1
on T=
2 2,
Race heal a
|
Dik, sinh?(kya)
Putting the value of ky and ky from Eq. (3) and (5), we get
1+
1
————. (24)
‘Thus T # 0, hence we can say that the particle has certain Probability of penetrating the barrier and
Teach the region III, which is contradictory to the classical prediction. ‘The transmission is based on
‘tunnel effect which may be stated as under :
'fa particle is impinging on a barrier with energy less than the height of the potential barrier, it will
{ot necessarily be totally reflected by the barrier but there is always probability that it may cross the
barrier and continue its forward motion. (Fig. 4.8).
The tunnel effect can be understood
in terms of the uncertainty principle; if we
say that the incident particle cannot enter
the barrier, then the uncertainty Ax in its
Position must be 0 there. But since
Ax Ap > 4/2, the corresponding
uncertainty Ap in the particle's
momentum must be infinite inside the
barrier. An infinite uncertainity in p means
that p, and E as well, must be infinite,
which is not compatible with the finite
momentum and energy of the particle.
Therefore, the particle must be able to
enter the barrier, and once inside it has
the possibility of continuing on,
‘The tunnel effect actually occurs, notably inthe case of alpha particles emited by certain radioactive
nuclei. An alpha particle whose kinetic energy is only a few MeV is able ne escape from a nucleus
Fig. 4.8 SIMPLE SOLUTIONS OF SCHRODINGER EQUATION 121
whose potential wall is perhaps 25-MeV high. The probability of escape is so small that the alpha
particle might have to strike the wall 10°8 or more times before it emerges, but sooner or later it does get
out. Tunneling also occurs in the operation of certain semiconductor diodes in which electrons pass
through the potential barriers even though their kinetic ‘energies are smaller than the barrier heights.
4,S:HARMONIC OSCILLATOR ~~
A parti le undergoing si iple harmonic motion is called a harmonic oscillator. In a harmonic
oscillator. the force applied is directly proportional to the displacement and is always directed towards
the mean position.
If applied force displaces the particle through x, then Restoring force F is given by
Fa ed
or F=~kx _ (kis force constant) en)
The potential energy of the oscillator is
= —f Fax
or Va kf ade = (2)
(3)
@ = \[-~ is called angular frequency.
The classical frequency of thé oscillator v is given by
wo 1 fk
2x 2aVn on)
There are various ways to write the solution to Eq. (3). A common one is
x= A cos (wi +) = A cos (27v1 +)
where v is the frequency, A is the amplitude and
@ is the phase angle which depends upon what x is g ENERGY a
altime t= 0 2
Ifa graph is platted between V(x) and x, the graph
will be a parabola as shown in fig. 4.9.
ITE is the total energy and A is the amplitude of
the motion, we find that at points x = + A, where
YE are called turning points
Fig.4.9 .gMPLE SOLUTIONS OF SCHRODINGER EQUATION 15
v. Penetration distance of the particle inside the step
1 h h
Axe set
ky © f2m(Vy-E) © 2n,/2m(Vo —E)
: 6625x1074
2x3442x V2%4x 107! x2.x 1075
= 22x 10-2 m
Example 10. Find the barrier penetration factor for electrons of kinetic energy 10eV through a
barrier 2A thick and width Vp = 20 eV.
Solution, Here E = 10eV = 10 x 1-6 x 10-95 = 1-6 x 10-18 J
a= 2A =2x 10 mVo= 20 eV =3:2 x 108 m= 91 x 103! kg
Barrier penetration factor
1
ve ‘2m(Vo - E)
1+ ‘i inh? 0
N25 ef
Ve _ G2x107!8)? a
4E(Vg—E) © 4x16x10-'® x16x107
Y=
sinh |2"¥o—E) e ee
Tz
2
Since
= ———} = 0006208
1+(126516)
Example 11. What is the condition under which a particle travels through the barrier without any
reflection ?
Solution.
The barrier penetration factor (ie. transmission coefficient) for a particle having kinetic energy E
through a barrier of thickness ‘a’ and with V9 is given by
Nb
+— 0 _
4E(Vo - E)
For perfect transmission, T = 1
1
—=1
2 =
1418 inn? [2m = BD,
4E(Vq - B) W
2 2m(Vo — 8) i
or Vi ginn? |MM0- Bg
EM -E) W
fam(Vo - E)
or sinh? pre, =0 y
MODERN'S ATOMIC AND MOLECULAR PHYSicg 22
126
2m(Vo —E)
or :
or
or
= nl2 :
Hence the barrier thickness should be integral multiple of half the de-Broglie wavelength for Petey
transmission of the particle.
seeps eee
OBJECTIVE TYPE QUESTIONS
5
1, The energy of a particle in one-dimensional box of width L varies as
@L OL v=
(©) Lt (@ L
2. Particle in a box is
(a) one dimensional barrier problem.
(6) Two dimensional barrier problem. 5
(c) three dimensional barrier problem *
3. The energy of a particle in ‘one dimensional box of width L
(a) increases with width
() decreases with width
(©) independent of width
4. The energy of a particle in one-dimensional infinite well is
(@) Ean (DE « n2
1
OE« + Obes
5. The reflection coefficient for a Particle on a potential step with energy less than step height is
@1 Oo
1 . 1
> 6 @ 5.
6 The transmission coefficient T for a Particle on a potential step with energy more than step
height.
@T= “ @T<1
(T=0 @T=0
7. The zero point energy of a harmonit¢ oscillator is
(@) zero ©) hw
1 3
() zhe (d) zhw
8. The energy of one dimensional harmonic oscillator in first excited state is
@o (0) Srey
3 hy 5
> @ Sho
a _—
