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Exercises in Quatum Mechanics (Kluwer Texts in The Mathematical Sciences 6)
Exercises in Quatum Mechanics (Kluwer Texts in The Mathematical Sciences 6)
The titles published in this series are listed at the end of this volume.
Exercises in
Quantum Mechanics
A Collection of Illustrative Problems
and Their Solutions
Second Revised Edition
by
Harry Mavromatis
Department of Physics,
King Fahd University of Petroleum and Minerals,
Dhahran, Saudi Arabia
and
Tn f.p.a un f.uTiv
Table of Contents
Preface IX
Preface to Second Edition Xl
Schematic Illustration Xlll
IX
Preface to Second Edition
More than five years have passed since I prepared the first edition of this mono-
graph.
The present revised edition is more attractive in layout than its predecessor, and
most, if not all of the errors in the original edition (many of which were kindly pointed
out by reviewers, colleagues, and students) have now been corrected.
Additionally the material in the original fourteen chapters has been extended with
significant additions to Chapters 8, 13, and 14.
Three new chapters, Chapters 15-17 were added in order to make this volume more
comprehensive and more complete in its coverage of Elementary Quantum Mechanics,
principally by including material on angular momentum coupling and tensor algebra.
As a result of these additions and the revisions of the original fourteen chapters, the
present monograph includes 228, as opposed to the 114 solved exercises in the first
edition.
The author would like to acknowledge the support of the King Fahd University
of Petroleum and Minerals in this project.
Xl
Schematic illustration of
various approaches to
calculating Energy Levels
of
Quantum Mechanical Systems
Energy Levels:
Approach for
High-lying States:
Generally useful
approaches: 1) Wilson-Sommerfeld
Quantization Condition
1) Schrodinger equation (Chapter 1)
in Momentum Space
(Chapter 3)
2) Poles of Scattering
Amplitude
(Chapter 6)
3) Schrodinger equation
in Coordinate Space
(Chapters 8, 9, 12, 16)
4) Perturbation Theory
(Chapter 11) Approaches for Ground State:
1) Uncertainty Principle
5) Dalgarno-Lewis (Chapter 5)
Technique
(Chapter 14)
2) Variational Technique
(Chapter 10)
Xlll
CHAPTER 1
The hydrogen atom, when treated using Bohr's admixture of classical and quan-
tum concepts involves an electron circulating about a proton (subject to the attractive
Coulomb force - (e 2 147rfor2) r) in orbits which satisfy the condition:
Since ADe Broglie = hlp this reduces to p27rr = nh, which may be generalized to
the Wilson-Sommerfeld quantization condition:
0, 0< x < a,
V(x) = {
00, x < 0, x> a.
EXAMPLE 1.1
Find the energy levels for a particle in a box with infinite walls:
0, 0< x < a,
V(x) = {
00, x < 0, x> a.
f .J2mEdx = nh
where a cycle involves x varying from 0 --7 a and from a --7 O.
Integrating one obtains:
n 2 h2
2a.J2mE = nh or E = - 82 ' n = 1, 2, 3 .... (1.2)
ma
2 Chapter 1
By contrast the quantum-mechanical treatment of this problem involves solving
the Schrodinger equation:
"liZ dZ
[- 2m dxz + V(x) ] 'I/;(x) = E'I/;(x), (1.3)
V( xl
for 0 < x < a with boundary conditions '1/;(0), 'I/;(a) = 0, 'I/;(x) being zero for
x < 0, x> a.
The properly normalized eigenfunctions of Eq. (1.3) which satisfy these boundary
conditions are:
(:2 k
"li 2 2
'I/;(x)=V~ sinkx with ka=mr, where 2m =E.
If
Thus
'1/;(0) = sinO = 0,
and
while
Wilson-Sommerfeld Quantization Condition 3
by construction.
Since
this implies
One can gain a little more insight as to the range of applicability of the Wilson-
Sommerfeld quantization condition by studying slightly more complicated systems.
EXAMPLE 1.2
Find the energy levels of a particle in the potential:
0, 0< x < a,
V( x)
Vo
~~----------~--------------~--------x
a o+b
( 1.4)
On the other hand, solving the Schrodinger equation in the regions 0 < x < a
and a < x < a + b ('IjJ(x) being zero for x:::; 0, x ~ a + b) yields
'IjJ(x)=Bsink2(x-a-b), a<x<a+b,
since 'IjJ(0) and 'IjJ(a + b) must be zero.
The continuity of 'IjJ(x) , d'IjJ(x)jdx at x = a then implies
kl
tan kl a = - k2 tan k2b. (1.5)
One notes that the conditions specified in Eq. (1.4) and Eq. (1.5) are differ-
ent. Only if k2 rv kl i.e. E > > Vo that is if the total energy is large compared to
the potential energy does Eq. (1.5) reduce to Eq. (1.4) since then tan kla rv - tan k2b
which is satisfied if
kla + k2b = mr, n = 1, 2, 3 ....
A second example which illustrates the range of applicability of the Wilson-
Sommerfeld quantization condition is the finite square-well problem.
EXAMPLE 1.3
Find the energy levels for a particle in a square well
0, Ixl > a,
v- {
-IVoI, Ixl < a,
where E < o.
Wilson-Sommerfeld Quantization Condition 5
The kinetic energy
p2
T = -
2m
= IVoI - lEI for Ixl < a.
The Wilson-Sommerfeld quantization condition therefore yields in this case
l.e.
(1.6)
v (x)
-0 o
----------------.---------r--------.---------------- x
- - - - - - - - - - - - - - - - 1 - - - - - -lEI
T
L---_ _ t -IVol
+--_~
On the other hand, solving the Schrodinger equation in the regions Ixl < a,
Ix I > a yields respectively
I.e.
If V(x) = Alxl P one can obtain the form of the energy sequence according to the
Wilson-Sommerfeld quantization condition Eq. (1.1) as follows:
or generally:
{ I
AII/Ph }2P/(P+2)
lEn I = n 2p /(p+2) n = 1, 2, ... (p > -2), (1.8)
V2m I(p)
f -Iul du
where
I(p) = )1 p if En > 0,
I(p) = f Vlul
and
du P - 1 if En < o.
As p - t 00, En in Eq. (1.8) becomes ex n 2 , the result Eq. (1.2) for a particle in a
box with infinite walls. [In detail 1(00) =4, E(X> = n 2Aoh 2/32m = n 2h 2 /32m. This
corresponds to a = 2 in Eq. (1.2), i.e. V = 0, Ixl < 1, V = 00, Ixl > 1.]
In several cases I(p) can be easily evaluated directly.
EXAMPLE 1.4
Find the energy levels for a particle in the well
(
A )1/2 h
En = n 2m 1(2) ,
where
l.e.
En = n'hlff., n= 1, 2, 3 .... (1.9)
(1.10)
8 Chapter 1
EXAMPLE 1.5
Find the energy levels for a particle in the well:
00, x < 0,
using the Wilson-Sommerfeld quantization condition.
This problem goes through like Example 1.4, except
1(2) = 2 1
o
1
~ du = -
1r
2
and hence
En = 2nhV{2A
-;;;:, n = 1, 2, 3 ... , (1.11)
EXAMPLE 1.6
Find the energy levels for a particle in the well
1 vr=x
where
1 8
1(1) = 4 dx = -,
o 3
l.e.
n = 1, 2, 3.... (1.13)
as compared to the solution of the Schrodinger equation (see Eq. (3.31) ) for this
problem in the limit of large En namely:
and hence
EXAMPLE 1.8
Find the energy levels for a particle in the well:
IAI
V(x) = -~' all x.
where
1( -1) = 410 J~ - 1 du = 27r,
1
I.e.
E __ 2mlAI2 1
n - 1i,2 n2 '
(1.15)
which is identical to the energy levels obtained for this problem using the Schrodinger
equation (see Eq. (3.32) ).
10 Chapter 1
EXAMPLE 1.9
Find the energy levels for a particle in the well:
-IAI/x, x> 0,
V(x) = {
00, x < O.
1(-1) = 210 J~ -1 du =
1
7[",
and hence
n = 1, 2, 3 ... , (1.16)
which is identical to the energy levels obtained for this problem using the Schrodinger
equation (see Eq. (3.23) ).
EXAMPLE 1.10
Find the energy levels for a particle in the well
1.e.
En = n 2/ 5 (
A2h 15
V2rri
)2/5 ' n = 1, 2, 3.... (1.17)
2m 32
EXAMPLE 1.11
Find the energy levels for a particle in the well:
Ax1/2, x> 0,
V(x) = {
00, x < O.
EXAMPLE 1.12
Find the energy levels for a particle in the well:
IAI all x.
V(x) = -lxI 1/ 2 '
1.e.
IAI- 2h) -2/3
( .,fiiTi
En = _n- 2 / 3 7r ,n = 1, 2, 3 .... (1.19)
EXAMPLE 1.13
Find the energy levels for a particle in the well:
-IAlx-l/2, x> 0,
V(x) = { (E < 0)
00, x < O.
One proceeds as in Example 1.12 except
Generally
( 1.21)
= ±B (~ ~) _ 2v1iT ( {I / p} + 1 )
p 2' p - r( {1/p} + {3/2} ) .
12 Chapter 1
EXAMPLE 1.14
Find the energy levels for a particle in each of the following wells:
f
Hence
P¢ de/> = n¢h, n¢ = 1, 2, 3 ... , (1.26)
which implies
P¢ = n¢n,
and
fpp dp= nph, np = 1, 2, 3 ... , (1.27)
I.e.
The integral in Eq. (1.28) can be evaluated analytically for certain problems.
EXAMPLE 1.15
Find the energy levels for a particle of mass m in the potential
Wilson-Sommerfeld Quantization Condition 13
TABLE 1.1
Energy levels for various potentials Vex) = AlxlP
Wilson-Sommerfeld
p Range quantization condition Schrodinger result
1 x ;:: 0 E
n
= n 2/3 ( A2/;2
m
)1/3 ( 3". )2/3
2T2 En
= (n _ 1)2/3
4
( A2/;2t3( 311: y/3
m 2T2
(for large E)
2 (:Ay/2
= (n - t)
2 -00 <x< 00 En = n (A~f/2
2m
!l '7r
En 2m !l
".
1/3 -00
- 2/7 (A h35i )2/7
< X < 00 E n-n 3
,~,
One can either evaluate the integral in Eq. (1.29) using complex integration l , or
by elementary methods.
Thus defining
2nph = f VA + ~u + Cu 2 du
= 2 A (l umax du
Umin UV A + Bu + Cu 2
B l
+-
2 umin
umax du
VA + Bu + Cu 2
+ ~ lumax d(A + Bu + CU 2 ))
2 umin VA + Bu + Cu 2
__ (1 .[
A~arcsm
2
Bu + 2A
UVB2_4AC
] B 1 .
+"2 V_Carcsm
[-2CU - B ]
VB2_4AC
+VA + Bu + CU2rm~)
mIn U
where Umax and umin are obtained by determining where the integrand
VA+ Bu + Cu 2
u
vanishes
I.e.
-B-VB2_4AC
Umax = + (since B > 0; A, C < 0)
min 2C
with the constraint
B2 :2': 4AC I.e. E:2': nq,nw.
This yields:
or
E = (2np + nq,) nw, where np} = 1, 2, 3....
nq,
(1.30)
Wilson-Sommerfeld Quantization Condition 15
By comparison, the standard Schrodinger equation result for this system (see
Chapters 8 and 12) is:
Besides its shortcoming, that it gives quantized energies which are as a rule only
approximately correct for energies large compared to the potentials involved, the
Wilson-Sommerfeld procedure says nothing about the evaluation of probability dis-
tributions, transition rates etc. for which there are standard techniques in Quantum
Mechanics.
On a more positive note the quantization condition Eq. (1.1) is also a conse-
quence of applying the W.K.B. approximation to the Schrodinger equation2 with the
modification that nh must be replaced by (n + {1/2}) h in order to get the W. K. B.
approximation result.
References
The delta function is defined to have the following properties (in one dimension):
i: 6(x - x') dx = 1.
( 2.1)
i:
These have as a consequence that
One way to get some insight into this useful function and expressions for it in
terms of standard functions is to use 'the principle of completeness'. The principle
of completeness allows one to expand an arbitrary function in terms of any complete
orthonormal set. Thus if 'IjJ( x) is an arbitrary function,
(2.3)
n
(2.4)
i: i:
if the complete set 4>k(X) involves continuous functions, where
Expanding the delta function 6(x - x') in terms of a complete set of discrete
functions implies:
i.e. 00
EXAMPLE 2.1
Suppose one uses as a complete discrete set the eigenfunctions of a particle in an
infinite square-well potential (a box with infinite walls):
0, -a/2 .:::; x.:::; a/2,
V(x) ={
00, x < -a/2, x > a/2,
for the expansion in Eq. (2.6), with the choice x' = 0. The normalized even subset of
the above eigenfunctions (the rest, i.e. the odd subset is zero at x =:= 0, and does not
contribute to the integral in Eq. (2.5) for an, and hence to the sum in Eq. (2.6) ) is
h'(x) = ~
a n=O
f cos (2n + 1)n:x
a
--2 <
-
a
x <-
- 2 '
a
( 2.9)
a
= 0, x <--
2'
EXAMPLE 2.2
Show Eq. (2.9) is consistent with Eq. (2.1). One notes, interchanging integration
and summation7 that
1 -2 L cos ---7rX
00
-00 a
2n + 1
00
n=O
dx
a
= -
a
2
Ll
00
n=O
a/ 2
-a/2
2n + 1
cos ---7rX dx
a
= :;
4
E
00 (_l)n
2n + 1 = 1,
consistent with the integral in Eq. (2.1).
Considering the first two terms in the expansion of Eq. (2.9) as a crude approxi-
mation one gets the approximate representation:
2 (7rX 37rX) 4 7rX 27rx
h'(x) rv - cos-+cos-- = -cos-cos--, (2.10)
a a a a a a
18 Chapter 2
which is plotted in Figure 2.1.
a!)lx)=6"lc})
x
a
Figure 2.1: Plot of c5(x) '" (4/ a) cos (7rX/ a) cos (27rx / a).
Considering the first four terms of the expansion given in Eq. (2.9) one gets a
somewhat better approximate representation of the delta function:
EXAMPLE 2.3
Consider instead for the complete, discrete set in the expansion of the delta func-
tion, the eigenfunctions of a particle in a harmonic-oscillator potential:
The Delta Function, Completeness, and Closure 19
The eigenfunctions of this potential which are non zero at x = 0 are:
<Pn{x)
1 (1)1/2(
= 2n/2n!
1)1/4 exp (X2)
7rb2
(X)
- 2b2 Hn b ' (n even). (2.12)
as I x I=SI-a-I
8
-----------4-+4-4-~-+~+----------.-L
a
Figure 2.2: Plot of 8( x) rv (8/ a) cos (7rX / a) cos (27rx / a) cos (47rx/ a).
(2.13)
where one need not specify the sum is only over even n since Hn(O) is zero for odd n.
8() 1 r [1 {X2 (1 + t 2) }]
X = ..jit~ b~exp -2b2(1-t2 ) ,
(2.15)
Figure 2.3: Plot of 8(x/b) = b 8(x) '" (3/ [2..ji ])exp (-x 2 /2b 2 ) (1- 2x 2 /3b2 ).
( 2.16)
The Delta Function, Completeness, and Closure 21
S(t1:bS( xl
-5 4 5
igure 2.4: Plot of 8(x/b) = b 8(x) ~ (15/ [8 Ji]) exp (_x 2 /2b2) (1 - 4x 2/3b2 + 4x 4 /15b4 ) •
EXAMPLE 2.4
Show that Eq. (2.13) is consistent with Eq. (2.2) for f(x) = exp (_x 2 /2b 2 ).
One notes, interchanging integration and summation, that since Ho(O = 1, and
the H's are orthonormal9 ,
1-0000 (X2)
exp - 2b2 8(x) dx = Ji1 b 1-0000 (X2) E
exp - b2
00 1 (X)
2nn!Hn b Hn(O) dx =
EXAMPLE 2.5
Show that Eq. (2.13) is consistent with Eq. (2.1).
22 Chapter 2
One must verify that
Interchanging the integration and the summation and defining ~ = x/b in this
expression,
EXAMPLE 2.6
Use as a continuous representation of the delta function the set of free-particle
wave functions (V(x) = 0, all x),
8(x) = IAI2jOO exp (ikx) dk = IAI2 lim exp (ikx) -: exp (-ikx) = 21AI2 lim sin kx .
-00 k-+oo zx k-+oo X
The Delta. Function, Completeness, a.nd Closure 23
One can obtain, using the property of Eq. (2.1) J~ 6(x) dx = 1,
that:
1 = 2\A\2 hm .1
k--+oo
00
-00
sinkx
- - dx = 2\A\211",
X
(a result independent of k).
Hence
C() = -
uX
1 1.I msin-kx
-, (2.17)
11" k--+oo X
is a second expression for the delta function in terms of a limit. Using the above
value of A, to within an overall phase the set of free-particle wave functions with
'delta function' normalization becomes:
8(x) = 1
-2
11"
1 exp(ikx) dk
00
-00
= -1
211"
1 coskx dk 11" 1 coskx dk,
00
-00
= -1
0
00
( 2.19)
since the integral J::"oo sin kx dk = 0 , the integrand here being an odd function, while
the integrand cos kx being even,
1 cos kx dk
00
-00
= 2
Jo
roo cos kx dk .
J8(r' - iJ)
where
dr= 1,
11
I.e.
roo 8(r -
Jo
r') dr
-1
8( cos 0 - cos 0') d cos 0 r
Jo
21f
6(4)- 4>') d4> = l.
If one multiplies both sides of Eq. (2.20) by ~q(O, 4»~*q(O', 4>'), and integrates
over dO. dO.' one obtains
8(r - r')
~--:-2~
r
= ,,*
L.J Rnq ()
n
r Rnq (')
r ,
24 Chapter 2
and for three-dimensional systems quite generally one can thus write for the delta
function (for any choice of orbital quantum number 1):
00
where unl(r) is the solution, subject to the condition Unl(O) 0, of the radial
Schrodinger equation:
The choice of central potential V (r) determines the detailed form of Unl (r). The
corresponding one-dimensional expression is Eq. (2.6) where x extends over all space,
and ¢n (x) is the solution of the one-dimensional Schrodinger equation:
1i2 cP }
{ -2mdx 2 + V(x) - E ¢n(x) = 0, (-00 < x < 00),
with the choice of V (x) similarly determining the detailed form of ¢n (x).
For continuum states Eq. (2.21) is replaced by
(2.22)
EXAMPLE 2.7
Obtain an expression for 6(r - r') if V(r) is the three-dimensional harmonic-
oscillator potential:
1i 2r 2/2mb\ r 2:: 0,
V(r) = {
undefined, r < 0.
Inserting the detailed solutions Unl( r) for this potential (d. Eq. (8.13) ) in Eq.
(2.21) one obtains:
( 2.23)
The Delta Function, Completeness, and Closure 25
for each permissible value of 1 (1 = 0, 1, 2... ), and where r, r' > O.
If I = 0 for example
( 2.24)
(2.25)
n.
'r( n + 3/2) = (2n 2+2nI)!
+1'
-..Ii
The Eq. (2.24) can be written in a form similar to Eq. (2.25),
namely
00
Hn (rib) Hn (r'lb)
(2.26)
n=1, 3,5
The Eq. (2.26) involves a sum only over odd n terms, for which Hn(O is zero if = o. e
Thus 8(r - r') in Eq. (2.26) vanishes if either r or r' is zero. Also, an additional
factor 2 arises in Eq. (2.26) as compared to Eq. (2.24) because x, x' extend from
-00 to +00 whereas r, r' extend from 0 -+ 00.
Using the Hille-Hardy formula3
+ 1)y} /2) ~
( xy)a/2 exP (-2({x + r(n + a:, + 1) 1 F1 (-n., a: + 1., x) 1 F1 (-n·, a: + 1., y) t n
r a:
~
n=O n.
_ r
-l-t
a/2
- - exp ({I2
l+t}) I (2(x yt)1/2)
- -(x + y)--
1-t 1-t a'
or
For I = 0, since4
But as f -+ 0,
2rr/) 1 (2rr/)
sinh ( - f - -+ 2exp - f - ,
EXAMPLE 2.8
Verify Eq. (2.26) is consistent with Eq. (2.2) if f(r) = Hm(rjb)exp( -r2 /2b 2), (modd
According to Eq. (2.2)
The Delta Function, Completeness, and Closure 27
Multiplying Eq. (2.26) by Hm(r /b) exp (-r2 /2l?) (modd), and integrating both
sides over r one obtains
EXAMPLE 2.9
Suppose a particle is in the ground state of the potential:
One wishes to find the probability the particle will be in any (say the ground) state of
this new potential. What is involved in this case is a displacement of the equilibrium
position (from x to Xl) and a change of frequency (from Wo to wd of the potential,
as illustrated in Figure 2.5.
1 )
<Po (X, bo) = ( bo";;
1/2 (X2 )
exp - 2b5 .
28 Chapter 2
The potential changes frequency where:
and is displaced so the complete set of states which now describes the system is
¢n (x - Xl, bd. To find the probability one merely uses Eq. (2.3).
L: an¢n (x -
00
----------~~----------------------~~~----------.- X
Xi
i:
where
EXAMPLE 2.10
Consider a particle wave function:
0, Ixl < b,
Vex) = {
00, Ixl > b.
What is the probability the particle is in the ground state of this potential?
fl fl
Vb cos kx = Vb cos 2b '
7rX
where
Hence
I.e.
ao = -8v15
3 - '" 0.9993,
7r
thus laol 2 = 0.9986 '" 1,
as it should be since the wave function forms are very similar (d. Example 13.1,
Figure 13.1), as too their energies:
30 Chapter 2
EXAMPLE 2.11
Consider a particle bound by the potential:
-Ivai c5(x).
The potential suddenly changes to:
0, Ixl < b,
V(x) ={
00, Ixl > b.
Find the probability the particle will be in one of the even-parity states of this
new potential.
if;o( x ) -- JlVolm
h2 exp (_IValmlxl)
h2 ,
an = l b
-b
J'Valm
-,;,z- exp
(IValmlxl) {l
h2 Vb cos
(2n + 1)7rX d
2b x
if;m(x) = Vb . (m1rx)
(l sm -b- .
EXAMPLE 2.12
A particle is originally in the ground state of the well
0, 0 < x < b.
The Delta Function, Completeness, and Closure 31
Suddenly the wall at x = b is shifted to x = 2b. Find the probability the particle
will be in the ground state of the new potential which results from this shift.
The wave function is originally:
4>o(x) = {
{iib sin (7fX/b), °< x < b,
0, x < 0, x> b,
and one is interested in the overlap:
Thus
rb f2 . 7rX {1 . 7rX d 1
Jo V"bsmTV"bslllT x = V2.
Thus the probability the energy is unchanged is 1/2. The probability the new energy
is more than the original energy is
1- (
32
97r2
1)
+ 2" .
One can also use complete set expansions in related problems. For instance:
EXAMPLE 2.13
Given a particle with wave function:
All the bn 's are zero since '¢( x) is an even function, whereas the
1 . (
;::;Slll
yC
n + 1) -7I"X
c
,
s
an = l 1 ( 21) -,¢(x)dx=
c
-c
;::;cos n+-
yC
7I"X
C (n
v'6
+ 1/2)
2
71"2
EXAMPLE 2.14
Verify the sum of the probabilities la n l2 in Example 2.13 is unity.
The Eq. (4.22) of Chapter 4 lists some other representations of the delta function.
These can be compared to Eqs. (2.9), (2.13), (2.15), (2.17), (2.19), (2.23), (2.25), and
(2.30), which were discussed in this chapter.
The Delta Function, Completeness, and Closure 33
References
2. Op. cit., v. 1, p. 5.
3. Op. cit., v. 2, p. 189, v. 3, p. 272.
Momentum Space
Working in momentum space involves taking the Fourier transform of the eigen-
function 'Ij.;(x, t) of the Schrodinger equation. Thus if:
1
<p(p, t) ==..j'i; Joo exp (ipx)
-00 -T 'Ij.;(x, t) dx, (3.1)
~
271'
Joo exp (iY(X 1i- Xl))
-00
dy = 1:( _
1i u x
')
x,
1
that
1 1i exp (ipX)
T <p(p, t) dp. (3.2)
00
'Ij.;(x, t) = ..j'i; -00
The function <p(p, t) is called the wave function in "momentum space". Assuming 'Ij.;,
and <p are normalizable (i.e. vanish at ±oo so one can integrate by parts and drop
surface terms), it can readily be shown that:
"'()
p", P t = -1-
, ..j'i;
1
00
-00
exp (ipx)
- - -1i o'lj.;(x, t) dX'
1i i ox '
0 <p(p, t) =
-T1i op 1
..j'i; 1 00
-00 exp (ipX)
-T x'lj.;(x, t) dx.
More generally for any operators A(p), B(x) :
B (-~ ~) <p(p,t) 1
..j'i; 1 00
-00 exp (ipx)
-Ii: B(x)'Ij.;(x,t)dx.
Similarly
Momentum Space 35
(3.4)
Also
84>(p, t) _ _
8
t
1
- /?L
v2~
1 00
-00
exp
(_ iPx) ~.I'( ) d
t
It
8 'f' X, t x.
t
(3.5)
Thus
[-p2
2m
+ V (h
--;-- + -;--
z 8p
h
z at
8) 8] 4>(p, t)
(3.6)
2 2
00
-t: - 2m
$11-00 exp (iPX)[ h 8x2
8 + Vex) + ih8]
8t '1f;(x, t)dx.
But since the integrand on the r.h.s. of Eq. (3.6) vanishes, '1f;(x, t) being a solution of
the Schrodinger equation, the momentum-space function 4>(p, t) satisfies an analogous
equation:
p2
[2m (h8) h8]
+ V -i 8p + i 8t 4>(p, t) = 0, (3.7)
L: '1f;*(x, t)n(x)'1f;(x, t) dx
X 1~~~: ¢>*(p', t) exp ( - iP~X) dp' 1:~: exp C~X)n ( -~ ;p) ¢>(p, t)dpdx
(3.8)
n abyn-;-'\7
--a etc.
i x z
Six simple problems follow which illustrate the usefulness of the momentum rep-
resentation and the fact that for certain potentials it is easier to work in momentum,
rather than coordinate space.
EXAMPLE 3.1
Consider the case of a free particle (V{ x) = 0). In momentum space the Schrodinger
equation, (Eq. (3.7) ) for this system is:
(3.9)
I.e.
¢(p) = 8 (~_ v'2;:E) .
vk J:
Since generally
'IjJ{x) = ¢(p) exp C~X)d (~) ,
if one suppresses the time variable in Eq. (3.2), in this case
EXAMPLE 3.2
Consider a particle in the momentum-dependent potential
V{x) = a~~
z ax
= ap.
In momentum space the Schrodinger equation (Eq. (3.7) ) for this potential is:
and as above
1/J( x) =
A
y'2; exp
(iPIX) B
T + y'2; (ip2X)
exp -11,- .
EXAMPLE 3.3
Obtain the exact solution of the problem
Ax, x > 0, (A> 0),
V(x) = {
00, x < 0,
(illustrated in Figure 3.1), with the help of the momentum representation.
v (x)
~----------------------~~x
In momentum space the Schrodinger equation (Eq. (3.7) ) for this potential is:
{ -p2 - A -;--
11, d }
- E <jJ(p) = 0 (E > 0), (3.11)
2m z dp
1.e.
38 Chapter 3
Integrating this expression yields:
i {p3 } {<p(p)}
Ali 6m - Ep = In C '
I.e.
V27rA Ali 6m
(i
- -Ep }) .
<p(p) = -1- exp - {p3 (3.13)
Since generally
'IjJ(x) = v'2i
1 1 <p(p)
00
-00 exp (ipx)
T dr;" (P) (3.14)
in this case
'IjJ(x) = -1-
27rvA
l P=oo
p=-oo
exp ( - i {p3
- - Ep }
Ali 6m
+ -iPX) d (P)
li
- .
li
(3.15)
For this problem the wave function 'IjJ(x) satisfies the boundary condition 'IjJ(0) = 0,
since V(O) = 00. Hence for this example
=
1
27rvA li
[jOO cos [p3/ 6m
-00
- EP] dp + .joo.sm [p3/ 6m
Ali
- E P] dp] .
Ali
2 -00
J OO
-00
•
sm
[p3/ 6m - EP] dp
Ali
Momentum Space 39
is odd, making the latter integral automatically zero.
Defining u == pj(2mAfi)1/3, Eq. (3.16) becomes
2m
q, ( -En { A2fi?
}1/3) = o. (3.17)
. (21 1
q, ( X ) -+ Ix11
1/ 4 sm 3" x
3/ 2
+ 4"71") .
Hence in this limit:
n = 1, 2, 3... ,
I.e.
E =n 2 / 3 ( - -
n m
A2fi2) 1/3 (32\1'2'
~
)2/3
EXAMPLE 3.4
Obtain the exact solution for a particle in the potential
p2 A }
{ 2m + -(fiji) (djdp) - E cp(p) = 0, (E < 0), (3.19)
40 Chapter 3
I.e.
_ (iA/,h - p/m) dp = d¢(p) = _ d (p2/2m + lEI) + (iA/h) dp
E - p2/2m ¢(p) p2/2m + lEI p2/2m + lEI·
V( x)
A------------------------x
1 00
-00
1"'( )1 2d (E.)
<f' P h
= 1= IC121°O
-00
dp/h
(lEI + p2/2m)2 .
Hence:
Momentum Space 41
To within a phase one therefore has:
0-- IEI3
1 (- -
- 7r 2mTi2
)1/4100 1 ([IAI~m
-00 lEI + p2/2m cos - Ti -arctan
lEI
{p}]
J 2m lEI
.. [IAI
-z sm lET arctan {p
TV{2ffi J lEI }]) dp.
2m
The integral
is automatically zero since the integrand is odd. Thus the even integral
Ti. IAI 2m 7r
Ti. AI
TAT sm [ TI ~
lET () "/2] = IAI sm [~]
2m
10 T lET '2 . (3.22)
]
Hence
The energy eigenvalues IEnl of this problem thus satisfy the equation
42 Chapter 3
n = 1, 2, 3... ,
or
(3.23)
With IAI = ahc this reduces to the well-known Bohr result and corresponds to
the energy of the state uno(r) (as well as of the states unl(r) since the energy levels
for hydrogen are independent of I, an effect known as "accidental" degeneracy) of the
hydrogen atom.
Substituting Eq. (3.23) into Eq. (3.21) one obtains a general expression for the
wave function in the momentum representation:
'" ( ) _ (2h,Bn/1r)1/2exp(-2inarctan{,BnP}) nh
'l'n P - 1 + (,Bnp)2 , ,Bn == mlAI ' n = 1,2,3 .... (3.24)
Using this expression one readily obtains:
\/2Pm
2
) = -En.
These two equations allow one to evaluate .6p~, the "variance" of p. In particular
(3.26)
(3.27)
h4 2
(X2) = 2" (5n 2 + 1) m~A12 . (3.28)
These results imply that .6x n , the square root of .6x~, the variance of x:
(3.29)
Momentum Space 43
Combining Eqs. (3.26) and (3.29) one obtains:
h h
t1xt1p = 2"v'n 2 + 2 > 2"' (3.30)
EXAMPLE 3.5
Solve exactly the problem of a particle in the potential
A
V(x) = !xi ' -00 < x < 00.
The potentials of Examples 3.5 and 3.6 are symmetric potentials i.e. if one plots
V(x) vs. x, the potential for x :::; 0 is the mirror reflection (about the V(x) axis) of
the wells for x > 0 in Examples 3.3 and 3.4 (Figures 3.1 and 3.2). One can proceed
here using methods similar to those used in Examples 3.3 and 3.4. However, instead
one can compare (cf. Eqs. (1.12) and (1.10) ) the solutions of the problem of the
standard harmonic oscillator potential restricted to x > 0 i.e. V (x) = AX2, 0:::;
x < 00, V(x) = 00, x < 0, to the oscillator extending over all space i.e. V(x) =
Ax2, -00 < x < 00. The former potential's allowed energies are
and correspond to odd-parity solutions (see Eq. (10.12) ), while the latter's allowed
energies are
and both odd and even parity solutions are allowed. One can thus obtain the solutions
in the latter case from the solutions in the former by letting n -+ n/2.
Similarly if one considers the infinite well V(x) = 00, x < 0, x > a, V(x) =
0, 0 < x < a, its solutions are the odd-parity wave functions tjJ( x) = )2/ a sin kx
(where ka = mr) i.e.
44 Chapter 3
whereas if one considers the infinite well V(x) = 00, x < -a, x > a, V(x) =
0, -a < x < a, its solutions are tf;{x) = V1/asinkx (odd parity), and tf;{x) =
V1/a cos kx (even parity), where ka = mr or (n -1/2)11", n = 1, 2, 3... , i.e.
2
E = h k 2 = ~ (~)2 11"2,
2 n = 1, 2, 3... ,
2m 2m 2 a
Again the solutions for the latter case can be obtained from the former by letting
n -+ n/2.
A third example which illustrates the fact that this procedure may be applied
generally is the potential weIll
1 + 8mVo
a h
]2 , n = 1, 2, 3... ,
2 2
has solutions
(s-n+1)/2
tf;(x)= ( 1-e ) 2 Fl(1-n,2s-n+2js-n+2j{1-0/2),
where
1 8mVo n = 1, 2, 3 ... ,
+ a2 h2
Thus in this case as well one obtains the solutions for the symmetric well by letting
n -+ n/2 in the solutions for the well which extends only from 0 < x < 00.
Momentum Space 45
The solutions for Example 3 are
(3.31 )
n = 1, 2, 3... , (3.32)
and that this includes both even- and odd-parity solutions. This result agrees pre-
cisely with the Wilson-Sommerfeld result (Eq. (1.15) ).
EXAMPLE 3.7
Obtain the ground-state wave function in coordinate space for the Hamiltonian
in Example 3.4 starting with the momentum-space wave function Eq. (3.24).
From Eq. (3.24) one notes that the ground-state function (n = 1) is:
'" ( ) =
'l'IP
(2h (.l )
7r1-'1
1/2 exp (-2i arctan {flIP})
1 + (fllp)2 , (3.33)
~1 (x) 1 Ii
= v'2i 100
-00 ¢1(P) exp (ipx)
T d (P)
1i,
46 Chapter 3
Substituting Eq. (3.33) in this equation
1/J ( ) - (2/i
1 X -
(3 )1/2
-:; 1
1
V2i n
1 00
-00
exp (ipx//i - 2 arctan {(31P}) d
+
1 (filP)2 p.
With the change of variable u == arctan /3IP this becomes
2 ( 1 )
1/Jl(X) = -; (31/i
1/2 1:/2/2 cos (/i~1 tan u - 2u) du.
Evaluating this expression3 one obtains finally:
(x)
= (1)3 10roo exp (2X)
4 (31/i
3 3(31/i 3/i2
- /i(31 x dx = -2- = 2mlAI '
References
where A(p') is a function concentrated about p' = p. Thus if A(p') is a delta function,
(cf. Eqs. (2.1), (2.2) ):
A(p') = 8 (pI ; p)
EXAMPLE 4.1
.fi
Suppose
W(x,O) = ~
28
7f
lp'_oo
pl =oo (Ip' - pi +T
exp-
iP'X)
8 (d{) ,
or
W(x,O) = ft.
837f exp Ct:PX ) x + h /8
2
1
2 2 •
(4.4)
____~--~~--~-+--~~~~------~~pl
p-26' p-6' p p+6' p+26'
The amplitude of the function given by Eq. (4.4) (ignoring the phase) is drawn
in Figure 4.2. There is a spread about x = 0 given approximately
by tJ..x = 2h/8. Thus tJ..x tJ..p '" 2h/8 28 = 4h.
A more accurate estimate of tJ..x tJ..p is possible since
Wavepackets and the Uncertainty Principle 49
21i31x=oo x 2 dx 1i 2
.6.x2={x2)= 63 7r "'=-00 (x2+n2j6 2)2 = 62 •
Similarly
( )=
P
!!.l
P '=oo,
fJ p'=-oo P exp
(_ 21p' -
fJ
pI) (dP')
fi
=
P,
while
62 .
<P2) = P2+"'2 I.e. D..p =
6
V2 '
and
fi 6 fi
D..x D..p = -.M = M rv D.71fi, (4.5)
6y 2 y2
in this case. Thus the uncertainty in the position multiplied by the uncertainty in the
momentum of a localized wavepacket is of the order of fi. Other A(p)'s yield similar
results.
50 Chapter 4
EXAMPLE 4.2
Consider the case
1 f3i"l P'=P+li,
W(x,O) = v'2-iV W p'=p-li (8 -Ip - pl)exp T (dT·
(iP'X) P')
A (pi>
r-____~------+------+--------------~~pl
p-s p
\IT(x,O) = -2
1 ~8
~t exp ~
(iPX) sin 2 (8x/21i) (4.7)
"It /l (8x/21i)2
[The normalization of this particular \IT(x,O) may be easily verified using the result
1o
00 sin4 u 7r]
- - du=-.
u4 3
The amplitude of the function of Eq. (4.7) (ignoring the phase) is drawn in Figure
4.4.
There appears to be a spread in x of approximately 21i7r / 8, giving an approximate
6.x 6.p ,...., (21i7r / 8) X 8 = h .
..LJ36
2 lTh
2liTf 2li1l"
-5 -8-
Hence,
v'3 n v'3 n 8 [3
~x = -8-' and ~x~p = -8-JTIj = ViO n = 0.55n,
in this case, a somewhat smaller result than that obtained in Example 4.1.
Obviously W(x, t) of Eq. (4.2) also satisfies the free-particle Schrodinger equation
just as Eq. (4.1) does, namely:
n2 f)2 n f)
- - II 2 W(x, t) = --;- ll.I. W(x, t), (4.8)
2m uX Z UL
1
v'2i 1 A(p') (p,2
00
-00
dp' = 0,
2m - E(p') ) exp { Ii [p'x - E (p') tl } T
if
p2
2m = E(p).
Further, independent of the form of A(p), since it is the wave function in momen-
tum space, one can write:
Substituting Eq. (4.9) into Eq. (4.2), and dropping the prime for the p's one
obtains:
W(x, t) = 1:&'=00
:&'=-00
W(x', O)~
27r
l P=oo
p=-oo
exp (i [Cx - x')p _ E(P)t]) dnPdx'.
n n (4.10)
Defining
1 )..*( ')).. C)
-00
00
'Pp x 'Pp x exp
{_iECP)t}dP
n n'
Wavepackets and the Uncertainty Principle 53
where the </>p(x )'s are the properly normalized free-particle wave functions (cf. Eq.
i:
(2.18) ), one can write Eq. (4.10) as follows:
The function G(x, x', t) of Eq. (4.11), known as the free-particle Green's function,
can be evaluated explicitly by integrating Eq. (4.11):
,
G(x, x, t) =
(m
27riht
)1/2 exp (m(x
-
_ X')2)
2iht . (4.13)
This function also satisfies the Schrodinger equation Eq. (4.8) and for t ----+ °
limG(x,x',t) ----+ 6(x - x'),
t-+O
(Eq. (4.13) having in this case the delta function form of Eq. (2.15» as it must
since for t = 0,
111 (x, 0) = JW(x',O)G(x,x',O) dx'.
A useful formula in calculating reflection and transmission times for wavepackets,
(which is a result independent of the details of A(p') but assumes it is peaked about
p' = p) involves expanding E(p') about p = p' in Eq. (4.2)
, p,2 p2
E(p) = 2m = 2m
dEep')
+ ~p'
I '
(p - p) + ....
p'=p
Keeping only linear terms (i.e. assuming only values about p' = p are important)
yields:
= _1 exp
~
{_~
h
(Lt _
2m
dEep')
dp'
I
p'=p
t p)}
a speed:
dE(p')
-d-'-
I .
p,2
. Smce E(p ) = 2m'
dE (p'), p'
= m == Vg . -a;p-
p p'=p
This is known as the group velocity of the wavepacket and is just the classical
speed of a free particle.
EXAMPLE 4.3
J21ro3fi
Given
A( ') = sin 2 {(p' - p)jo} (4.15)
P {(p' _ p)jO}2 '
find \J!(x, 0).
One can proceed as in the previous examples or note that since, according to Eq.
(4.2) (where if one uses k rather than p, the equations look more symmetric)
\J!(x, 0) = .~
v21r
1 A(k')
00
-00
exp (ik'x)dk', (fik = p),
if
¢>(x)= 1
tn=
v21r
1 A(k')exp{i(k'-k)x}dk'
-00
00
(4.16)
A(k') = .~
v21r
1 00
-00
\J!(x', 0) exp (-ik'x')dx' = ~
v21r
1 00
-00
¢>(x') exp {-ix'(k' - k)}dx'.
Hence
A(k + k') =
v21r
1
tn= 1 ¢>(x')
00
-00
exp (-ix'k')dx' = 1
tn=
v21r
1 ¢>(x')
00
-00
exp (ix'k')dx',
if ¢>(x) = ¢>(-x), or
Comparing Eqs. (4.16) and (4.17) one notes that if one identifies A(k') with a
particular (even) function ¢>( x' - x) one can then identify ¢>( x) with the corresponding
A(k + k').
Wavepackets and the Uncertainty Principle 55
In Example 4.2 for instance,
~ [38{sin{(k'- k)8/21i}}2
2y;r;, (k' - k)8/21i '
one obtains the corresponding
EXAMPLE 4.4
Consider the case
A(')
p
e3
= J2---;-Ti 1
(p' --p""-')2"'-+-e-=-2 . (4.19)
\If(x, 0) = ~JeTi
7r
1 00
-00
exp (ip'x/Ti) dp'
(p'-p)2+e 2 Ti
Je Ti
exp
(iPX) .!.
Ti 7r
1 exp(p'{i(p'- p)2- p)x/Ti}
00
-00 +e
d( , _ )/Ti
p p 2
(x) = 0,
I.e.
n
~x~p= V2'
The form of these distributions is given in Figures 4.1 and 4.2 with the appropriate
identifications. The symmetry between the A(p') and W(x, 0) in this example and the
W(x,O) and A(p') in Example 4.1 can be understood in the light of the remarks in
Example 4.3.
What is of some interest is that one can extract a representation of the delta
function from this example, namely:
This follows from the observation that when W(x,O) is evaluated using A'(p) rather
than A(p), then
W(x 0) = _1 exp (iPx) exp
, y"h n (_~)
n
and as e --+ 0 this expression for W(x, 0) becomes just a plane wave
1 (ipx)
y"hexp T .
This simplification occurs whenever a delta function 6( {p' - p} In) is substituted for
A(p') in Eq. (4.2), since then W(x, t) in this equation reverts to a plane-wave expres-
sion. Hence the A(p') above is a particular delta-function representation in the limit
Wavepackets and the Uncertainty Principle 57
e - t O. The procedure thus involves essentially determining the right overall factor
by which to multiply A(p') such that in some limit the resulting w(x, 0) reduces to a
plane wave. The A(p') multiplied by this factor is then a delta function in that limit.
By a similar analysis one can extract several other delta-function representations
from the A's used in this Chapter's examples. Some of these are listed in Eq. (4.22):
(4.22)
(vi) 8(u) = lim.-+o (1 -Iul/f)/f, lui < f (Ex. 4.2)
(ix) 8(u) = (1/16) lim......o (l/f) (3 -lul/f)2, 1 < lul/f < 3 (Ex. 4.5)
=0, lul/f> 3
(Ex. 4.11)
W(x,O) = _1 J 201i
.j2; 1l1r8
100
-00
(sin(pl- P)/8)3 exp (ipIX)d (pI) .
(pl-p)/8 Ii Ii
pex ,0)
--3~~~----~~---O+----h~--~--~~~------~X
-T -0 ~ T
Hence1 :
W(x,O) = J~~~exPC~X)[~(3_8~~2)],
Wavepackets and the Uncertainty Principle 59
(4.24)
u!:()
x = -311"4 l'1m
<-+00
E
(Sin
--
W)3
lOU
(4.25)
Similarly one may obtain representations of the delta function which involve higher
powers of sin (w) / w,
e.g.
limE (SinW)4
-3
--
211" .-+00 lOU '
1/ (-l)k(1/ - 2k)V-1
N(I/)-l = 2,,-1 ""'
L.,
O<5:.k<,,/2 k!(1/ - k)!
a result which reduces to Eq. (2.17) for 1/ = 1, and Eq. (4.22) (iii) - (iv) for
1/ = 2, 3, 4.
= "81 .
}!..~8 3[( 832 -x 2)] , 0<
1
Ixl < 7i '
8(x) =
1
16
}~~ 83[(~ _ Ixl) 2] , 7i1 < Ixl < 7i3 ' (4.26)
3
= 0, x> 7i .
Higher powers of other delta function expressions, for instance of
EXAMPLE 4.6
Consider:
A(p') =
hf(2v + 1) ((pi ~ P)2 + 1) -1'-1/2
(4.27)
Eft f(2v + 1/2)
a normalized 2 function peaked at p' = p.
Find the corresponding '1f (x, 0).
From standard tables 3 one obtains:
If v = 3/2,
fs If;
and
'1f(x, 0) = {liE + I} exp (_ f~l) exp
ZPX) .
(T (4.30)
8(u) -
- \hTT(v + 1/2)
1 lim
<-0 f
~ (M) K (M) (v>
2E
v
l/ f '
1) ,
--2
EXAMPLE 4.7
Find
\l1(x, t) if
A(p') = 1% exp ( _Ip' ~ pI),
and assuming the linear approximation (previously mentioned in this Chapter, d.
Eq. (4.14) ):
'T'(
'¥ x t
,
)-
-
Ml°O
-
27r8 -00
exp {IP' -
8
pi + -p
Ii
iE(p)t
i ,x - - --
Ii
i dE(p')
-
Ii
--
dp'
I ('p - P)}
p'=p
t (dliP').
\l1(x,t) J 7r!1i exp[~ {px - E(p)t}] 1°O exp (-~) cos {* (x - vgt)} (4.32)
X du= ~
C3li3 (
7ru
1
(x - Vgt) + Ii
2 2/
82
[in
) exp t{px-E(p)t}. ]
62 Chapter 4
If t = 0 this reduces to Eq. (4.4) of Example 4.1. Eq. (4.32) shows that to the
extent the linear approximation Eq. (4.31) is valid, the wavepacket moves forward at
a speed Vg , but its form does not change, i.e. there is no spreading. To get spreading
one must keep at least quadratic terms in the expansion for E(p').
EXAMPLE 4.8
Show that
alGI 2+ ~~ {G*aG _ aG* G} = 0 (4.33)
at ax 2mi ax ax '
where G(x,x',t) is the Green's function for a particular system (i.e. relates W(x,t)
to W(x,O) according to Eq. (4.12) ).
Since G(x, x', t) satisfies the time-dependent Schrodinger equation (possibly with
a potential Vex), assumed real),
a
1i2 2 ] 1i
[- - - - + V(x) G = --:--G,
a
2m ax 2 z at
and
[ -~~
2m ax
+ V(X)] G* = ~~G*.
2 z at
Premultiplying the first of these equations by G* and the second by G one obtains,
after subtracting that
Hence
~~
ax 2mz
{G*~G
ax
- G~G*} + ~IGI2 = o.
ax at
An equation identical to Eq. (4.33) is obviously satisfied when G is replaced by
W, and G* by W*. This latter equation is known as the Continuity equation for the
current density
namely
(4.34)
Wavepackets and tbe Uncertainty Principle 63
I:
EXAMPLE 4.9
Show that
G*(x,x',t)G(x,x",t) dx = 8(x' - x"), (4.35)
where
G(x, x', t) = ; , <p~(X')<Pn(X) exp ( -i E;t), (4.36)
(cf. Eq. (7.3) ). (This expression for G is the counterpart of Eq. (4.11) if the basis
one is using is discrete rather than continuous.)
I:
Hence show additionally that
Substituting Eq. (4.36) into the integral on the 1.h.s. of Eq. (4.35) and rearranging
the order of the summations and integration one obtains:
'"
n,n'
x exp (iEnt)
~ <Pn (') -r,,- <Pnl x exp (iEnd)
* (") --r,,- _ <Pn*()
00
1
x <Pnl ()
x dx
00
where one has assumed that the <p's satisfy the standard orthonormality and closure
conditions, (cf. Eq. (2.6) ).
Eq. (4.37) can be obtained by considering the case t goes to zero in Eq. (4.35)
since then G(x, x', t) and G*(x, x', t) go to 8(x -x'), while G(x, x", t) goes to 8(x -x").
The same result, Eq. (4.35) also follows if
= 1:~: cPk(X') exp { iE~k)t} dk 1~~~: cPkl(X") exp { iE~k')t } dk' (4.39)
64 Chapter 4
EXAMPLE 4.10
Consider the momentum distribution
A'(') 20:" (
p = -exp -0:"
Ip' - pI) sinO:"(p' - p)/n
7r n (Y(p' - p)/n .
-00
20:"
-exp
7r
( -0:" Ip' - pI) sin O:"(p' - p) /n exp -:t:P'x
n O:"(p' - p) /n n
(i) (dnP')
= ~ exp C~X) ~ arctan C;2).
As 0:" -+ 00 one notes that \Ii(x, 0) -+ a plane wave.
Hence
· A'(')
11m Ip' - pI) sin (O:"(p' - p)/n) =
p = 1·1m -20:" exp ( -0:"--- u$: (p'
---p) . ( 4.40)
"'-->00 "'-->00 7r n O:"(p' - p) /fi fi
The functions A'(p') and \Ii (x, 0) (ignoring the phase of the latter) are illustrated
in Figures 4.6, 4.7. One notes that
fi7r
f),p rv - , while f),x rv 20:"-J2, I.e. f),p f),x rv 2-J2 fi7r = -J2 h.
0:"
EXAMPLE 4.11
Consider the momentum distribution
A '(')
p = -0:" arctan {21i2}
2( )2.
27r 0:" p' - P
1 (ipx) exp(-x/O:") . (/ )
\Ii ( x,O ) = v'2i exp 1i x/O:" sm x 0:" . (4.41 )
Wavepackets and the Uncertainty Principle 65
From this latter equation it is clear that:
. a
hm -211" arctan
{2fI,2}
2( )2 = b
(pI _ p)
-·t- . (4.42)
01---+00 a p' - p It
ACp')
_ _ _- L_________~b-~~----L---L---L---~~~L------ p'
p _1'fn p _ 11" p + 11_"
~ 20c ~
.---~ I
~ .. X
~ [8 - Ip' - pI] , IP' - pi < 8 tJ!{ (8x /2fi)-2sin 2(8x /21i)exp( ipx /Ii) (Ex.
0, Ip' - pi> 8
I!£ {(p' - p)/8r 2sin2 {(p' - p)/8} tl¥ [2 -11] exp (ipx/fi) , Ixl::; 2fi/8 (Ex.
0, Ixl > 2fi/8
vm°<
if
[t(3-8 2x 2/fi 2)] exp(ipx/fi),
lxi/ii < 1/8
0, if lxi/ii> 3/8
Uncertainty Principle
and
Ground-State Energies of Quantum-Mechanical Systems
(5.1)
But tlxtlp rv n (cf. Chapter 4), i.e.
n
tlp rv tlx
and one expects p2 2:: {tlp} 2 = {1i, / tlx }2 since generally p is expected to be at least
of the order of tlp.
Hence one can write for the ground-state energy E :
E 1i,2 A (tlX)n
= 2m {tlx }2 + 2 '
where tlx is assumed greater than zero.
The choice of !:::.x which minimizes E is such that:
implying
{tlxr+2= 1i,22An.
nm
Uncertainty Principle and Ground-State Energies ... 69
For this choice of .6.x
I.e.
EXAMPLE 5.1
Consider the case n = 2, -00 <x< 00 .
E = ~ {'li2A}1/2 = _1 {'li2A}1/2
222m J2 m
The exact ground-state energy of this system is also
_1 {'li2 A}l/Z
J2 m
EXAMPLE 5.2
Consider the case n = 1, -00 <x< 00.
This can be compared to the ground-state energy of this system (for large argu-
ments of the relevant Airy function (d. Eq. (3.31) ) namely'" 0.89 {'li2 A2 1m f/3.
Meanwhile a variational calculation (Example 10.3) yields
EXAMPLE 5.3
Consider the case n = -1, -00 < x < 00.
This agrees exactly with the ground-state energy of the system (d. Eq. (3.32) ).
70 Chapter 5
EXAMPLE 5.4
Consider the case n = 1/2, -00 <x< 00.
E
5/2 {n2 A4 }1/5
2 7/ 5 m/2
= _5 {~}2/5 {~}2/5
212/ 5 7r fiiTi
0.599 {
hA2
~
}2/5
y2m
If
E =p2/2m+Axn
only for x > 0, and V(x) = 00 for x < 0, the above derivation must be modified in
that Llx rv x and
EXAMPLE 5.5
n: f/2 ,
If n = 2, x ~ 0,
E= ~ { ~~ f/2 = Vi {
compared to the exact ground-state energy in this case (d. Example 8.1),
n2 A}1/2
Eground =.J:4.5 { -;:;:;:
EXAMPLE 5.6
If n = 1, x ~ 0,
Uncertainty Principle and Ground-State Energies ... 71
which can be compared to the variational calculation for this problem (d. Example
1/3
10.2) Eground < 1.86 [ A2h,2 Jm ] and the lowest energy of this system for large
1/3
arguments of the relevant Airy function, namely 1.84 [ A 2h,2Jm] (d. Eq. (3.18) ).
EXAMPLE 5.7
If n = -1, x 2:: 0
which agrees exactly with the ground-state energy of the system (d. Eq. (3.23) ).
One should emphasize that Eqs. (5.2) and (5.3) are very rough estimates of the
ground-state energy of quantum-mechanical systems, but are nonetheless convenient
if one is interested in a result which is of the right order of magnitude.
EXAMPLE 5.8
If n = 1/2, x 2:: 0,
E1
= {15}2/5
16
{~}2/5
v'2ffi rv
2.03
{~}2/5
v'2ffi
EXAMPLE 5.9
Consider a particle moving in the attractive potential:
IVoIE (5.4)
V(x) = - (2 + E2)·
11" X
and
oE
ox =
72 Chapter 5
v (x)
I\X}2
{ L...l = 40'(;2 h
werea=
4-a
Therefore
(5.5)
As E ~ 00
E mm
. ~ [ 11101
--+11,
7rE
One can also obtain energy estimates for states other than the ground state pro-
vided one makes some assumption about b..x b..p for these states. For instancel one
may assume b..x b..p '" qn, which is not however generally true. Thus for the hydrogen
problemb..rb..p=nJq2+2/2 (d. Eq. (3.30) ),andifq»J2, b..rb..p"'qn/2.
Since this involves a further approximation, the resulting calculations for excited
Uncertainty Principle and Ground-State Energies ... 73
states will be even less reliable than the ground-state energy estimates made above.
With this further approximation the excited energy estimates can be obtained from
the above results by replacing Ii by qli in the relevant expressions.
References
that the wave function on the left side of a one-dimensional potential is:
this choice implies the particle is incident on the potential from the left.
Additionally
The poles of the transmission amplitude correspond to the allowed bound states
for that particular potential, and continuity considerations require
(6.4)
In addition an incident wavepacket can be written (cf. Chapter 4) as
t) = ~ JT(k')A(k')
and
Wtrans(x, exp [i {k'x - E(k')t/Ti}]dk', (6.7)
respectively.
Using standard procedures (d. Eq. (4.14) ) one can then obtain from Eqs. (6.5)-
(6.7) the time required for reflection off (the so called 'time delay') and transmission
through a particular potential.
EXAMPLE 6.1
Discuss the problem of particles incident on a potential
V(x) = Vac5(x).
If
'ifJL(x) = Aexp(ikx) + Bexp(-ikx),
(6.8)
Fexp (ikx),
continuity of the wave function at x = 0 implies:
A+B=F. (6.9)
V( X)
1i 2 d2
- - - d2'I/J(X)
2m x
+ Vo5(x)'I/J(x) = E'I/J(x),
and integrating across x = 0,
1i
- 2m
2
j'
_, d (d'I/J)
dx + j'_, Vo5(x)'I/J(x) dx = j'
E _, 'I/J(x) dx.
lim{d'dx
,-+0
I/Jl _d'I/Jl
dx x=-€
}=2m2Vo 'I/J(0),
1i
(6.10)
x=€
I.e.
ik(F-A+B)-
- 2mVo
1i 2 F • (6.11)
exp (i5r )
(6.12)
while,
(6.13)
In this case
1
IRI2 k21i4/m2V02 +1 '
(6.14)
k21i4/m2Vi
ITI2 =
k2n4/m2V02 + 1 '
dk'
(6.16)
dk' I
= -1 d8 = Ttrans
t
x = 0 at t .
Vg k'=k
Thus
(6.17)
v (X)
Thus
B _ -2mValli 2 -kcotka-ik _ ('C)
R - - 2 - - exp lor ,
A 2m Valli + k cot ka - ik
Free Particles Incident on Potentials, ... 79
(6.20)
One notes IRI2 = 1. In fact B I A in this case is both the reflection amplitude and
the transmission amplitude since there is no transmission beyond x = O.
The allowed negative energies satisfy the equation:
2mVo .
-,;r + k cot ka = zk. (6.21)
Defining
2a { csc2 ka } 2a
7 ref -+ Vg 1 + cot 2 ka = Vg ,
where jz, nl are the usual spherical Bessel and Neumann functions and DI( k) is the
"phase shift" for a particular "wave" or angular momentum I component of the wave
function.
In terms of these phase shifts a standard derivation 1 shows the scattering am-
plitude, the three-dimensional analogue of the transmission amplitude in Eq. (6.3)
IS:
1
k:L
00
fk(O) = eiSz(k)sinDI(k)PI(cosO), (6.23)
1=0
80 Chapter 6
while the (scattering) cross section
a(k) (6.24)
z=o
As in the one-dimensional case, for a given potential, the poles (for each I) in the
scattering amplitude it gives rise to determine its allowed negative energies (for the
corresponding angular momentum).
The phase shifts Ez(k) may be obtained exactly, by requiring that the wave function
(and its derivative, if V has no infinite discontinuities) in the region where there is
a potential, match smoothly onto the external wave function Eq. (6.22) (and its
derivative) at r = a, where a is the "range" of the potential.
Alternatively at high incident particle energies, or for weak potentials one may
have recourse to the partial-wave Born approximation:
or else use the (first) Born approximation, which for central (l independent) potentials
reduces to
iB(k') = - :~ roo
sinkk'r' V(r')r,2 dr " (6.26)
n Jo 'r'
(with k' = 2ksin(}/2), where the differential cross section is:
:~ = If(k'W, (6.27)
EXAMPLE 6.3
Consider a particle scattered off the three-dimensional potential
Ao 2mVo .
--,,- cos (ka
oos~
+ 80 ) - Bo cos ka =- k
~
2 Bo sm ka. (6.30)
2mVo
cot (ka + 80 ) - cot ka = k~2 ,
I.e.
~2k )
cot 80 =- ( cot ka + 2m Vo csc 2 ka
V( r )
a
~---+-------------r
or
sin80 (k) = _ 1 ,
(esc ka h/1 + 2A oot ka + A2 csc2 ka
where
82 Cbapter 6
The 1=0 contribution to the scattering amplitude (cf. Eq. (6.23) ) is
kh? ) 2
1+2 +(
k'h,2 )
( 2mVo cotka 2mVo csc2 ka = 0,
i.e. when
k1i2
( 1 + 2m Vo cot ka
)2 = - (2mkfi2Vo )2 '
which is in agreement with the result of Eq. (6.21), as it must be.
For higher l's different (additional) bound states result. The I = 0 contribution
to the scattering cross section is:
O'(k) = 47r
(P csc 2 ka) { 1 + (k1i 21m Vo) cot ka + (k1i2 12m Vo f csc ka}
2
If a ---t 0 sin60 (k) ---t -2mVoka 211i2 ---t 0, and with it the 1= 0 contribu-
tion to the scattering amplitude fk(O) and the cross section O'(k) which goes to
47ra 2 (2mVoalfi2r ---t O.
From the expression above for sin60 (k) one notes that 60 (k) depends on the sign
of Vo. Moreover, if k is large, i.e. A is large (where A = {h2k} I {2mVo}), then
1
sin 60 ( k) '" --::----:----:-- = (6.31)
csc ka A csc ka
while the partial-wave Born approximation I = 0 phase shift may be easily evaluated:
As a-+O, (da)/(df!) -+ {(m2V02a2){2ak sin (61 /2))2} / {1i4k2 sin2(61 /2)} -+ (2m Voa 2/1i 2f
with a(k) -+ 41l' (2mVoa 2/1i2f, in agreement with the partial-wave results.
EXAMPLE 6.4
Consider a particle scattered off the three-dimensional potential:
For
0< r < a, uo(r) is the solution of the equation:
1i2 J2 21i2 }
{ - 2m dr2 + 2mr2 - E uo(r) = O. (6.32)
The solution of Eq. (6.32) which does not diverge at the origin is Borjl(kr).
V( r )
,
,
,
______-+____________ ~ __ ~ __ r
a
Hence one can easily find the 1 = 0 phase shift for this system by requiring
continuity of the wave function and its derivative at r = a :
84 Chapter 6
Thus
where
. () sin p cos p
Jt P = - - - - - ,
p2 P
I.e.
80 ( k) = arccot [: In {pjt (PH]
P
I - ka.
p=ka
If a is very small (i.e. the potential has a very short range) or k (i.e. the energy)
is small such that the product ka is small,
In the Born approximation the total differential cross section for this potential
may be obtained by first evaluating the scattering amplitude:
If one allows a - t 00 this integral can be performed analytically and one may
write:
Free Particles Incident on Potentials, ... 85
The cross section in this case (a ~ 00) for scatttering between () = ()1 and () = ()2
1S
71"2 r02 sin () d() ~ 271" r02 2 sin (() /2) cos (() /2) 2d( () /2)
4k2 271" }01 sin 2 (() /2) = 4k 2 }01 sin 2 (()/2)
EXAMPLE 6.5
Consider a particle scattered off the potential:
V( r )
101 -ivol
Figure 6.5: Potential in Example 6.5.
where
2m
K= -,;: {E + lVol} ,
and the potential V = -lVol has a range 0::::; r ::::; a.
At low energy
=
_ 2m
'h
2
la
0
sin (k'r') {
k'r'
-
Ill,0 I + -21 mw 2,2
r
} ,2 d ,
r r
For small k
EXAMPLE 6.6
Evaluate the differential and total scattering cross section for the potential:
V( r)
V(r) = Voexp (-2r22 ) ,
a
- Va
-2m
li 2
- 1
0
00
sin k'r'
---exp
k'r'
- - r ,2 dr '
(r'2)
2a 2
= _ m Vo
2h 2 k'
lr
'=oo
r'=-oo
sin k'r' exp (_~) d {rI2}
2a 2
= _ mVo
211,2 k'
Iml r
'=oo
r'=-oo
eXP{ik'r' _ ~}d{r'2}
2a2
=
mVo (k,2 a 2 ) T
'=oo
- 2h2k' exp --2- 1m r'=-oo exp - 2az
I
((r' - ik'a 2)2)
dr.
{,2}
Defining u == r' - ik'a 2 , r' = u + ik'a 2, dr' = du, dr'z = 2 (u + ik'aZ ) duo
With this substitution:
fB(k')
I.e.
.,fiii m Vaa 3 exp (-k'2 a 2 /2)
fB(k') = liz (6.36)
O'(k)
Thus
Free Particles Incident on Potentials, ... 89
O"{k) =
(6.37)
a result independent of the sign of Va. This problem may also be solved using Cartesian
coordinates.
EXAMPLE 6.7
Using the partial-wave Born approximation find the S-wave (I = 0) phase shift if
a particle is scattered off the potential of Example 6.6, namely:
-2 Vo
-2m -
1i k
1 2kr (r22a ) dr
0
00
sm
•
exp - -
2
- - - 1 {l-
mVa r2) dr
00
cos2kr}exp ( - -
1i k
2 0 2a 2
(6.38)
_ mVo [ roo exp (_~) dr _ Re roo exp {2ikr - ~} dr]
1i k
2 Jo 2a 2 Jo 2a
2
1i2kVa V'2
- ma -2 a 2)} .
{if" { 1 - exp (k2
Do(k) ""' - maVa f!.. 2k2a2 and fk ""' Do(k) = _ ma3Va .J2; .
1i 2 k V'2' k 1i2
Correspondingly if only 1=0 contributes to the cross section, using Eq. (6.24):
90 Chapter 6
which agrees with the result Eq. (6.37) of Example 6.6, in the limit k -+ o.
Analogously the approximate scattering amplitude obtained above, namely
ma3 Vo
+k '"
J. ---.j'2;
1i,2 ,
is consistent with the Born approximation result Eq. (6.36) if ka <t:: 1 since in this
limit one can write for Eq. (6.36):
...& mVoa3
1i,2
EXAMPLE 6.8
Find the Born-approximation scattering amplitude if a particle is scattered off
the potential:
V( r )
r
0[2
Figure 6.7: Potential in Examples 6.8, 6.9.
Defining u == r' - ik'a2 , and taking the imaginary part of this integral yields:
m v;0 k ,2 a
---exp ( - - -
2) 00 , 2 2 ,3 6
{{3ka u - k a }exp - -
( U 2·) du
~~~ 2 h 2~
fB(k') (6.39)
EXAMPLE 6.9
Using the partial-wave Born approximation find the S-wave (1 = 0) phase shift if
a particle is scattered off the potential in Example 6.8, namely:
Var2
V(r) = 2a 2 exp - 2a 2
(r2 ) •
x 2ika2)2) ~ d(_r )}
{...fi4 _exp (-2k 2a2)Reh{OOexp (_ (r - ~ ~ ~a
21i 2Va
= - ma {if { 1 -
k V'2 ( 1 - 4k 2a 2) exp (-2k2a 2)} . (6.41 )
92 Chapter 6
If ka <: 1
and
EXAMPLE 6.10
Evaluate the differential and total scattering cross section for the potential:
v; r
V(r) = _o_exp (r2
- -)
,j2 a 2a 2
-
2 mvo
TT
,j2 an?
1° 00' sm k" r , r
- - - r exp - -
k'r'
(,2 ) r
2a 2
,2 d
r
'
- 2mVo
,j2 ak'n?
1m 1°
00
e x{'k"
pzr--
2a 2
r,2} r ,2dr ,
- 2mVo exp (k,2
,j2 ak'1i 2
- --a2) 1m
2
1° 00
exp ( - - 1 {r' - zk
2a 2
.,a 2}2)'r2 dr.,
Defining u == r' - ik' a2 , r' = u + ik'a 2 , r,2 = u 2 + 2ik'a 2u - k,2 a4 •
With this substitution:
h(k')
EXAMPLE 6.11
In the preceding problem,
V(r) =
v; r
a~exp
(r2
- 2a
) 2
evaluate the S-wave phase shift using the partial-wave Born approximation.
~~:k 10 00
{1- cos (2kr)} exp ( - ;;2) (;;2)
d
-1/2 V{r)
Vo e " ~--
<l $0
Figure 6.8: Potential in Examples 6.10, 6.11.
94 Chapter 6
EXAMPLE 6.12
Evaluate IB(k') if V(r) = Vornexp(-ar).
- Vo
-2m -
fi?
10
00 sin (k'r') r In exp ( -ar') r ,2 dr ,
k'r'
-2mVo
- - Im
ti 2 k'
1 0
00
t r , - ar ') r m+1d'
exp (·k' r
2mVo Im(
--2-
tik'
1.k) +2
a-z'n
10
00
exp ( -u ) u n+l du
2mVo(n + I)! .
ti2k'(a 2 + k,2)Hn/2 1m exp {z,B(n + 2)} where ,B == arctan (~)
2 2mVo(n
( +2)I)! / sm
. [(n+2)arctan (k')
-
]
ti k' a 2 + k' Hn 2 a
Special cases of interest include: (i) n = 0 i.e. one has a Yukawa potential
V(r) = Voexp(-ar).
In this case
EXAMPLE 6.13
Find the reflection time for a particle incident with energy E on a step barrier:
0, x < 0,
V(x) = {
Vo, x > ° (Vo > 0, Vo > E).
Free Particles Incident on Potentials, ... 95
For x <0
'IjJ(x) = Aexp (ikx) + Bexp (-ikx);
while for x >0
'IjJ(x) = Cexp(-'I}x),
where
k = J2;2E, 'I}(k) = J2m (~2 - E) = J2~;o - k2 .
Matching boundary conditions at x = 0 one obtains:
B = A [k - ~'I}] .
k + ~'I}
Constructing wavepackets:
j A(k,)k'-i'l}(k') [-'{k'
k' + i'l}(k') exp ~
E(k')t}]
x + -n,
dk'
where
hk
Vg =- .
m
EXAMPLE 6.14
Consider the two-step barrier:
V(x) = !0,
Vo,
VI,
x < 0,
0<x <
x> a.
a,
A particle is incident on this barrier from the left with energy E. Assume E >
Va, E> VI (See Figure 6.9.) Find for what values of a the transmission is a minimum
and for what values of a it is a maximum.
V (x) V( x)
---+-----'---t----x
d a
Thus
But
and
Tmin - v~ ~{ 4 }
(1 + V{E -
2 ,
max E Vi} IE) + {Vo(Vo - Vi)} / {E(E - Vo)}
where the upper value is for Va > Vi and the lower value for Vo < Vi .
This example shows that the condition kl a = mr does not necessarily yield max-
imum transmission. This is the case if Va > Vi. The opposite is the case if Va < Vi.
In this case the transmission is a maximum if kl a = ({2n + I} /2) 7r.
98 Chapter 6
EXAMPLE 6.15
Consider a particle scattered off two identical delta-function potentials, namely:
1
-00
Hence, defining
_ m/vol
1I=~,
A+B C+D
Cexp(2ika)-Dexp(-2ika) = F(1-2ill),
which imply
A (1 - ill)C - illD
mlVoI
// = --:=-U:. "
1i 2 i",
Eq. (6.44) then reduces to the equation for the allowed bound states
2f -1
tanh2",a= 1 - 2 f + 2 f 2 '
-0 0
------.-----~----_T----------. X
Eq. (6.45) corresponds to even-parity bound states while Eq. (6.46) to odd-parity
bound states.
If a -+ 0 Eq. (6.46) has no solution, while Eq. (6.45) has only one solution,
namely
i.e. x = a at t = 2a/vg which as expected is the classical transit time for crossing
these two potentials.
Free Particles Incident on Potentials, ... 101
References
Heisenberg Representation
Starting with the expression for the expectation value of an operator Os in the
Schrodinger representation (at some time t) :
G(x,x',t) = 1 001
--exp
V2i
- 00
(iP'X') 1
- - - --exp
fi V2i
(iP'X)
-
fi
exp (iE(P')t)
- - - - d (p,)
fi
-
fi
whereas for a particle in a potential (which is assumed time-independent) (7.3)
G(x,x',t) = f<p:(x')<pn(x)exp(-i~nt),
n=O
G(x, x', t) = 1 00
-00
_1 exp (_ iP'X') exp (_ iH(X)t) _1 exp (iP'x)d (p,)
V2i fi fi V2i fi fi
fi - 00 V2i
1
exp (_ H(X)t) 00 _1 exp (_ iP'X')_l exp (iP'x)d (p,)
fi V2i fi fi
iH(X)t)c(
exp ( ---fi- U x - x
') ,
iH(X)t)
G(x,x',t) = ~<p:(x')exp ( - - iH(X)t)
f i - <Pn(x) =exp ( - - f i - 8(x-x'),
Heisenberg Representation 103
(d. Eq. (2.6) ), i.e. generally
iH(X)t)
\II (x, t) = exp ( - - h - \II (x, 0). (7.5)
(O)t = 100
-00 \II * (x,O)exp (iH(X)t)
- h - Osexp ( - iH(X)t)
- h - \II(x,O) dx, (7.6)
I.e.
(7.7)
where
OH -= exp (iH(X)t)
- h - 0 s exp (iH(X)t)
--h- (7.8)
and the subscripts Sand H stand for the operator in the Schrodinger and Heisenberg
representations respectively.
In Eq. (7.7) one thus has simpler wave functions than in Eq. (7.1) i.e. only
\II(x,O), independent of the time, but more complicated operators OH rather than
Os.
The operator OH can be seen to satisfy the differential equation:
(7.9)
SInce
dOH
- i
- = -exp (iHt)
- (HO s - OsH)exp (iHt)
- - +exp (iHt)
- aDs
- - exp (iHt)
--
dt h h h hat h'
and where
-
HH-exp (iHs(x)t)H
h sexp (iHs(X)t)
- h -- H s·
104 Chapter 7
If 0 = x or P and H =p 2 /2m+ V(x),
then
dXH i PH
Tt=r;{HH,XH}= m' (7.10)
dPH i aVH
Tt = h {HH' PH} = - ax = FH , (7.11)
(7.12)
The standard Heisenberg representation results Eqs. (7.10) - (7.12) look exactly
like the corresponding classical expressions for velocity and force. In fact Eq. (7.12)
looks just like Newton's second law. This analogy has formal merit.
A word of caution is however in order here. Both PH and XH are quantum-mechanical
operators and are more complicated than their classical analogues. Thus
h
Rather since {XH,PH} = ,
z
h
XHPH = PHXH - -;- .
z
(7.14)
EXAMPLE 7.1
Show that generally
d(OH)2 = ~ {H (0
dt h H, H
)2}
and
Hence
. .
d0 2 z z
-.!L
dt
1i {HH, OH} OH + Ow:;;, {HH' OH}
dOH 0 0 dOH
T t H+ HTt
l.e.
(7.15)
EXAMPLE 7.2
Show
d(X2)H = d(XH)2 = 2x dXH ~
dt dt H dt + mi .
From Eq. (7.15)
1-00
00 w*(
x,
0) dOH W( 0) d = / dOH)
dt x, x \ dt t
d (O)t =
dt
EXAMPLE 7.3
Evaluate
d () d /1 d]OO *( ) 1
dt VH t = dt \2'mw XH t = dt -00 w x,O 2'mw xH W x,O dx,
2 2) 2 2 ( )
1
Vex) = 2'mw 22 1
x, i.e. where VH (x) = 2'mw 22
XH .
i: ¢~(X)XHPH¢O(X) i: ¢~(x)
But
dx = x [~!] ¢o(x) dx
= -in,]00 * mwx
-00 ¢o(x)x-n,-¢o(x) dx
2
--;-
]00 mw 2 x 2
¢~(x)-2-¢o(x) dx
zw -00
n,
etc.
Hence
(d;; ) t = - i~ + i~ = 0,
and the expectation value of the kinetic energy of the ground (and by a similar
calculation of any) state of a simple harmonic oscillator is independent of t.
EXAMPLE 7.4
Generalize the result of Example 7.3 for any state of the simple harmonic oscilla-
tor.
Defining
±=
aH - ~ 1 [p H ±.zmwxH, 1
v2m
one can quickly show, using Eq. (7.13) that {a1f, all} = -nw, and that
Thus
jdX'k)
\ dt t
-.zmw1_1
-00
00
4>~(x) [(at)2 - (alif - nw] 4>n(X) dx +~
mz
h h
= --. +-. =0,
mz mz
since (allY operating on 4>n(x) produce states orthogonal to 4>n(x). For non-diagonal
matrix elements (i.e. min), it may happen that (d/dt) (nl mw 2x'k/2Im}t i 0
(d. Example 7.7).
EXAMPLE 7.5
Show
dTH _ PHFH _1_ {F }
dt - m + 2m H, PH . (7.17)
where TH is the kinetic-energy operator in the Heisenberg representation.
108 Chapter 7
From Eq. (7.15)
Therefore:
dp2
d: = 2PHFH + {FH, PH},
or
dTH _ PHFH _l_{F }
dt - m + 2m H, PH .
Thus for example if VH = mw2x~/2,
-dPH
dt
aVH
= ---
ax
= FH = -mw 2 XH ,
and
EXAMPLE 7.6
Evaluate
d
dt (x}t
for a particle in the ground state of a simple harmonic oscillator potential:
d{x}t
dt
= (dXH)
dt
= i{{H
Ii
})
H, X H t·
t
EXAMPLE 7.7
Evaluate
d \2
dt 11 2 21) t =
/ 2'mw xH 0 d
dt 1 4>2
00
-00
1 2
*( x ) 2'mw 2
xH4>o ()
x dx,
where <Po{x), <P2{X) are the ground and second excited states of the simple harmonic
oscillator:
1
VH{X) = 2'rnw XH .
2 2
One notes, using the results of Examples 7.3-4 and the fact <Po{x), <P2{X) are or-
thonormal, that
EXAMPLE 7.8
Evaluate
d
dt (TH}t
for a particle in the ground state of a simple harmonic oscillator potential:
mwx2)
W(x,O) = 4>o(x) = Nexp ( -'ih '
= _w 2 1 4>~(X)pHXH4>O(x)dx + 2i
00
-00
'hw2
= _w 2 1 00 'ha x4>o(x)dx +
4>~(X)-:--a
'hw 2
-2.
+ -. 1
-00 Z x Z
nw21°O 2w mw 2x 2 'hw2
+ -2.
00
= --.- 4>~(x)4>o(x)dx 4>~(X)-2-4>0(x)dx
Z -00 Z -00 Z
P'i:,
H H = 2m 1
+ '2mw xH = TH + TJ'
2 2
vH, an d 'T,(
'I" x,
0) = '1'0 X.
A.. ( )
Thus the expectation value of this Hamiltonian does not change with time. This
is not surprising since H does not depend explicitly on time and generally using
Ehrenfest's expression:
What is more surprising is that (TH}t and (VH}t do not change with time. This
is because one is evaluating the time evolution of the expectation or "average" value
of these operators, not of the operators themselves.
CHAPTER 8
(8.1)
where
L: l1l!n(xWdx = l.
The radial equation for a particle in a three-dimensional radial potential Vj(r) is
(8.2)
where
Unl(r) I
1 = 0, 1, 2, ... , 1l!nlm(r, (), 4» = - - Ym«(),4», -I ~ m ~ I,
r
1 unl(r?dr
and
00
= l.
If 1 = 0 and Vi(x) = Vj(x) Eqs. (8.1) and (8.2) are identical. However,1l!n(x)
in Eq. (8.1) extends from -00 ~ x ~ 00 while Unl(r) must be zero at r = 0 in order
that Unl(r)Jr be finite at the origin. In addition Unl(r) extends only from r = 0 to
r = 00. A consequence of the above is that some solutions acceptable for Eq. (8.1)
are not acceptable for Eq. (8.2). Radial solutions of Eq. (8.2) with potential Vj(r)
are identical to solutions of the one-dimensional problem Eq. (8.1) if:
If
V,()-¥() h2 1(l+1) x> 0,
lX-3 X + 2mx 2 '
and moreover Vi(x) = Vi(-x) then the odd-parity solutions (i.e. those solutions
which vanish at x=O) of 1l!n(x) (n = 1, 3, 5 ... ) are identical to Unll(X)J...ti (n' =
0, 1, 2, ... ,1 = 0, 1,2, ... ).
112 Chapter 8
EXAMPLE 8.1
Consider the potential Vi. (x) = (h 2 /2mb4 )x 2 • For this potential the solutions ofEq.
(8.1) for the energy En are En = (n+ 1/2)h 2 /mb2 (n = 0, 1,2 ... ). The lowest energy is
;,,2 /2mb2 and the ground-state wave function wo(x) = {l/(bJ"i )} 1/2 exp (_x 2 /2b 2).
Consider now the potential ¥J(r) = (;,,2 /2mb 4 )r2 , and the case 1 = O. The min-
imum energy Eoo for a particle in this potential is 31i? /2mb 2 • Examine why this is
so.
The three-dimensional radial function uoo(r) cannot be proportional to (the even
function) Wo(r) since wo(x) does not vanish at x = o. The second energy eigenvalue
for the one-dimensional problem is E1 = 3h 2 /2mb2 , with (odd) eigenfunction
2
WI (x) = ( b.ji
)1/2 (i) exp (2 )
-;b2 .
This is acceptable as the lowest eigenfunction of Eq. (8.2) (to within an overall factor)
since WI(O) = o. The normalization must be modified however since:
while
Thus
uoo(r) = (bV: (7;)
)1/2 exp (-;~).
Similarly all odd-parity solutions W3(X), ws(x) are acceptable (see Example 10.3)
solutions since for these solutions W(O) = o. Thus
etc. and
E(n-1)/2,o = (n + 2"1) mbh 2 '
2
n = 1, 3, 5 ... ,
i.e.
EXAMPLE 8.2
Consider a particle in the three-dimensional well:
0, 0< r < a,
V3 (r) = -IVoI, a < r < b,
0, b < r < 00.
Two-, Three-, and N-, Versus One-Dimensional Problems 113
Compare this and the analogous one-dimensional system:
0, x < a,
Vt(x) = -IVoI, a < x < b,
0, b < x < 00.
V( r) V( X)
J
~-----aT-----~~b----~r --+------a~-----r.b----~-x
These results can be compared with the energy levels for a particle in the one-
dimensional well given in this example. The solutions of Eq. (8.1) for this potential
are
Aexp (klxl), x < a,
\li'(x) = Bsin(Kx + 15), a < x < b,
Cexp (-kx), x> b.
Matching boundary conditions one obtains
1 tan(Ka + 6)
"k= K (8.7)
tan(Kb+h) 1
K --"k' (8.8)
One can rewrite Eq. (8.8) as
Thus the energy levels for this system are obtained by solving the transcendental
equation
K K/k + tanK(b - a)
(8.9)
- k = 1 - (K j k) tan K (b - a) .
Two-, Three-, and N-, Versus One-Dimensional Problems 115
a -+ 00
c == b-a
b -+ 00
where c is a constant, in which case the boundary condition at the origin is unimpor-
tant.
(8.10)
where
and
Here wnm(p) must be zero at p = 0 so that wnm(p) will be finite at the origin.
vp
Comparing Eqs. (8.2) and (8.10) and noting that
indicates that if one has a solution Unl(r) of Eq. (8.2), then wnm(p) is Unm -l/2(P).
One notes both u(O) and w(O) must be zero, as too u(oo), and w(oo), (if the particle
is bound) i.e. u(r) and w(p) have identical boundary conditions.
EXAMPLE 8.3
Suppose one has a particle of mass M in a two-dimensional Coulomb potential
well:
Ze 2
V2(p) = --4- .
'!rEoP
Find the corresponding negative energies and wave functions.
116 Chapter 8
Since, as standard texts report, for the three-dimensional well
Ze 2
Va(r) = --47rEor
- ,
(8.12)
1Ft (-n +m + ~i2m+ 1;2Kp) ,
where
Enm =
Z 2 a 2 Me 2
2n 2
K = ZMea,
nn n = 2"
1 3 1
2' ... , m = 0, 1, ...n - 2' .
Here n must be a positive half-integer so that -n + m + 1/2 is a negative integer
or zero, making 1Ft a terminating series. Otherwise wnm{p) blows up as p - 00.
Thus
, ....
9
EXAMPLE 8.4
Suppose one has a particle of mass M in a two-dimensional oscillator well:
1
V;(p) = 2'MW 2p2.
Find the corresponding energies and wave functions.
Since, as standard texts report, for the three-dimensional well:
1
Va ()
2 2
r = 2'Mw r ,
wnm(p}-
_ {2 (n + m)!
b2 n.I
}1/2 pm+1/2 exp
bm
(_p2 /2b 2)
I IFI
(_. . p2)
n,m+1'b2'
m.
(8.14)
EXAMPLE 8.5
Suppose one has a particle of mass M in a two-dimensional well:
0, 0 < p < a,
V=
00, a < p < 00.
Solve this problem.
To find the eigenvalues and eigenfunctions of this system one notes that for the
analogous three-dimensional case the standard result involves spherical Bessel and
spherical harmonic functions:
where k= J2ME
'li 2 '
with allowed energies corresponding to values of k such that jl(ka) = O.
For the two-dimensional case therefore
Wnm(p,</J) = CnJn(kp)exp(±im</J},
with allowed energies when the cylindrical Bessel function In(ka) = O.
118 Chapter 8
EXAMPLE 8.6
Treat the finite square-well system in two dimensions:
2m (IVoI-IEI)
K= 1i,2
By analogy
But
Therefore
Matching the wave functions and derivatives at p = a gives one the appropriate
quantization condition for the energy.
The less frequently encountered, but all the same interesting, N-dimensional prob-
lem (N > 3) of a particle of mass m in a potential VN(r), which is a function only of
the radial distance
2
r = ( Xl + X 22 + X32 + ... X N2 )1/2 ,
(or of N one-dimensional particles in such a potential) can also be written l in a form
similar to Eq. (8.2), namely:
(8.15)
Two-, Tbree-, and N-, Versus One-Dimensional Problems 119
where
w(T)
cPnl(r)
= r(N_l)/2S1m e,
( )
Slm(e) are polynomials of degree 1 in e, and the index m runs over the set of values
A(N, I), where
1000
cP!l(r)dr = 1. (8.16)
One notes that Eq. (8.15) reduces to Eqs. (8.1), (8.10) and (8.2) if N = 1, 2 and
3 respectively.
EXAMPLE 8.7
Suppose one has a particle of mass M in an N-dimensional Coulomb potential
well:
Ze 2
1;2(p) = --4-' { r = ( Xl2 + X 22 + X32 + ... XN
2 )1/2} •
1rfor
Find the corresponding wave function and energy levels.
Making a direct comparison of Eqs. (8.2), and (8.15) enables one to generalize
Eq. (8.11) (by making everywhere the identification 1-+ 1+ N/2 - 3/2):
where
K= ZMca, e2
0:=--,
nn 41rfonc
n = N/2 -1/2, N/2 + 1/2 ... , 1 = 0, 1, ... n - N/2 + 1/2.
Here increasing the dimension N by two units is equivalent to increasing 1 by one
unit in the wave function but not in the expression for the energy. As N increases
the minimum energy increases since
120 Chapter 8
EXAMPLE 8.8
Solve the N-dimensional Schrodinger equation for a particle of mass m subject to
a potential
1
V3 (r) = 2mw2r2.
Here one generalizes Eq. (8.13) (with the identification 1--+ 1 + N/2 - 3/2):
2r(n+Z+N/2)}1/2rl+N/2-1/2eXp(_r2/2b2) ( N r2)
tPnl(r) = { b3n! lJ+N/2-3/2r (1 + N/2) IFI -n; 1+ "2; b2 '
(8.18)
One notes here that as N increases the minimum energy increases since
It is clear that the results in Examples 8.7 and 8.8 are consistent with the N =2,
3 results in Examples 8.3, 8.4. Increasing N effectively pushes the particle away
from the origin since it increases the numerator of the positive I/r 2 term on the
l.h.s. of Eq. (8.15). Finally one also notes that whereas the level spacing of the
N-dimensional harmonic oscillator in Example 8.8 is nw independent of N, the level
scheme for the N-dimensional Coulomb potential is more involved. In particular the
spacing between the ground and first excited state is :
EXAMPLE 8.9
Suppose a particle of mass M, and energy E, is in an N-dimensional potential:
0, 0 < r < a,
V=
00, a < r < 00.
Solve this problem.
Two-, Three-, and N-, Versus One-Dimensional Problems 121
By analogy with Example 8.5 one has
EXAMPLE 8.10
Treat the finite square-well system in N dimensions by analogy with the standard
three-dmensional results given in Example 8.6.
By analogy with the results in Example 8.6 one obtains:
0< r < a,
(8.20)
I+N/2-3/2 (·k)S
B Ir3!2-N/2h(1)~· (t) ,
trim." a < r < 00.
where
K=
Matching 111, 111' at r = a gives the quantization condition on the energy, while
the normalization condition:
gives a further relation between At. and B l , hence one can also obtain the wave
function exactly with no undetermined parameters.
122 Chapter 8
EXAMPLE 8.11
Consider a particle in the potential well:
VCr) = -IVoI, 0< r < a,
fi2['(l' + N - 2)
2mr2
r > a, (8.21)
h
were r = ( Xl2 + X 22 + X32 + "'XN
2 )1/2
•
Find the allowed energies assuming E < 0 and that [ = O.
V( r)
----~r-----~~a----------------------~-- r
-Ivol
Figure 8.2: Potential in Example 8.11
For the standard three-dimensional case,
Windr) = Ajo{I<r)Yo°{O, ¢), 0 < r < a,
Wext.(r) = Bh}!){ikr)lt{O, ¢), r > a,
References
d? {2m
dr2 unl(r) = fi2(V(r) - E) + 1(l+1)}
r2 unl(r), (9.1)
with boundary conditions that Unl(O) = 0 and unl(r) ---+ 0 as r ---+ 00.
Assuming Unl (r) is a real function one can readily show, integrating by parts
(where all integrals are from r = 0 to r = 00), that given a constant k,
(provided rku~l(r) ---+ 0 both when r ---+ 0, and when r ---+ 00), while
JdUnl(r)
dr r
10 dUnl(r) d
dr r
-
-
k(k -1) (10-2)
2 r -
JUnl ()r r10 d?unl(r)
dr2
d
r
__ 2_
k +1
JdUnl(r)
dr
rkH d2u l(r) dr
dr2'
n
Substituting Eq. (9.1) into Eq. (9.3) and using Eq. (9.2) one obtains after
regrouping terms:
If one studies in detail the restrictions under which Eq. (9.4) is valid, it is obviously
not valid if the constant k = -1. The constant k need not however be an integer.
If k = 0, Eq. (9.4) reduces to:
E=p+2(V(r)}. (9.5)
2
But E = (H) = (T) + (V). Thus for any quantum-mechanical state Inl} of H,
If k = 1,
2m(p+ 6)
(where l' = 1 since VCr) is a central potential) with similar expressions for higher
moments.
The above equations apply equally well to one-dimensional problems. For such
problems unl(r) becomes 'l/JN(X), the complete eigenfunction for the problem in ques-
tion, while 1must be set equal to zero. That 'l/JN( x) has different boundary conditions,
namely 'l/JN(X) ---+ 0, as x ---+ ± 00, merely implies the limits in the various integrals
are x from -00 to 00 in the one-dimensional case, rather than r from 0 to 00, and
that the conditions are for instance:
Thus:
EXAMPLE 9.1
Consider the one-dimensional harmonic oscillator: Vex) = mw 2x 2/2, (i.e. p = 2)
where EN = {N + 1/2} 1iw.
Obtain expectation values of various powers of x.
With the above substitutions in Eq. (9.12) one obtains:
(9.13)
V{r) =
Q1l,e
r
En = 1
--Q
2
2
me-
n2
2 1 ( where Q
e2
= - - '" -
41rE{)1l,e
1)
137 '
and
1
V(r) = _mw 2r2,
2
En! = (2n + 1+ 3/2)1l,w,
obtain recursion relations.
Substituting into Eq. (9.4) one gets for the first of these potentials, V(r) = Qnc/r,
Kramers' well-known formula:
EXAMPLE 9.4
Show that if
Ax4 x> 0,
V(x) = { '
00, x < 0,
then
(nlxV(x)ln) = 1.5 (nlV{x)ln) (nlxln).
In this case °
< x < 00 in the integrals of Eq. (9.12) though this is a one-
dimensional problem.
Using Eq. (9.12) with k = 1,
p+4
-2- (xV(x)} = 2E (x).
128 Chapter 9
But from Eq. (9.5) E = {(p + 2)/2} {V}, (whether the system is one or three
dimensional);
therefore
If p = 4,
(xV(x)} = 1.5 (V(x)} (x).
EXAMPLE 9.5
Given the potential:
V(x) = ax\
show that:
(9.18)
Substituting directly into Eq. (9.10), with p = 4, 1=0,
31i 2
(r2V(r)) = 1.8 (r2) (V(r)} + 20m'
The same result applies to the one-dimensional case with r -+ x.
If V{x) = ax 4 for all x, the integrals extend over all x.
If
ax4 x> 0,
V(x) = { '
00, x < 0,
the integrals extend over x 2:: 0.
EXAMPLE 9.6
Given
ax, x> 0,
V(x) ={
00, x < 0,
show that:
9 31i 2
= "7 (nlx2In) (nix In} + 14ma . (9.20)
'Kramers' Type Expressions, Tbe Virial Tbeorem, ... 129
Substituting the value p = 1 in Eq. (9.17) ,
6
5' (ax) {x},
(xax) =
which yields Eq. (9.19), while substituting p = 1, I = 0, r -+ x in Eq. (9.10) one
obtains:
EXAMPLE 9.7
If V(x) = alxl, show that:
lo
oo 18100 4>n(x)x 4>n(x) dx 100 <Pn(x)x<Pn(x) dx + -
4>n(x)x 3 4>n(X) dx = -7
0
2
0
31i- .
28am
2
(9.21 )
Substituting p = 1, I = 0 in Eq. (9.10), and taking into account that <Pn(X)2 =
4>;,(-x) since <Pn(X) has a definite parity (because V(x) = V(-x) in this case), one
immediately obtains Eq. (9.21).
EXAMPLE 9.8
Obtain expressions for Xrms = J{Nlx2IN) , if p = 1, 2, i.e. V(x) = A1x, or
V(x) = A2X 2.
If p = 1, one has from Eq. (9.17):
#s ! .
Therefore
xrms = (9.22)
( Nlx2IN) = ~ (N +~)
mw 2
= _2
mw 2 2
nw (N +~)
2
E
2 (mw 2 /2) .
Therefore
(9.23)
130
Chapter 9
where (NlxIN ) = 0 for both of the above potenti als.
(9.25)
if p = 1,
and
(9.26)
if p= -l.
Substit uting k = -3/2 into Eq. (9.4) yields Eq. (9.25), while the
substit ution of
k = -1/2 into Eq. (9.4) yields Eq. (9.26). Both these results are
indepe ndent of A.
EXAM PLE 9.12
Obtain the two-dimensional analogu e of Eq. (9.4).
From the results of Chapte r 8 one makes the identifi cations m
-+ M (for the
mass), r -+ p, and 1 -+ m - 1/2. The result is:
Ifk=O
E= P;2 (V(p)) ,
'Kramers' Type Expressions, The Viria] Theorem, ... 131
while if k = 1
E = (p + 4) (pV(p») + -n? (m 2 - 1/4) (p-I) /M .
4 (p)
EXAMPLE 9.13
Obtain Kramers' relation for
k (k2 - 4m 2) / k-2)
4(k+1) \p
_ M 2w2 {k +
li 2 k+1
2} \p/ k+2)
(9.28)
+
2Mw(2n+m+1) /
Ii \p
k)-O
- .
With k = 0:
(9.29)
while if k =2:
(9.30)
etc.
EXAMPLE 9.14
Obtain the analogue of Eq. (9.4) if
(9.31 )
The interesting and useful thing here is that using Kramers' techniques one obtains
the values of, or relations between various matrix elements, not only without having
to evaluate these matrix elements, but without even having to obtain the associated
wave functions.
References
(10.1)
If .,pt( a, (3, ... ) is a normalized 'trial' wave function with parameters a, (3, ... , one
can define the integral
Since the Wn's constitute a complete set one can expand .,pt(a, (3, ... ) in terms of
the Wn's in Eq. (10.1) which are assumed normalized in what follows. Thus
00
(10.4)
n=O
EXAMPLE 10.1
Consider the system H = T +V where
V X> 0,
(10.6)
00, x < o.
The exact ground-state wave function for this system and the corresponding ground-
state energy are in fact known:
( 1 ) 1/2 2x (X2 )
b.,fo b exp - 2b2 '
(10.7)
n,2
Eground exact = v'2.25 mb2 •
--------------~----------------~--x
(20'.)2n+1
'if;t= xn exp (-O'.x),
~-..:.....,-:--
(2n)!
The condition
oE O. l' 4 (4n2-1)(n+1)
ocr = Imp Ies cr = 2b4 '
EXAMPLE 10.2
Consider the system H = T + V where
Ax, x> 0, (A> 0)
Vex) = {
00, x < O.
V( x)
--------------~-------------------x
Figure 10.2: Potential in Example 10.2.
136 Chapter 10
This yields
(2a)2n+I n
(2n)! x exp(-ax)
= (
27(2n + 1)2)1/3 (1i2A2) 1/3 with optimal n= 1.5.
32(2n -1) m '
If
( 1i2 2) 1/3 (1i2 A2) 1/3
n = 1, E(I) = (1.5)5/3: '" 1.97 --:;;;-
If
n=2, E(2) = (~225) 1/3 (1i::2) 1/3 '" 1.92 (1i::2) 1/3
Finally if one chooses the optimal n = 1.5
It is interesting to note that even with the best two-parameter trial wave function
'I/J~2) one does not do as well as with the one-parameter trial wave function 'I/J~I). In
other words increasing the parameters in one's wave function does not necessarily
result in lower energies, i.e. better results.
Consider the trial wave function
2 )1/2 ( 2)
'I/J~3\ x) = ( b.,fi exp - ;b2
1i 2 Ab
E(b) =- b + v7r
4m 2
,-'
The constraint
2.,fi
BE
fib = o·Impl'les b3 = 1i2mA .
Substituting this value of b into E(b) implies
27 )1/3 (A 1i
E(bopt'1mal) = ( -167r -m
2 2) 1/3
'" 0.81
(A- 1i2) 1/3
2
m
138 Chapter 10
This is much less than 1.86 (A 2h2 /mf/:
the best value obtained with the other
two trial wave functions! But this wave function does not satisfy the boundary con-
ditions and hence is unacceptable. In particular it is not zero at x = O. Hence this
particular result is wrong!
The lowest energy for large arguments of the relevant Airy function is El = 1.84 (A2h2/mt
(see Eq. (3.18) ).
EXAMPLE 10.3
Consider the system H = T +V where
Then
PH(x)tfJ(x) = H(-x)tfJ(-x) = H(-x)PtfJ(x) = H(x)PtfJ(x)
for this case since for the V of this example Vex) = V( -x),
V (X)
-----------------&--------------------x
Figure 10.3: Potential in Example 10.3.
Hence in this case H(x) = H( -x). Thus for this problem (indeed whenever Vex) =
V(-x) )
[PH(x) - H(x)P]tfJ(x) = 0, I.e. [P, H] = O.
Upper Bounds and Parity Considerations 139
But this has consequences on the eigenvalues and eigenfunctions of H. Assuming
[H, Pj = 0 consider the Schrodinger equation Eq. (10.1) :
Premultiplying by P
(10.11)
i.e. PWn(x) is proportional to Wn(x).
But Eq. (10.11) is just the eigenvalue equation for P. Thus whenever [H, Pj = 0,
the eigenfunctions of the Hamiltonian are also eigenfunctions of P!
Consider now the eigenvalue problem for P. If Po are the eigenvalues of P,
Pf(x) = Pof(x)
= f(-x) (10.12)
P 2 f(x) = p~f(x) = f(x).
Hence Po = ± 1.
Thus in Eq. (10.11) A = ± 1, and
Thus whenever, as is the case in this problem, V(x) = V( -x) and the system is
nondegenerate, the eigenfunctions of H have either even parity or odd parity.
Going through the derivation for upper bounds Eqs. (10.1) - (10.5), one sees that
in this case Eq. (10.5) applies independently to the odd- and even-parity solutions
since Eq. (10.3) will be an expansion either in terms of the even or the odd eigen-
functions 'lin. Hence working with odd-parity trial wave functions one gets an upper
bound to the lowest odd-parity state energy and similarly for even-parity trial wave
functions an upper bound to the lowest even-parity state energy.
A simple (though inadequate, since its derivative is not continuous at x = 0)
even-parity trial wave function for Example 10.3 is:
The condition
8E+ O· Ii b3 = 121i2
7ib = Imp es Am
(where one uses the representation of the delta function
d?
dx21xl = 28(x) ).
For optimal b,
If
8E+ b3 = 1i2../i .
7ib = 0, 2mA
For optimal b,
~t(x) = ( bv'i
2 ) 1/2 ~ exp (2
- ;b
) 2 '
Upper Bounds and Parity Considerations 141
with free parameter b, yielding
If
EXAMPLE 10.4
Consider the system H = p2/2m - Vo6{x), Vo > O.
V( x)
'ljJt(X) = ( mw)1/4
h7r exp
(mwx2)
-21i
(the ground-state wave function of the one-dimensional harmonic oscillator), with
free parameter w. One obtains directly
hw (mw)1/2
E(w)=--Va -
4 h7r
Requiring
oE(w) = 0 implies ~ _ Va (~)1/2 _1__
ow 4 2 h7r W1/2 - 0,
I.e.
4mVo2
Woptimal = 7rh3 .
Hence for this trial wave function,
vs. the exact ground (and only) state and only energy of this system (cf. Eq. (13.8»:
mV,2
Eground exact -- - 2h2 .°
One again notes
mv,2
E (Woptimal) = -0.318 h20 > Eground exact = -0.5 t/ '
mv,2
EXAMPLE 10.5
Consider the system H = p2/2m + V (x)
where
(mw')3/4 2x (mw'x 2)
(1)
'l/;t (x) -
_
T '/r1/4 exp --v;- .
(This is the lowest eigenfunction of H' = p2/2m + V'(x) where
x 2:: 0,
V'(x) = {
00, x < 0,
with eigenvalue 3nw' /2.)
Using this trial wave function,
3 /{ 8ma} 3 nw2
4"nw 1 + 3n2 + 4"7 .
x + -xa2 + ( W,2
1 2 1
p2
H = -2m + -mw
2
,2 2
-w - )
1 -mw x
2
/2 2
Jo[00 ol't(l)*(X)
'f/
~mw'2
2 x2 ol't(l)(X)
'f/
dx = ~
2 (~nw')
2 c. Eq. (9 .5) ) . 1
(f
From the constraint
one obtains
, w
w optimal = V1 + 8ma / 31£
~2 •
Hence
E (1) ( Woptimal
I ).J33
= -2- i:
nW 'V 2.873 nw > 2.5 nw,
as expected.
One may use instead:
(2,8)2n+l n
(2n)! x exp (-,8x),
For optimal ,8
which has values 2.556 nw and 2.535 fiw for n = 3 and 4 respectively, while for optimal
noptimal 3.74,
'V
As expected one again gets an energy greater than the exact energy, but ¢F) (x) is
seen to give a better upper bound than ¢(l)(x).
If a = 3n2/m, 6fi 2 /m, 10fi 2/m etc. again one knows the exact solution which
one can compare with the upper-bound results that arise in these cases.
Thus for a = 3fi 2 /m, and 1 = 2, Eexact ground = nw/2, while
and
a . _ Jmw [(2n + 1)(2n -l)(n + 1)nfi 2] 1/4
t"Optlmal - 1i 2(n1i2 + 4am)
Thus
If
~~3\X) = C~f/2 (m;'r/4x2exp (- m;~x2)
is used as trial wave function,
E(3)( ')
w
= (!..- 2am) fiw'
12 + 3fi2 + ~4 fiw
2
Wi ,
146 Chapter 10
with
, w
Woptimal = J7/15 + 8exm/15h 2
Substituting this value of w',
If
E(3) (W'optimal) = 5/2 hw = Eexact ground,
which implies that ~P)(x) is the exact ground-state wave function for this value of
ex, while if
_ 3h 2
a - m' E
(3) ( ' .
WoptImal - 2
) _ ~J155
3 hw
rv ~_
3.59 hw > 2 hw - E ground exact·
Thus ~~3\ x) gives a better upper estimate for Eground than ~?) (x) while the best
upper limit for this case is given by ~}2).
EXAMPLE 10.6
Consider the system H = p2/2m + V( x), where
-ahe/x, x 2': 0,
V(x) = {
=, x < 0,
with ground-state eigenvalue of E ground exact = -mc 2 a 2 /2.
Estimate the ground-state energy of this system using as trial wave function:
~)
~t (x) -
_ 2 1
b ( byf1r )
1/2 x exp - 2b2
(2 ) X
•
4
= -_mc2a 2 '" -0.424 mc2a 2
37r
> Eground exact'
as it must be. This result is quite close to the exact ground-state energy. Other trial
wave functions do not do as well.
Thus, if instead one uses:
(2) _ 2 J2
2 (X2 )
'!f;t (x) - b2V~ x exp -2b2 '
one obtains
71i2 41ica
E(b) = 12mb2 - 3b..,fi .
8E(2)(b) b . _ Th..,fi
8b = 0, implies optimal - 8mca .
Hence
16 32
= _mc2a 2 - _mc2 a 2
2b 2b
16
= -217rmc2a2 '" -0.243 mc2a 2.
If one uses:
one obtains
3
= _gmc2a 2 = -0.375 mc2a 2•
Though both E(2) (boptimal) and E(3)(bopt imal) are above Eground exact,
neither is as close to it as is E(1)(boptimal)'
.1,(4)( ) _
'f't X -
V2
b2 x
3/2 (x2 )
exp - 2b2 '
yields
8E(4) b . _ 51i
--m;- = 0, results in optImal - 2macV; .
EXAMPLE 10.7
Consider the Hamiltonian:
(all x).
tPt(X,w') = 1
7r 1 / 4
(mw')
T 1/4
exp
(mw'x
----y;-
2)
,
evaluate E (w') and find the minimum upper bound to the ground-state energy with
this trial wave function for the case a = 1.
Upper Bounds and Parity Considerations 149
Evaluating I.,p; H.,pt dt, one obtains:
liw' liw 2 3aliw3
E(w') = 4" + 4w' + 4W,2 ,
hence
8E(w') Ii liw 2 6anw 3
---::a:-'-w""'"-"- = '4 - 4W,2 - 4w,3
The condition 8E(w')/8w' = 0 yields the result:
W,3w'
----6a=0.
w3 w
Thus if a = 1, w' = 2w, and E(2w) = 13/16 nw = 0.8125 nw.
This can be compared to the exact answer (obtained by numerical methods) in
this easel =0.803771... liw .
If one substitutes w' = w then E(w) = liw/2 + 3aliw/4, which is the zero (nw/2),
plus first order (3anw/4) perturbation contribution if one writes H = Ho + V with
Ho = p2/2m + mw 2x 2/2, V = aliw (Jmw
/Ii x) 4, a decomposition which for a = 1
results in a much worse upper bound E(w) = 1.25 liw, and a diverging perturbation
series 2 (for all values of a).
EXAMPLE 10.8
Consider the Hamiltonian (cf. Example 10.7):
If a=O, t h e con d ·,
ItIon ---a;;-
8E(b) = O'ImpIies:
b = (30)1/4 J mw
Ii rv 2.340 Jmw
Ii .
Hence
E (boptirnal) = f[; liw rv 0.55 liw VS. 0.5 Tiw, the exact result.
Similarly
EXAMPLE 10.9
Consider the Hamiltonian :
(all x).
Ixl > b,
find E(l)(w',a), E(2)(b,a) and the minimum values for E(1), E(2) for arbitrary a.
Upper Bounds and Parity Considerations 151
By a straightforward calculation (d. Example 10.7) one obtains:
nw' nw 2 a15nw 4
= 4 + 4w' + 8W,3
aE(1) (w', a)
ow' 4" - 4W,2 - 8W,4
-
The minimization condition is thus:
Similarly
and
OE(2)(b a)
ab' = 0, implies 5au8 + 7u 4 - 210 =0 where u
Jmw
= b T'
I.e.
uoptimal
. = Jmwn (-7 + V49lOa+ 4200a )1/4
If a = 8/9, boptimal rv 1.57 Jmw/n, and E(2) (boptimab 8/9) rv 0.910 nw. This
indicates 'I/'~1) is a better trial function than 'l/'F).
EXAMPLE 10.10
(d. Eq. (5.2) where the analogous result is obtained using the Uncertainty Principle.)
One obtains:
nw (n + 1) A (~)n/2
+ _1 r
E(w, n)
4 Vi 2 mw
oE(w, n) ~ _ ~r (n + 1) A (~)n/2 (~)n/2+1
ow 4 2Vi 2 m w
152
Cbapter 10
Hence
. _ (2nr ([n + 1]/2) An(n-2)/2) 2/(n+2) and
WoptImal - ~ mn/2 '
(10.13)
= (nnr ([n + 1] /2) A( n + 2)(n+2)/2) 2/(n+2)
~ (nm)n/22n+1
n2 A) 1/2
while if n = 2, E (Woptimab 2) = ( 2m = Egroun d exact, etc.
2 6Abn
E(b, n) -3n- + -;---;--~--:-:--;-
2mb2 (n + l)(n + 2)(n + 3)
----::-;-
8E(b, n) 3n 2 6nAbn- 1
8b --m-b3 + (n + l)(n + 2)(n + 3)
and
b . _ ((n+1 )(n+2 )(n+3 )ti 2 )1/(n+2)
optImal - 2nAm
Thus
E(boptimab 1)
E( boptimal, 2)
EXAMPLE 10.12
x < 0,
Given H = T + V(x), V(x) ={ 00,
Axn , x> o.
Find E(b, n) and E(boptimab n) if 'l/Jt(x, b) = 2/b (1/bVi)1/2xexp(-x2/2b2).
One obtains
Thus
3n/ 2Ahnnf([n + 3] /2)] 2/(n+2)
E(boptimab n) [
m n / 2 2 n Vi
[
3n/ 2Ahn(n + 2)(n+2)/2f([n + 3] /2)] 2/(n+2)
(nm )n/22n Vi
Ah2)1/2
E(boptimal, 2) = Eground exact(n = 2) (
3 2m '
etc.
EXAMPLE 10.13
oE(b)
fib
Hence
and
EXAMPLE 10.14
Consider the system (cf. Example lOA)
EXAMPLE 10.15
Consider the system (d. Example 10.3)
p2
H = 2m + Vex), Vex) = Alxl , for all x.
io2 4 )1/3
b- ( n7r
- 2Am (7r - 4)
2
Hence
This result can be compared to the results 0.81 ( A2'/i2/m ) 1/3 and 0.86 ( A 2h2/m )1/3
of Example 10.3.
156 Chapter 10
One notes in passing3 that for all the Hamiltonians discussed in this Chapter of
the form
H=T+Axn,
the Virial Theorem (cf. Eq. (9.6) )
is also satisfied if
References
3. H. A. Mavromatis, to be published.
CHAPTER 11
Perturbation Theory
H= Ho+ V. (11.1 )
If one knows the eigenfunctions (cPn) and eigenvalues (En) of H o, i.e.
(11.2)
and wishes to find the eigenfunctions (1/Jn) and eigenvalus (En) of the Schrodinger
equation:
(11.3)
where 1/Jn reduces to cPn as V --+ 0, one can formally expand each eigenfunction 1/J in
terms of the complete set cP :
(11.4)
m=O
L (H - E)amcPm = 0, (11.5)
m=O
where for notational simplicity the subscripts n have been omitted from the 1/J's and
E's.
Premultiplying Eq. (11.5) by cP; and integrating over the relevant variables one
obtains:
00
where
158 Chapter 11
and
Vpm == J4>;V4>m dr = (4)plVl4>m). (11. 7)
Hoo-E
The eigenvalues E of Eq. (11.6) are the exact energies of the system Eq. (11.3)
and the corresponding coefficients am when substituted into Eq. (11.4) give the
corresponding eigenfunctions.
Consider for simplicity the special case when Eq. (11.6) is a 2 x 2 matrix. The
determinant of this matrix must be zero i.e.
(11.9)
{Hoo + H11 ):!: (Hoo - H 11 ) (1 + 2V(n Vio/(Hoo - H11)2 + ...)
- 2
Keeping only the first two terms in this expansion results in the following expansions:
Eo
IT
flOO + HooVOl-VioHu = Eo + VOO + -
TT
- -V(n-Vio- - -
fO + Voo - fl - ViI
V, volVio
= Eo + 00 + (fO - fl)( 1 + (Voo - Vid/(fo - fl) ) ,
(11.10)
H 11 + Vio VOl = f1
Vio VOl
+ V;11 + ---::-:--"-~':---::-::,-
Hu - Hoo f1 + ViI - fO - VOo
= fl Viovol
+ V;11 + ..,..--~--,----,-----:---:-:---~
(fl - fO) { 1 + (ViI - VOO)/(fl - fo) )
Upon expanding the denominators in these expressions one obtains:
Perturbation Theory 159
= { E - Hoo } { E - Hoo }
tPo ao <Po + VOl <PI -+ <Po + VOl <PI ,
(11.12)
if in addition one requires {<P011f10} = {<P111f1l} = 1, i.e. that the 1f1'S are 'cross-
normalized' functions.
Substituting Eo and El of Eq. (11.11) into Eq. (11.12) yields:
(11.13)
'" <Po VOl <Po Voo Vln <Po VOl Vll
1f1l = '1'1+--+
fl - fo (fl - fO)
2- (fl - fo) 2+····
One can generalize the results in Eq. (11.11) as follows:
= fn + Vnn + L
00 v.nm v.mn +
(11.14)
mIn En - fm
{
~
L..J
VnmVmpVpn _ V.
nn L..J
~ VnmVmn
2
}
+ ... ,
m,#n (En - Em) (En - fp) mIn (fn - fm)
which is the standard Rayleigh-Schrodinger expansion for the exact energy to third
order in V. The first term on the r.h.s. of Eq. (11.14) is called zero-order. The term
on the r.h.s. of Eq. (11.14) involving V once (the second term) is called first order.
The term on the r.h.s. involving V twice (the third term) is called second order, and
terms involving V thrice (the fourth and fifth terms) are called third order, etc.
160 Chapter 11
One can generalize the results in Eq. (11.13) as follows:
(11.15)
which is the standard Rayleigh-Schrodinger expression for the exact wave function
to second-order in perturbation theory when one has cross-normalized functions 'ljJn
i.e. (¢nl'ljJn) = O. Fourth and higher-order terms and third and higher-order terms
in Eqs. (11.11) and (11.13) respectively may be obtained by keeping more terms (in
expanding the radical) in Eq. (11.9). The usefulness of Eqs. (11.14) and (11.15) in
turn depends among other things on whether the expansions converge.
EXAMPLE 11.1
Consider a particle subject to the Hamiltonian:
Ixl ::; a,
Ixl > a.
Potential Energy V ( x )
_ _ _ _ _ _ _ _ _ _ _ _- L _ _~~~---L---------- __ x
-a a
H=Ho+V,
where
Perturbation Theory 161
Ixl < a,
Ixl > a.
To first order in V one then has
where En, <Pn are the standard eigenvalues and (real) eigenfunctions of the one-
dimensional infinite harmonic oscillator.
This problem illustrates one important limitation of perturbation theory. It pre-
dicts here an infinite, discrete set of energies En. However, if E > mw 2 a2 /2 the
particle is no longer bound, but rather is free i.e. can have any energy!
In fact only if E « mw 2 a2 /2 (i.e. (n + 1/2) « mwa 2 /2n) does one expect
to get reasonably accurate results using perturbation theory.
Classically for this system it makes no difference what the potential is for x greater
than Xmax where Xmax = J2E/mw 2 • The quantum-mechanical treatment of this
problem, however, shows that the potential for x > Xmax also affects the particle.
If a --t 00 the exact energies of the system go to En. For finite a however, the exact
energies En are less than En since Vnn < O. Roughly speaking this is because there is
more likelyhood the particle will be in the region x > a for the potential V = mw 2 a 2 /2
than for the more repulsive potential mw 2 x 2 /2. On the other hand the more the
particle spreads, the bigger its wavelength A, and smaller its energy since k '" 1/)",
while E '" k 2 •
EXAMPLE 11.2
Consider a particle in the potential
Ax, x> 0,
v(x) = {
00, x < O.
Suppose one wishes to know the ground-state energy of a particle in this potential.
The Hamiltonian of the system is
H = T+Ax, x> O.
But one can rewrite H as
162 Chapter 11
where
(x> 0),
and b is a parameter.
With this decomposition ofthe Hamiltonian one can treat (Ax - { Ii? /2mb4 } x 2 )
and
One particular choice for b makes the first-order energy contribution zero, namely
b3 = b3 = 3h2v:;r
1 - 8Am .
vex)
--------------~~~-----------------x
f: VanVnO = f: (0IAx-1i2x2j2mb4In)2(nIAx-1i2x2j2mb410),
(11.16)
n~O Eo - En n=1, 2... -2nn /mb 2
smce
En = (2n +"23) mb1i 2
2 •
etc.
Considering the first (n = 1) term in Eq. (11.16) one has
All additional second-order terms are also negative, hence add to the magnitude
of the second-order result, but should be small compared to Eq. (11.17). Indeed the
next second-order term (n = 2) is:
= 1
__ (~)1/3 (A 21i2) 1/3 = -0.0015 (A21i2) 1/3
320 811" m m
E = G) 2/3 ( A~2) 1/3 C~) 2/3 = (8~) 2/3 ( A~2) 1/3 ~ 1.84 ( A~2) 1/3
(3:::)
With the first choice for b
(11.19)
'" cPo (bt) + (0.153 + 0.048) cPt (bt) = cPo (bt) + 0.201 cPt (bt) ,
if one includes only the first excited state in Eq. (11.15).
_~ ________-==-t_ X
b
~1 (b)
~-~-~--+----~~~X
{~ = c:::) t/3 which minimizes the energy to first order, i.e. makes 8Hoo /8b = o} ,
166 Chapter 11
the matrix element VCn is zero so there is no contribution to the exact ground-state
wave function from f/J1 for this choice of b :
(11.20)
to second-order in V.
The Eqs. (1.19) and (11.20) are less dissimilar than they look since they involve
different b's with b1 '" O. 794 ~. Thus though f/Jo (bd of Eq. (11.19) is more compressed
than f/Jo (b 2 ) of Eq. (11.20), this is compensated for by the small admixture of f/J1 (b 1 )
in the former expression as can be seen by considering Figures 11.3 and 11.4.
EXAMPLE 11.3
Consider a particle subject to the Hamiltonian:
o ::; p ::; a,
V= {O,
-mw2p2J2, p> a.
Potential Energy
~_----L- _ _ _ _;
a
Figure 11.5: Potential in Example 11.3.
The ground-state wave function for Ho is (see Eq. (8.14)):
( p2)
Woo(p) = ( b2)1/2
2 p1/2 exp - 2b2 '
Perturbation Tbeory 167
with b = Jh/mw, and EO = hw.
To first order in V one then has
Eo = fiw - -21
b2 a
00
(1-mw
2
2p2)
fiw - fi; { _ exp ( _ p2 / b2) (1 + ~:) [ } (11.22)
(laOO WlO(P) (-mw 2p2/2) woo(p) dp)2 (_ {fiw/2} {exp (_p2 /b 2) (1 + p2/b2 + p4/b4) I:;"}) 2
-2fiw -2fiw
Hence approximately:
(11.23)
where
Alxl P - n2 x2
__
2mlfl
can be treated as the perturbation V. With this decomposition the ground state
energy of this sytem can be immediately calculated using first-order perturbation
theory, with
(oIAlxl P- __ 2
2mb4
n2 x I)
0 = -AbP
Vi
(P---1) ! - -n-
2
2 .
2 4mb
The choice
11'+2 = n2 Vi
4mA([p -11/2)!
makes the first-order energy zero, and yields
Eo =
1
2(2p-2)/(p+2)
( ;"P
(p - 1)!1 m P/ 2
A) 2/p+2
(11.26)
Perturbation Theory 169
These results may be combined:
E
o
= 1
2(71- 2)/(71+ 2)
(r ([P + 11/2) liP A) 2/(71+ 2)
7r 1 / 2 m 71 / 2 for arbitrary p. (11.27)
li 2271 / 2- 1
bfJ+2 = .
mAp(p-1)!!
For p odd in this case
p +2 (Ahp(P _1)!!)2/(71+2)
Eo '" 2(371+2)/(71+2) (pm )71/2
These results may be combined yielding (d. Eq. (10.13) ):
for arbitrary p. For p = 2 Eqs. (11.27) and (11.28) both yield fiw/2 which as expected
is the right result (where A = mw 2 /2).
EXAMPLE 11.5
Consider the Hamiltonian
H=Ho+V(x,y),
where
170 Chapter 11
while
V(x, y) = >..mw 2xy .
Suppose one wishes to find the (non-degenerate) ground-state energy of this system.
The unperturbed ground-state energy of this system is nw with corresponding
wave function <Po(x)<Po(Y) (cf. Eq. (12.4) ).
The first-order correction to this energy is zero since
The only term which contributes in second order because of the nature of this par-
ticular V is <Pl(X)<Pl(y) at energy 3nw.
Hence the second-order contribution to the energy is
>..2nw
Eo = 21 nw { ~ + v'1'+1" } = nw - -8- + .... (11.29)
The exact normalized wave function for this state (see Example 12.9) is
'l/Jo = <Po (X, w = WI) <Po(Y, w = W2),
where
while
mw)I/4
<po{e,w) = ( 1i1r exp
(mwe)
--u '
1.e .
• 1. (
'1'0
)
X, Y
= (mw) 1/2
n1r
(1 _ A\2) l/S exp (_ mwvr=-x
21i
X2)
exp
(_ mwv'fD Y2)
21i '
or
(11.30)
x exp ( -
mw{ Jf='141i+ v'f+1' )y2)
exp
(mw( vT='1'21i- v'fD )x y ) .
Perturbation Theory 171
If ,\ « 1 one can write Eq. (11.30) as
On the other hand, to second order, perturbation theory yields for the wave
function:
tPo(x, y)
(11.32)
smce
while N ,..., (1 + >..2/16 + ... )-1/2 if one assumes (as in the case of Eq. (11.30) ) that
(tPo(x,y) ItPo(x,y)} = 1.
The Eqs. (11.31) and (11.32) are identical to order >..2 if one substitutes
N,..., 1 - >..2/32 in Eq. (11.32), since
<Pl(X) = V~
T-h- x <Po(x) and <P2(X) 1 (
= -.,fi 1-
2mw x2) <Po(x).
-h-
172 Chapter 11
EXAMPLE 11.6
Consider the Hamiltonian
p2
H= -+v(x)
2m
where
Voc5(x), -a ~ x ~ a,
vex) = {
00, Ixl > a.
To obtain the exact result one writes the Schrodinger equation as follows:
where
p2
Ho = 2m' Vex) = Voc5(x) and x ~ 14
Thus
1
tjJ(x) = A {Voc5(x)tjJ(x)} , (11.33)
E - p2/2m
where the p2 operates on the term in the brackets { } .
vc x)
0, -a ~ x ~ a,
V= {
00, Ixl > a.
Perturbation Theory 173
between
1
and {l/oo(x)~(x)}
E - p2/2m
in Eq. (11.33) (where the odd eigenfunctions of this set do not contribute to
(n Ivoo(x)1 ~(x)) ) . One then obtains:
SInce
n = 1, 3, 5... ,
I.e.
h2 00 1
32 voma = nodd
fT L f3 - n 2 (11.35)
where
f3 = 32ma
2E
h2 •
If one plots the two sides of this equation one obtains Figure 11.7, where the
intersections correspond to acceptable values of E.
I
{3-n2 h2
::?;
1,3, ... 32 '{,rna
Vo > 0
16 20 25
P
h2
32Vo ma Vo < 0
Figure 11.7: Exact energies in Example 11.6, graphical solution of Eq. (11.35).
174 Chapter 11
If j3 = q2 + 8, (where q = odd integer)
h2 1 8 ,...., 32VQma
32VQma ,...., S ' h2 '
I.e.
j3 _ 2 32VQma
- q + h2 '
or
h 2q2 VQ Va
E=--+ - = f . q +-.
2 32ma a a
A more accurate calculation yields:
I.e.
implying
where
odd 1 h2 odd 1
Cl = L (2
n'i-q q - n 2)2'
C2=
32Vroma
- ~
L..J q2 - n2
n'i-q
•
Thus
Since
(11.36)
Perturbation Theory 175
which is just the perturbation result for Eq (q=odd) to third order since if r, s are
odd (<Pr IVI <p$) = Vo/a for this particular V and set of eigenfunctions of H o. For the
complimentary set of zero-order eigenfunctions,
1 . qrrx
<pq(x) = Va sm 2a' q = 2, 4, ... ,
But if (<pq 11jI(x)) = 1, (i.e. the wave function is 'cross-normalized') this implies:
Vo1jl(O) 1 _ 1
Va E - q2h2 /32ma 2 - .
Vo{
Vo odd
1jI(x) = <pq(x)+- 1 + - L 1
+ ... L
} odd <Pn(x)
,
a a mi-q Eq - Em ni-q (Eq - En) {I + Vo/(a [Eq - EnD + ... }
I.e.
1jI( X)
(11.38)
VO)2 (VO)2
+ (-a
odd <Pn(x) odd <Pn(x)
L
n,mi-q (Eq - Em) (Eq - En)
- -a L
ni-q (Eq - En)
2+···'
For this particular Hamiltonian one can also obtain the exact eigenfunctions of
this system in a form which unlike Eq. (11.37) does not involve infinite sums. This
can be done by writing
d.,p
dx I - d.,p
dx I = 2m Yo ·/'(0)
;,,2 '1/
(f
C.
E q. (6.10 )) .
x=€ X=-E
'II (x)
----~----------~--------~----~x
-0 o
1i 2 k
tanka = - - - . (11.40)
mVo
Thus the even-parity solutions 1jJ( x) are given by:
IAI 2ja
-a sin2 k(a -Ixl) dx = 1,
or
(11.42)
(Vo/a){(l - lxi/a) (q7r /4ya) sin (q7rlxl/2a) - (1/4ya ) cos (q7rX/2a)}]
+ q2 h 2/32ma 2 '
or
(11.43)
(q/2) ((7r/2) - u) sinqu
- (1/4) cos qu
EXAMPLE 11.7
Consider the Hamiltonian:
= Ho+V,
where
Ho = T + ~mw2x2 and V = Voexp ( _ :2).
Perturbation Theory 179
v
Vo if Vo>O
Vc 100
Eo
nw b.,fir
= 2+ -00 exp (X2) (X2)
- b2 exp --;- dx since ¢o(x) = ( b.,fi
1 ) 1/2 (X2 )
exp - 2b2 '
where b = J'fi/mw .
Thus,
Eo
hw Yo
2 + bft {1/b2+ 1/fV/2
100
-00 exp (_x 2{b21 + ~1 }) dx { b21 + ~1 }1/2 ,
I.e. (11.44)
fiw Va
= -+----:-=
2 {1+b2/f}1/2'
Sex) = 1 I¥
r.;lim - exp - -
v7r <-+0 f f
(x2) (see Eq. (2.15) ).
EXAMPLE 11.8
Consider the Hamiltonian
p2 1 afiw ( )
H = - + -mw x +
2 2
x ~ 0 .
2m 2 (Jmw/fi xf
180 Chapter 11
Treating
<P3(X) = (~w) 1/4 ~ 'Jrl/4 U (8u 6 _ 84u 4 + 210u 2 -105) exp ( _ ~2).
E(2) _ I < 01Y11 > 12 I < 01Y12 > 12 I < 01Y13 > 12
o - -2nw + -4nw + -61iw + ...
This is a slowly converging series. The exact result in this case can be obtained by
examining the three-dimensional simple harmonic oscillator system (cf. Eq. (8.13) ).
In detail:
Eground exact = (1 + ~)
2 hw '" (32" + 2a - 4a 2 3+...) hw,
+ 16a
where the series expansion converges for a < 1/8 ). Thus the second-order series
implies:
Perturbation Theory 181
EXAMPLE 11.9
Thus if
EO=Eo+Voo,
h2~2 h2~2
,/.. ,/.. ( ) 2. ~x . ~y
EO = En = 2mL2 { 12 + 12} = mL2 ' 'f'0 = 'f'00 L sm L
x, Y = Ism ' (11.45)
and
4 2
Voo = -LVi
L2
ii
00
L L . 2 -~x sm
sm
L
~y ( x - -
. 2 -8
L
L)
4
8 (y - -L)
4
dx dy = Vi.
Combining terms:
n2~2
Eo = mL2 + Vi. (11.46)
Hence:
182 Chapter 11
Thus
(11.47)
Comparison with Eq. (11.46) shows this is larger than to + Voo, the result to first
order in perturbation theory.
EXAMPLE 11.10
Consider the Hamiltonian:
where
Yrel. (Xl - X2) = ~mwi (Xl - X2)2 •
Find the exact energy of this sytem and the ground-state energy to second order
in perturbation theory, assuming V = Vrel. (Xl - X2)'
To obtain the exact energy one recasts the Hamiltonian in a more transparent
form:
where
= + X2
M == 2m, X C.M. -
Xl
2 ' /1 == m/2, xrel. == Xl - X2'
l.e.
H = ( P22M 1
C.M. + -Mw 2X 2 ) + (p2reI. + +_11
1 {w 2 + w2} X2 )
2 0 C.M. 2/1 2'- 0 I reI. .
Hence:
N, n = 0, 1. .. (11.48)
1 1 WI 2 1/2 1 1 { 1 WI 2 1 WI 4 }
-nwo + -nwo { 1 + (-) } "-'-nwo + -nwo 1 + - (-) - - (-) + ...
2 2 Wo 2 2 2 Wo 8 Wo
nwo 1 (w2)
+ -n .2. 1
- -n (W4)
-{ + .... (11.49)
4 Wo 16 Wo
Perturbation Theory 183
In the perturbation theory treatment of this problem one writes
From parity considerations the term XIX2 is seen not to contribute to this integral.
Thus
=
1(00 I mwixi/4 120)1 2 + 1(00 I mwix~/4 102)1 2 + .:...:.......-'--.!.-~:..:..-~~
1(00 I mwi2xlx2/4 111)1 2
-2nwo -2nwo - 2nwo
-~n (wt)
16 w5
Thus to second order:
1 (W2)
Eo = nwo + -n -1.. - 1 (w4)
-n ~ , (11.51)
4 Wo 16 Wo
and as expected this expression agrees with the first three terms of Eq. (11.49).
EXAMPLE 11.11
Consider the Hamiltonian:
p2
H = 2m +v +V = Ho +V
Ixl < a,
v = { 0,
(Xl, Ixl > a,
184 Chapter 11
v = { (Va/f) [I-Ixl/f], Ixl < f, f < a, (Va < 0) ,
0, Ixl > f.
Find the ground state of this system to second order in perturbation theory. Examine
the limit f ---+ o. (Note that: lim<-+o (I/f) (1 -lxi/f) = o(x) cf. Eq. (4.22) (vi) ).
One notes (cf. Example 11.6), that the ~ zero-order functions and energies
are:
1 mrx n 2 h2 h2
rPn(x) = va cos 2;;' En = 32ma2 ' n = 1, 3, 5 ..., I.e. fl = --.
32ma 2
Also the first-order contribution:
where
VIm = 2Va
fa
r (1 _ .:) (cos rrx2a cos mrrx)
Jo f 2a
dx
As E --+ 0,
Degeneracy
One-dimensional systems
The Schrodinger eigenvalue equation, Eq. (12.1) for the simplest possible case,
namely a one-dimensional system:
h2 d2 )
{ - 2M dx2 + V(x) 1/;(x) = E1/;(x) (12.1)
!~~ol'
Consider for instance a particle in the well:
x < 0,
1/;(x)=Cexp(-kx) or Dexp(kx), k-
-
J2MIEI
h2 •
However, the wave function in this case satisfies the boundary condition that it van-
ishes at x = 0 where the potential is infinitely repulsive, as well as at infinity since
the particle is localized in the well. Hence
must be discarded. One thus has only ~ acceptable solution which, together with
its derivative, must be made continuous for all x > 0, in particular at x = a. This in
turn imposes a quantization condition on the energy namely:
Degeneracy 187
K
tanKa = --.
k
vex)
______________~~-----ar_-----------4~X
Two-dimensional systems
Consider the case where V = V(p), p2 = X 2+y2. The radial Schrodinger eigenvalue
equation for this system is (d. Eq. (8.10)):
;,,2 d2
{ - 2M ;,,2(m2 -1/4)}
dp2 + V(p) + 2Mp2 wnm(p) = Enmwnm(P), (12.2)
Independent of the details of Wnm (p) (unless m = 0) there are here at least two
normalized solutions for each energy eigenvalue, namely:
EXAMPLE 12.1
Consider the two-dimensional oscillator potential V (p) = M w2p2 /2. Examine the
degeneracies which arise in this case.
Solving the problem in cylindrical coordinates yields:
= Ntiw N= 1, 2 ....
A simple tabulation shows the degeneracy increases as the energy increases, in
fact is N, where Ntiw is the energy of the system. These results are tabulated in
Table 12.l.
It is of interest to compare these with the degeneracies which result if one solves
the same problem in Cartesian coordinates. This particular potential can also be
written V(x, y) = Mw 2 (x 2 + y2) /2 and has the Cartesian-coordinate solutions:
where
1 1 (1) 1/2
2n/2 (n!)1/2 b,Ji Hn
(X) (X2 )
b exp - 2b2 '
(12.4)
Table 12.2, which is similar to Table 12.1 shows that the number of degeneracies
for a given energy are, as they must be, basis independent.
In case there is no degeneracy (in the ground-state) the wave functions are iden-
tical. Thus if E = tiw:
( 1)
bJ7r
1/2 (X2) ( bJ7r
exp - 2b2
1) 1/2
exp - 2b2
(y2 )
=
(1) (p2 )
by'i exp - 2b2 .
Degeneracy 189
However in the cases there is degeneracy the wave functions are not identical. Thus
the E = 2 nw states are
TABLE 12.1
Energy levels in Example 12.1, using cylindrical coordinates
Partial Total
Enm n m
Degeneracy Degeneracy
1nw 0 0 1 1
2nw 0 1 2 2
1 0 1
3nw 3
0 2 2
1 1 2
4nw 4
0 3 2
190 Chapter 12
TABLE 12.2
Energy levels in Example 12.1, using Cartesian coordinates
11iw 1 0 0 1
1 0
21iw 2 2
0 1
2 0
31iw 3 1 1 3
0 2
3 0
2 1
41iw 4 4
1 2
0 3
"-)
(p, 'I' .,pl0(X, y) ± i.,p01(X, y)
XO±1 = V2
Generally:
00
where the sum is over all degenerate states at the same (in this case n",+ny = 2n+m)
energy as Xnm(P, ¢) and reciprocally:
EXAMPLE 12.2
Discuss the degeneracies for a particle in a two-dimensional Coulomb potential
(cf. Eq. (8.12) ).
The energy for this system is
1 3
n= 2' 2····
The degeneracy is:
n-1/2
2n = 1 + L: 2,
m=1
since aside from m = 0 all other terms are two-fold degenerate, while m varies from
o to n -1/2.
Three-dimensional systems
Consider the case V = VCr). The Schrodinger eigenvalue equation is then (see
Eq. (8.2) ):
192 Chapter 12
where (12.7
This equation has at least a (21 + I)-fold degeneracy because Eq. (12.7) is
independent of the integer m which can take all values from -1 to 1. There may
be additional degeneracies which depend on the details of V(r), i.e. on how many
different n, 1 combinations yield the same energy Enl •
EXAMPLE 12.3
Discuss the degeneracies of the three-dimensional simple harmonic oscillator.
For the three-dimensional simple harmonic oscillator the energies are given by
in Cartesian coordinates.
One can easily verify that if E = (N + 1/2)1iw the degeneracy is:
EXAMPLE 12.4
Discuss the degeneracies of the three-dimensional Coulomb potential. For the
three-dimensional Coulomb problem
Degeneracy 193
(see Eq. (8.11)) and the degeneracy is:
n-1
2:(21 + 1) = n2•
1=0
EXAMPLE 12.5
Consider the system
or
1/1~~2m2(1, 2) = ~ {Y,!:l (I)Y,!;2(2) ± Y,!:l (2)Y'!;2(1)} ,
(where the 1/ V2 is required for normalization purposes and the latter function is
symmetric (or anti symmetric) under interchange of the coordinates 1, 2 ).
For a given II, 12 there are generally (211 + 1) (212 + 1) symmetric wave functions
and the same number of anti symmetric wave functions where for symmetric functions
1/1(1,2) = 1/1(2,1) while for antisymmetric wave functions 1/1(1,2) = -1/1(2,1). In the
special case it = 12 there are only (21 + 1)2 wave functions at the energy C2n21( 1+ 1)
of which 21(21 + 1) are symmetric and (21 + 1) are antisymmetric.
These results can be easily illustrated by listing the wave functions for II = 1, /2 =
1; h = 1, l2 = 2.
194 Chapter 12
(a) h = 1, 12 = 1, E = 4C'h2,
1/>(1,2) = Yl 1(I)Yl1(2); Yl 1(1)Yi1(2); Yl 1(1)Yd(2); Yo1(I)Yl1(2); Yo1(I)Yd(2);
or
Yl(1 )1-;1(2);
(1/../2) [1-;1(I)Yo1(2) ± 1-;1 (2)Yci (1)] ;
Yo1(I)Yo1(2);
1/>(1,2) =
(1/../2) [1-;1(I)Y!1(2) ± 1-;1 (2)Y!1(1)] ;
(1/../2) [Y_.\(I)Yo1(2) ± Y!1(2)Yci(I)];
y1-1 (l)y1-1 (2)-,
or equivalently
1-;1(1 )1-;1(2);
(1/../2) [1-;1(I)Yo1(2) + Yo1(1)1-;1(2)];
(1/../6) [2Yo1(I)Yo1(2) + Yl(I)Y!1(2) + Y!l (1)Yl (2)] ;
(1/../2) [Y!1(I)Yo1(2) + Yci(I)Y!1(2)];
yl-1 (l)yl-1 (2).,
1/>(1,2)=
(1/../2) [1-;1(I)Yo1(2) - Yci(1)1?(2)];
(1/../2) [1-;1(I)Y!1(2) - Y!1(1)1-;1(2)] ;
(1/../2) [Yo1(I)Y!1(2) - Y!1(I)Yo1(2)] ;
i.e. there is a ninefold degeneracy. (This latter combination corresponds to the set
of eigenfunctions 1/>~ot. of the total angular-momentum operator
[Pl2 , H(1,2)] = O.
then
Pi277(1,2) = ,,\P1277(1,2) = ..\2 77 (1,2) = Pl2 77(2,1) = 77(1,2),
i.e. ,\2 = 1, hence..\ = ±l.
Since in this example Pl2 and H(l, 2) commute, the eigenfunctions of H can also
be written as eigenfunctions of Pl2 , i.e. as combinations which have eigenvalues +1
or -1 under particle interchange.
One can remove the degeneracy of this system for instance by adding the term
to the Hamiltonian. With this additional term the Hamiltonian no longer commutes
with the exchange operator Pl2 (unless al = a2) and different projections have differ-
ent energies so there is no degeneracy. If al = a2 = a there is still 'exchange degener-
acy', though states with different projections are no longer degenerate. For example
in the case It = 12 = lone then has one (symmetric) state with energy 4Ch 2 + 2an,
two states (one symmetric and one antisymmetric) with energy 4Cn 2 + an, three
Degeneracy 197
states (two symmetric and one antisymmetric) with energy 4Ch 2, two states (one
symmetric and one antisymmetric) with energy 4Ch 2 - ah, and one (symmetric)
state with energy 4h2 - 2ah. In the case 11 = 1,12 = 2, one has two states (one
symmetric and one antisymmetric) at energy SCh 2 + 3ah, four (two symmetric and
two antisymmetric) at energy SCli 2 + 2ali, six (three symmetric and three antisym-
metric) at SCli 2 + ali, six (three symmetric and three antisymmetric) at SCli 2 , six
(three symmetric and three antisymmetric) at SCli 2 - ali, four (two symmetric and
two antisymmetric) at SCli 2 - 2an, and two (one symmetric and one antisymmetric)
at SCli 2 - 3ali.
EXAMPLE 12.6
Consider the Hamiltonian:
1 1
H ( 1,2 ) =T1 +T2 +2"Mw
22 22
r1 +2"Mw r 2 •
where the subscript ± stands for symmetric and antisymmetric wave functions re-
spectively and the 1/.../2 is inserted to ensure wave function normalization.
EXAMPLE 12.7
Consider a particle subject to the Hamiltonian:
H = In (1 + ~ (L! + L!)).
Discuss the energy levels of this system and their degeneracies.
One uses the identity:
to obtain
198 Chapter 12
Hence one deduces:
The first few levels and their degeneracies are illustrated in Table 12.4.
One notes that one can write for Elm, Elm = In (1 + na), n = 0, 1, 2 ... , with
different degeneracies for different values of n.
For small a,
Adding a term proportional to L z will remove some or all the degeneracy depend-
ing on the coefficient in front of this additional term.
Consider an energy level p which is say j-fold degenerate. If nil n2, n3, n4, ... nj
label the corresponding degenerate states, it may not be possible to use the pertur-
bation expansion Eq. (11.14) directly. In particular if the perturbation V connects
:s
any of the j degenerate states say n = nl and m = ni where 1 < i j, i.e. Vn1ni =
TABLE 12.3
Degeneracies of Hamiltonian in Example 12.6
Partial Total
Energy 1 m
Degeneracy Degeneracy
0 0 0 1 1
In(1+0:) 1 ±1 2 2
1 0 1
In (1 + 20:) 3
2 ±2 2
In (1 + 30:) 3 ±3 2 2
In (1 + 40:) 4 ±4 2 2
2 ±1 2
In (1 + 50:) 4
5 ±5 2
2 0 1
In(1 +60:) 3
6 ±6 2
In(1+70:) 7 ±7 2 2
(nl IVI ni) =f:. 0, there will be terms in this expansion with a zero energy denominator
lOnl - tOn, and a non-zero numerator Vnln ,. In this case Eq. (11.14) will consequently
be divergent. The way out of this difficulty is to use the fact ~ee Eqs. (12.5), (12.6) )
that one can take different combinations of the j degenerate functions, in particular
a combination for which all Vn,n,1 = 0, i =f:. if, where i, if S j. To do this one
diagonalizes V in each subspace of degenerate states. The resulting eigenfunctions
will have only diagonal matrix elements of V.
If one therefore uses this (rather than the original) basis in Eq. (11.14) it will not
diverge since terms with zero denominator also have zero numerator. Moreover the
eigenvalues of these diagonalizations are to first-order just the energies of each level
p since Ep = lOp + Vpp to this order and only the diagonal elements contribute to Vpp
in this new basis.
In the simple case of two degenerate states nl and n2 connected by V, the nor-
malized combination one must choose (which uncouples if 0: = 0) is:
(12.8)
2 Viz
tan 2a = V, V;' where Viz = (nIl V Inz) etc., (12.9)
11 - zz
(provid ed Viz = VZl )'
If one has three degene rate states nl, nz, and n3 connec ted by
V, a normal ized
combin ation (which uncoup les when a, 13 = 0) that one may choose
is:
(12.10)
where one wishes to find the energy of the second excited state.
More specifically, if
Vo = 0, EN = (N + l)1iw, and one is interes ted in the state with N
!
= 2.
Clearly the Cartesi an basis is conven ient here, where the basis
states for N = 2
are
12l) = ¢z(x)¢o(Y),
12z) = ¢l(X)¢I(Y),
12 3 ) = ¢o(x)¢z(y).
(cf. Eq. (12.4) ).
Using Eq. (12.11) , tan 2a = 2Viz/ (ViI - \l2z) = 0, tan a = \l23/Vi3
= 0, i.e. a = 0,
since ¢1(0) = o.
Degeneracy 201
Additionally
2Vi3 2<p~(0)<p~(0)
tan 2(3 = Vil _ Va3 = <p~(0)<p~(0) _ <p~(0)<p~(0) = 00,
i.e. 2(3 = 7r /2, (3 = 7r / 4.
Thus:
1
= v'2 {<P2(X)<PO(Y) + <PO(X)<P2(Y)}
Vomw
31iw + (2~ 1V 12~) = 31iw + 2Vo<p~(0)<p~(O) = 31iw + ~
-v,1o = 'L.J
nSt
" ( (n +n +l)1iw-E
ny :r: y
1 ) 4>n.,(O)4>ny(O),
2 2
I.e.
_~ _- 24>~(0)4>~(0).I.e. f -
./..2(0)./..2(0)
_ 2V,0'1'0 '1'2 ,
V,o -f
EXAMPLE 12.9
Consider the Hamiltonian:
H= Ho+ V,
where:
Degeneracy 203
which involves the two-dimensional oscillator as the unperturbed Hamiltonian Ho in
this decomposition, and where one wishes to find the energy of the first excited state
(i.e. if ,X = 0, EN = (N + 1)1iw, where N=1).
Clearly the Cartesian basis is convenient here, with basis states:
i.e. a = 7r /4.
Thus
(12.14)
= 2nw+ Anw
2
E 2 ~w _ Anw
10 = n 2'
1/;10 = ~ (~;) 1/2 (1 _ ,\2f/8 exp ( M W 7 X2)2X (~;) 1/2 (1- ,\)1/4
X exp (
M wv'f+'"1
21i
Y2)
1
y'2 {<Pl(X)<PO(Y) - <PO(X)<Pl(Y)} + O(A),
Degeneracy 205
and
results which are consistent with Eq. (12.14) to within an unimportant overall phase.
EXAMPLE 12.10
Consider the Hamiltonian:
h2 d2
H = - 21 d(p + Vah' ( ¢ - ¢o)
Treating _h 2/2I d2/d¢2 as Ho, there are two possible pairs of degenerate eigen-
functions, either:
or:
'if;l = (1 exp(in¢),
y?;; and 'if;2 = (1 exp(-in¢),
y?;;
(n n
each pair having eigenvalues En = 2 h2 ) /21, where must be an integer so that
'if;(¢ + 211") = 'if;(¢) , i.e. is single valued. Consider cases for which n "# o. (The
case n = 0 gives the non-degenerate ground state for which the wave function is a
constant.)
Choice 1: For the choice:
Va 2 Va Va. 2 -I..
Vil = -;- cos n¢o ; Vi2 = 211" sin 2n¢o ;
TT
V22 = -
11"
sm n'l'O ,
and
(2 Va/211") sin 2n¢o 2
tan 2a = 2
(Va/1I") cos 2 n¢o - (Va/1I") sin n¢o
= tan
-I..
n'l'O, I.e. a = n¢o.
206 Chapter 12
Thus
€n + -
Va 1211" sin2 n (</> - </>0) 0 (</> - </>0) d</> = €n ,
7r 0
a result independent of </>0 ,i.e. of the choice of original axis orientation.
Choice 2: For the choice:
InI} = ~exp(in</»,
v27r
and In2} = ~exp(-in</»,
v27r
one obtains:
En = tOn + (n~ IV In~) = tOn + V11 cos 2a + V22 sin 2a + ~ (V12 + V21 ) sin 2a
= fn+ V1I +
2
V22 V1I - V22
+ 2
2
cosa+
V12 + V2I . 2
2 SIna.
( Vll -V22 )( V12 -V21 ) ± ( V12+V21 h/( Vll -\I22 )2+4 V12V21
( Vll - V22 ) +( V12 +V2l )
Hence:
(12.18)
The Eq. (12.18) is quite general. In fact it involves the solutions of the eigenvalue
equations which result from diagonalizing the Hamiltonian H in the space of two
degenerate states nt, n2, i.e.
=0.
"21 H22 - En
Substituting in Eq. (12.18) the values of Vib "22, and Vi2 for the choice 2 one
obtains:
En
Va
= En + -, En = En ,
1f
which as expected are identical with the energies resulting from the choice 1 for the
degenerate basis, since measureable results should not depend on what degenerate
combination of states one chooses.
EXAMPLE 12.11
For the Hamiltonian in Example 12.10 calculate the second-order energy contri-
bution.
Using the choice 1 for the degenerate states one obtains:
depending on whether m is (1/ -Ji ) cos me/>, or (1/ -Ji )sin me/>. Also
{m I Yo 8 (e/> - 4>0) In~} = o.
Thus:
208 Chapter 12
a result, which like the first-order expression is independent of rPo, i.e. of the choice
of axis orientation. Thus:
Hence
h 2 /21,
2h2 /1+ Vo/7r - 31V02/8h 27r 2 + ... ,
etc.
EXAMPLE 12.12
The 2S1/ 2 and 2p1/2 states of the hydrogen atom are separated by an energy fj.E
known as the Lamb shift (where fj.E/h =10 9 Hz). Consider these two states in
the presence of an electric dipole field Vd = (Ame/h) z. Neglecting the other energy
levels of hydrogen, calculate exactly the two new eigenstates of the system and the
corresponding eigenvalues. Compare these results with the eigenvalues obtained using
non-degenerate and degenerate perturbation theory. (N.B. Consider carefully the
parity of the integrals involved.)
Defining:
me
V = hZ,
one obtains
Also
a2 = E1 - f1 _ (-(f1 - (2)/2 + -)(f1 - (2)2/ 4 + ,\2 (IIV12}2 )
a1 ,.\ {IIV12} - ,.\ {IIV12}
and
etc.
If
"\{IIV12} « (f1- f2)/2,
2{IIV12}2
E1 rv f1 + ,.\ + ... ,
f1 - f2
and
Also
,.\ (21VII)
a2 rv aI,
f1 - f2
etc., in agreement with non-degenerate perturbation theory for E and 1/J.
If ,.\ {IIV12} » (f1 - (2) /2, f1 rv f2 , i.e. the Lamb shift is much smaller than the
effect of the electric dipole field, and
and a2/a1 rv 1,
in agreement with the degenerate result (cf. Eq. (12.9) ) for the case tan2a = 00,
1.e.
EXAMPLE 12.13
Consider the same Hamiltonian as in Example 11.9, namely the Schrodinger equa-
tion for a particle which is confined to a two-dimensional square box whose sides have
length L and are oriented along the x and y coordinates with one corner at the origin,
and additionally subjected to a small perturbation:
but invesigate the first-excited state rather than the ground state.
In this case there is a two-fold degeneracy, namely:
h 2 7r 2 5h 2 7r 2
101 = 102 = 2mL2 (12 + 22) = 2mL2 .
Also one can easily show:
=0.
EXAMPLE 12.14
Consider the same Hamiltonian as in Example 11.10, namely
the Hamiltonian:
H = IT
nO + v:, h
were IT
nO = 2m
p~ p~ + 2"1 mwo2 (2
+ 2m 2)
Xl + X2 1 2 (Xl - X2 )2 ,
an d V = 4"mw1
tP01(X,y) = 4>O(X)4>t(Y)
{
tPlO(X,y) = 4>t(X)4>O(Y).
The unperturbed (or zero-order) energy of these two states is:
Setting up and diagonalizing the perturbation in this degenerate basis, after a bit of
calculating one obtains:
3fiw~ fiw 2
El = 2fiwo + - -, or E1 = 2fiwo + _ 1 .
4wo 4wo
This may be compared to the exact energies for these states:
E01 =
3
-fiwo
1
+ -fiwo 1+
(W- t )2 '" 21iwo + -fiw~ ,
2 2 Wo 4wo
(12.19)
= 1 3
-2fiwo + -2fiwo 1 +
(W- t )2 '" 2fiwo + -
3fiw~
-.
Wo 4wo
EXAMPLE 12.15
Find the minimum degeneracy in the N = 4,5 dimensional systems for "central"
potentials:
VN(r), r = Jd + r~ + r~ + ...rh.
Using Eq. (8.15), the number of m values for a given 1 is:
EXAMPLE 12.16
Find the degeneracy of the Mth energy level of the four-dimensional harmonic
oscillator.
The allowed energies of this system are given by (d. Eq. (8.18) ):
M-l
and for M even L (l + 1)2,
1=1,3, S
EXAMPLE 12.17
Find the degeneracy of the Mth level of the five-dimensional harmonic oscillator.
The energy of this system is (d. Eq. (8.18) ):
~l (l + l)(Z + 2)(21 + 3)
for M odd
L..J
1=0,2,4
6 '
EXAMPLE 12.18
Extrapolate the results of Examples 12.16, 12.17 to the Mth level of the N-
dimensional harmonic oscillator.
In the notation of Examples 12.16, 12.17 the degeneracy of the Mth level of the
three-dimensional harmonic oscillator is Cr+! = M(M + 1)/2 where M = n1 + n2 +
n3 + 1 = 2n + 1 + 1, while that of the Mth level of the two-dimensional system is
cf! = M ( d. Example 12.1), where M = n1 + n2 + 1 = 2n + m + l.
For the N-dimensional oscillator the degeneracy of the Mth level where M = n1 +
n2 + n3 + ... nN + 1 = 2n + 1 + 1, and E = (M + (N - 2)/2 )1iw, is
M+N-2 (M +N - 2)!
(12.22)
CN _ 1 = (N - l)!(M - I)!
for M odd 11
1=0,2,4
(21 +N - 2)(1 + N - 3)!
I!(N - 2)! '
and for M 1:
even 1=1, 3, 5
1
(21 +N - 2)(1 + N - 3)!
l!(N - 2)!
CHAPTER 13
Usually in Quantum Mechanics one is given the potential of a system and one
wishes to find the energy levels and eigenfunctions if the particle is bound, or the
wave functions and hence the amount of scattering off this potential if the particle is
free. Sometimes however, one knows the wave function (or phase shifts) and wishes
to find the potential which produces this wave function (or these phase shifts). In
the literature this is known as the 'inverse' problem.
Consider the one-dimensional eigenvalue equation:
",2 d2 }
{ -2mdx 2 + Vex) w(x) = EW(x).
EXAMPLE 13.1
Find Vex) for:
One evaluates
1 d2 w(x) 2
W(x) ~ x2 - a2 '
Ixl < a.
From Eq. (13.1) this implies
",2
Vex) = E + m (2
x -a 2)'
Ixl < a. (13.3)
To find Vex) and E individually and unambiguously, one must impose an addi-
tional condition.
Suppose one is also given the information that (WIVIW) = O.
This implies
The Inverse Problem 215
and
Ixl < a,
(13.4)
= 00, Ixl > a.
Figure 13.1 is a plot of the wave function in this example (and Figure 13.2 of
the resulting potential) and of the very similar function (in this region), cp(x) =
VIla Cos7rx/2a. _1_
1~ V':(x).~~(a2-x2)
~'/
/
/'
/
/
'/
V
__L -________________ r-________________ ~x
-0 o
Figure 13.1: Wave function in Example 13.1 (full line) and the similar
wave function cp(x) = VIla cosn;/2a (dotted line).
Other conditions, for example that V(O) = 0, or E = 0 merely shift the energy
reference.
v(x)
6(x) = ~ cPlxl
2 dx 2
for the delta function one obtains
1 d21li(x) 2 2Ct
Ili(x) dx2 = -2Ct6(x) + Ct - j;f .
Hence
2 2 r,, 2Ct [ 1
V(x) = E + r,,2m
Ct ]
- --;:;;- j;f + 6(x) ,
I.e.
V(x) = _ r,,:Ct [I!I + 6(X)] '. E = _ r,,;:2 . (13.6)
!Cx)
EXAMPLE 13.3
Suppose
w(x) = vaexp (-alx!), (13.7)
find Vex), E.
Evaluating
1 d2 w(x) 2
w(x) dx2 =a - 2a8(x),
v (x)
find V(x),E.
Evaluating
The identification
(13.10)
is acceptable.
This problem is illustrated in Figure 13.5.
fIx)
2 15/ 4
afc'/4)
If the form of the potential is known, the detailed parameters may sometimes
be deduced in a straightforward way from the scattering data. This is illustrated in
Example 13.5.
The Inverse Problem 219
EXAMPLE 13.5
Given a beam of particles of mass m and energy E incident on a step potential
Vo. If n is the fraction of the particles reflected, find the height of the potential.
This problem is illustrated in Figure 13.6, where E must be greater than Vo since if
E < Vo, n = 1.
v (x)
where
k- J2mE
- n,2'
Matching the wave function and its derivative at x = 0 one obtains
IBI2
A
= n = (~)2
k+k"
I.e.
v; _ [-8n + 4(1 + n)y'n] E (13.11 )
0- (1-n)2 '
where as n -+ 1, Vo -+ E, while as n -+ 0, Vo -+ O. If n = 0.36, Vo = 0.9375E, etc.
Three-dimensional inverse problems follow along the same lines.
EXAMPLE 13.6
Suppose the wave function describing a spinless particle of mass m, in a short-
range central three-dimensional potential, is:
220 Chapter 13
and
L z ( 4»w(r, 0, 4» = 0 = mlliw(r, 8, 4».
Thus I, ml are zero. Indeed this particular wave function has no 8, 4> i.e. no angular
dependence.
Also
uno(r) = rRno(r) = A {exp (-ar) - exp (-{3r)}.
Since the Schrodinger equation for uno(r) (see also Chapter 8) is like that for a
one-dimensional problem one can use Eq. (13.1) and
Thus generally
V r _ ~ [ (a 2 - (32)exp(-(3r) ]
(13.13)
( ) - 2m exp ( -ar) - exp ( - (3r) .
For small r,
V(r) '" Ji2 (a - (3)(a + (3) exp (-(3r) = _ li 2 (a + (3) exp (-f3r) .
(13.14)
2m ({3 - a)r 2mr
The potential Eq. (13.14) is a 'shielded' Coulomb potential, i.e. it looks like a
Coulomb potential for small r but for large r it goes to zero much faster than the
Coulomb potential.
If 1 =f 0 one easily generalizes Eq. (13.1) with the result:
EXAMPLE 13.7
If
Unl(r) = Nr2 exp (_ar2) ,
obtain V,(r) as a function of 1.
One quickly finds:
1 d2un l(r)
i.e.,
Unl(r) dr2 =
Using Eq. (13.15),
E _ 51iw 1i
= -21mw 2 r 2 + -mr
2
- 2 ' Vo(r ) 2 .
If 1 = 1,
E = 51iw
2 '
If 1 = 2,
E _ 51iw 1 2 2 2h2
- 2 ' V2(r ) = -2 mw r - --2 '
mr
etc.
(Various authors use sin SI( k) or tan SI( k) instead of SI( k).)
This approximation is known to be fairly good for channels where the potential
is "weak" in some sense, i.e., the phase shifts produced are small.
In Eq. (13.16) k = .j2mE/1i,2, where E is the energy, and m the mass of the
scattered particle. The function il(kr) is the usual spherical Bessel function.
Using the formula derived in reference 2:
where
d
O(p) == ( dp2
)1 dpd ( dp2d )1 '
one can extract the potential Vi(r) from Eq. (13.16). To do this one pre-multiplies
both sides of Eq. (13.16) by p/+2 and then operates on the resulting expression with
the operator O(k) of Eq. (13.17), (where if one writes p = kr, O(k) = r41+10(p) ).
Hence one obtains:
EXAMPLE 13.8
Given
Vo, r < a,
Vo(r) ={
0, r > a.
Use Eq. (13.16) to obtain the Born-approximation 1 = 0 phase shifts for this potential
and then assuming these phase shifts use Eq. (13.20) to retrieve the potential.
From Eq. (13.16)
Hence
k2 (_~ 80 (k») IV Vo {~ _ sin(2ka)}
2m k 2 4k '
and
~ {k2 (_~ 80 (k»)} IV Vo (sin(2ka) _ 2acos(2ka») .
dk 2m k 4 k2 k
Substituting this expression into Eq. (13.20) and integrating over k :
= -Vo (7r
-2a -7ra ) =0, r > a,
r7r 2
= -Vo (7r
-2r) = Vo, r < a.
r7r 2
224 Chapter 13
EXAMPLE 13.9
Given
Va(r) = Va exp ( -ar 2 ).
Use Eq. (13.16) to obtain the Born-approximation 1 = 0 phase shifts for this potential
and then assuming these phase shifts use Eq. (13.20) to retrieve the potential.
From Eq. (13.16)
= Va exp ( -ar2 ).
EXAMPLE 13.10
Given
Va(1-r/a), r < a,
Va(r) ={
0, r > a.
This potential is illustrated in Figure 13.7.
~------------~-- ___ r
a
= Yo [~_ (1 - cos2ka)] .
2k2 2 4k2a
Thus
= Yo [~_ (1-COS2ka)]
2 2 4k2a '
= Vo [_ (00 sin 2ka sin 2kr dk + ~ (00 (1 - cos 2ka) sin 2kr dk]
7rr io k2 a io k3
_~ b1(k)
2m k
rv Vi ~.!...
4 Y;' k4
{I + ~_
2a
(1 + 3k2 + k4) exp {_
2a a2
k2}}.
a
226 Chapter 13
Hence
References
(14.1)
(m # n) , (14.2)
One-dimensional Systems:
I:
Integrating:
CIi n2(x) d~;x) = 2h~ 1 [h(x) - EA1)] CIi~(x) dx,
X
(14.4)
= E (CIinlhICIim) (CIimlFnICIin),
m¢n
The Dalgarno-Lewis Technique 229
and using closure:
1 = E I~m} (~ml +
m
Jdk I~k) (~kl,
(where the second term on the r.h.s. arises if Ho also involves continuum states):
(14.5)
a result which involves only two, or only one additional integral if for some reason
(e.g. parity considerations) Ei1) = 0, as opposed to an infinite number of matrix
elements.
Similarly the wave function to first order (cf. Eq. (11.15) ) is:
(14.6)
m,pim
a result which needs only two additional integrals for its evaluation. As concerns the
expectation value of an operator 0, using Eq. (14.6), and assuming (<lin 10Fni <lin) is
230 Chapter 14
real,
(14.8)
where in this case N 2 = (1 + LlF; + ... )-1 . Some examples which illustrate the effi-
cacy of this technique are given below, while a concise listing of some of the Dalgarno-
Lewis expressions is given in Table 14.5.
EXAMPLE 14.1
Consider H = p2/2m + V, where
while a = e2/(47rfonc) is the fine structure constant a "" 1/137 which occurs fre-
quently in atomic physics. Treating p2/2m - anc/x as the unperturbed Hamiltonian
Ho, obtain the Dalgarno-Lewis function Fo(x). Use this to obtain the energy of the
ground state to third order, the wave function to first order, and two upper bounds
to the energy of this system.
For the partition Ho = p2/2m - anc/x, h = >.mw2x 2/2,
T
<I>o(x) = 2 J(amc)3 xexp (amcx)
--n- ,
and
(14.9)
One notes this series involves the (square of the) ratio of the energy-level parameter
(viXnw) for the Hamiltonian H' = p2/2m + h to the energy-level parameter for Ho,
The DaJgamo-Lewis Technique 231
(namely o?me2 ), and as ~xpected the bigger w, the more important the repulsive
first-order correction to the energy of this system.
Substituting in Eq. (14.4) with the convenient choice a = 00 one obtains:
4095 3{ fiw }6 2 2 55 2{ nw }4
(C)O 1FohFo I)
C)O = 16A Ot2me2 Ot me, and <C)o 1Fo21 C)O ) = '2A Ot 2 me2 •
5451
Eo(3) _- -32 \3{
1\
fiw
-2--2
}6Ot2me2.
Ot me
Thus
where N = 1, or
232 Chapter 14
If one uses as trial wave function in Eq. (10.2), CI>o, the ground-state wave function
of Ho in the decomposition H = Ho + h, one obtains:
Eo = Eexact ground state :::; E~O) + E~l). (14.11)
If one instead uses as trial wave function in Eq. (10.2), Wo from Eq. (14.6),
i.e. the wave function correct to first order (with N = (1 + ~FJ)-1/2), one obtains:
E(2) E(3)
E E < E (O) + E(l) + 0 + 0
0= exact ground state - 0 0 1 + Lm#o Vom VmO / EO
(-)Em
2
E(2) E(3)
= E(O)
o
+ E(l) +
0
+ 0
1 + ~FJ .
0 (14.12)
All the terms needed to evaluate Eq. (14.12) are known in this case, yielding
Eexact ground state :::; E~O) + E~l)
2a
->.?o?mc {~}4
2 mc2
{129/16 - (545LX/32) [1i.w/a 2mc2]2}.
1 + (319.\2/16) [1i.w/a 2 mc2]4
(14.13)
Both Eqs. (14.9) and (14.13) are upper bounds to Eexact ground state ,and
Eq. (14.13) is a better upper bound than Eq. (14.9) if [VX1i.w/a 2 mc2 t< 86/1817.
EXAMPLE 14.2
Consider the system
H =p2/2m+ V
x ~ 0,
x:::; 0,
p2 1
Ho = -
2m
+ -mw
2
2 2
x
'
and
Then
CI>o(x) = {7r/4~~4exp(-m;;2),
CI>l(X) ~{:;r/4 {2[v'T xf - 3v'T x} exp ( - m;;2) ,
The Dalgarno-Lewis Technique 233
)..ft2 E~l)
Eo(O) = ~ftw E~l) = 2)"ftw, and h(x) = -mx2 = 2mwx 2/ft .
2 '
If ).. = 1, E~O) + E~l) = 7ftw/2, as opposed to the exact answer in this case (see
Example 10.5 ), namely Eo = 5hw/2.
Evaluating the Dalgarno-Lewis function:
where
W{x) = ~~ {h{x) - E~l)}.
With the convenient choice a = 0 which satisfies <Po (a) = 0, and using6
Fo{x)
which satisfies Eq. (14.1) as one can easily verify. Substituting into Eq. (14.5) yields:
2[E~1)]2 {
10 10
00 00 }
Eo(2) -- Vifiw exp (_u 2 ) In u du - 2 u 2 exp (_u 2 ) In u du
[ (1)] 2
= 2 Eo {_ Vi (-y + 210 2) + 2Vi (-y + 21n2) _ Vi}
Vifiw 4 8 2
[ (1)] 2
= -~
fiw
= -4)..2fiw '
(where'Y rv 0.5772157, and one has used I;' exp (-ou 2 ) In u du = - (Vi/4)[ 'Y +
In 40 ] 0- 1 / 2 and derivatives ofthis expression with respect to 0 ). If).. = 1, E~2) =
-4fiw, and E~O) + E~l) + E~2) = 3fiw/2 + 2fiw - 4fiw = -fiw/2.
Substituting into Eq. (14.7) (using the expression 1000 exp (-ou 2){ln u)2du = (..;:;/8)
(b + In 40]2 + 7r 2/2)0- 1 / 2 and derivatives of this expression with respect to 0 ) one
additionally obtains
234 Chapter 14
Finally substituting into Eq. (14.12):
3 -4,X21iw + 16,X31iw
Eo = Eexact ground state::; '21iw + 2'x1iw + 1 + ,X2(7f2/2 _ 4) .
For'x < 1/4 this is a better upper bound than E~O) + E~l).
That the choice a = 0 is the correct one in this case can be verified by checking
that
(~olhl~l) = 2~ = (~olFol~l) .
fO - fl v6
Using this expression one can also compare:
2 + v'1 + 8'\ ) (3
Eexact ground state = ( 2 1iw'" '2 + 2,X - 4'\
2
+ 16'x3 -... ) 1iw.
EXAMPLE 14.3
Consider H = Ho + h, where
p2 1 2 2 ;mw x
= ,X1iwYT
Ho = 2m + 2'mw x , h (all x).
One can also evaluate the exact ground-state energy in this case Eo = nw /2 -
,X 21iw /2 since
The Da,lgarno-Lewis Technique 235
~
H=-+-{/
2m
~
2
~
n
2
x+>.} _>.2_=_+_ x+
~
2
~
2m
~
2
{ If } h
->.
mw
2
~
_>.2_,
2
EXAMPLE 14.4
Given H = Ho + h, where
p2 1 2 2
Ho = 2m + '2mw x ,
Find Fo(x), E~2), etc.
From Example 14.3 Ci>o and E~O) are known
E~l) = >.nw / Ci>o Imw2x21 Ci>o) ~ = >'hw ~nw ~ = A1i.w .
\ 2 nw 4 nw 2
= _ >.2 hw >.3 h
Fo(x) = -2">. [mw]
T x2, EO(2)
4 '
E(3) _
o - 4 w.
The exact ground-state energy in this case can easily be shown to be:
EXAMPLE 14.7
Obtain F1(x), and E~2), if
Here
CPl(X) = {T
mw }3/4.,fi Xexp (mwx2)
7r1/4 ---v;:- , and E(l)
1
-- )'~1i
2 w.
In this case
mwx2
Fl(X) = -).--v;:- ,
(the same result as for Fo{x) of Example 14.4), an expression which can easily be
shown to satisfy Eq. (14.1). Using F1{x) one obtains E~2) = _).2 3Tiw/4, which agrees
with the).2 term in the expansion of the exact first excited-state energy (31iw/2) (1+
2).)1/2 in powers of ). (cf. Example 14.4). (The Fn{x)'s for this system if n > 1 are
more complicated than Fl(X) = Fo{x). )
EXAMPLE 14.8
Given
Fo(x) =
and from Examples 14.6 and 14.7,
-AlJ~W x - ~2 {J~w x r,
I.e.
I, nWAi
Eexact ground state = 2nwy 1 + 2A2 - 2(1 + 2A2) ,
3, nWAi
Eexact 1st excited state = 2nwy 1 + 2A2 - 2(1 + 2A2) ,
expanded to order A2 •
EXAMPLE 14.9
Given the Hamiltonian:
H = - - - +A
p2
--,
anc n2
x 2:: o.
2m x 2mx 2
Treating h = An 2 /2mx 2 as a perturbation, study the energy of the ground state of
this system. The unperturbed ground-state and first-excited state wave functions are
iP o(x)=2V FIT-n-J
amc] 3
xexp
( amcx) ,iPl(X)= ~ [~]3 X(I- :.~) exp(-~)
--n- 2 n 2 n 2n'
and the unperturbed ground-state energy is
238 Chapter 14
The exact energy if ). = 2 is -a.2mc2 /8, which (E~O) + E~1) being an upper bound)
is less than (-1/2 + 2)0:2mc2 = 30: 2mc2/2.
Using Eq. (14.4) (with a = 00, for which value 4>o(a) = 0) one obtains Fo in this
case:
F.o(x ) = ).~
Ii x + ),1n 20:mcx
Ii .
1o
00 'Y In 0:
exp ( -o:u) In u du = - - - -
0: 0:
,
and derivatives of this expression with respect to 0:, and the constant 'Y '" 0.5772157.
Using Eq. (14.7) one can also evaluate E~3) with the help of the integral
EXAMPLE 14.10
Given the Hamiltonian H = Ho + h, where
<llo(x) = { mw}1/4
7rh
(mwx2)
exp - ' j j t .
By using
o 2 + 1 .. k=l
2k-2U2k+1
(-w )dw = 3exp (_u L:
[U 00
10 w 4 exp 2 (k )'"
2)
o k=2 2 + 1 ..
(results which may be obtained via integration by parts) in Eq. (14.4) one obtains
(14.14)
EXAMPLE 14.11
Given the Hamiltonian H = Ho + h, where
Ho = ;~ + ~mw2x2, and h = )'hw {j";,.w x} 4 , (x ~ 0).
Obtain Fo(x), etc.
Using
(U
10 w6 exp (-w 2 )dw = 15 exp (_u 2 ) E
00 2k-3U2k+1
(2k + I)!! '
in addition to the integrals in Example 14.10, and substituting in Eq. (14.4) with
a = 0 one obtains:
(14.17)
Hence
E(l) _ 15)'h
o - 4 w,
Evaluating
(q>olhlq>l) = _~). = (q> IF. Iq> ).
-2hw 2V6 0 0 1
This verifies that a = 0 (for which value q>o(a) = 0) is an acceptable choice and
one has:
EXAMPLE 14.12
Given the Hamiltonian H = Ho + h, where
The Dalgarno-Lewis Technique 241
Obtain Fo(x), E~l), E~2), etc.
By straightforward calculations one obtains:
o - ~An
E(l) -
2 w, Fo(x)
rmwx }2 ,
= -2"). {VT
Evaluating
~ 1 ~ 1
H = - + -mw 2(1 + 2).)x2 = - + _mw'2x 2.
2m 2 2m 2
For this Hamiltonian, Eo = 3Iiw'/2, where w' = w(1 + 2).)1/2. Thus
3 3 3 2 3
Eo = -nw + -)'liw - -). nw + -).3 nw - ....
2 2 4 4
EXAMPLE 14.13
Consider a one-dimensional system with Hamiltonian:
H :m +
2
Vex)
2
m e 3
Vex) = ).--x (Ixl < b), (14.18)
Ii
= 00 (Ixl > b),
where). is a dimensionless constant.
The obvious perturbation-theory decomposition of this system, (which cannot
be treated exactly analytically) is:
p2
Ho =
2m
hex) ).me2 {mc
fiX } , (Ixl < b), (14.19)
00, (Ixl > b).
Here
242 Chapter 14
and E(O) = (n + 1)2n211"2
n 8mb2
One immediately obtains
(14.20)
since h(x) has odd parity. (Using Eq. (14.7) one also obtains Ei3) = 0, in this case
since h and Fn have the same parity.) Substituting into Eq. (14.4) for Fo(x),
= SA ( ~: )' rOb "",' y' {(~' + ~(2(',", 2(' + eo, 2(')}1:~/" dy'
= mcb)3j1rX/2b {(y' - 2"1) sec y' + 2y' tan y' + 1
4>. ( n1l"
2
r
2
-sec2 y' ( {;: + {;:} sin [7rba ] + cos [;a/b1) } dy'. (14.21)
Here an ambiguity arises because there is no obvious choice for a. Two choices
suggest themselves, namely a = 0, and -b. The first choice however does not satisfy
the condition cp( a) = O. The second choice (a = -b) results in:
as opposed to
(14.23)
Evaluating this expression shows that the choice of Eq. (14.22), namely a = -b is
the correct one. Once one has evaluated this expression one can also immediately
The Dalgarno-Lewis Technique 243
display the first term contributing to the second-order energy, namely,
One may additionally confirm that «(«PO\FOI«P2) being zero from parity considera-
tions),
(14.25)
Thus
213 ).2mc2 [mCb] 4 _ 215 ).2me2 [mCb]4
I53 5 11"6 h 3555 11"6 h
=
,\2mc2 [mCb]
-(33.7119 + 0.0432 ... )---;;:s T 4 (14.26)
-33.7551 A;;;e
\2 2 [
m;b] ,
4
E o(2) -
-
showing that almost all the correction in this case comes from the first-excited state
and incidentally that :
212 {I 32 42 }
11"2
(1 - 11"2) 22
15 = 5"" (1 X 3)5 + (3 X 5)5 + (5 X 7)5 + (7 X 9)5 + ... (14.28)
is a very quickly converging series relation (giving 5 digit agreement after three terms,
and 6 digit agreement after four terms) which to the knowledge of the author is not
quoted in the literature3 , 4.
EXAMPLE 14.14
Consider a one-dimensional system with Hamiltonian:
p2 o.he
H = ---+V(x)
2m x
,\ 0. 2me2(20.me) = 1, 2... ),
Vex) = -h-x n , (x ~ 0; n (14.29)
afie
Ho =
2m x
h(x) =
\
AO:
2
me2(2ame)n
-fi-x , (x ;::: 0; n = 1, 2 ... ), (14.30)
00, (x < 0).
Here
Eo(l) -_ 4\(ame)3
A -- a 2 me2la (2ameX)n
OO
- - - exp (2ameX)
- - - - x 2dx
fi 0 fi fi
(14.31 )
SUbstituting into Eq. (14.4) for Fo(x) with the choice a = 00, for which value
iPo(a) = 0,
Fo(x) =
(14.32~
J xnexp(-x)dx = -exp(-x) E
n n!
(n _ k)! x n - k
The Dalgarno-Lewis Technique 245
If one substitutes Eq. (14.32) in Eq. (14.1) one sees that this latter equation is
satisfied by the Fo(x) obtained above. Also one can confirm that the choice a = 00
in Eq. (14.32) is the correct one by verifying (for various n's) that for this value of a:
(14.33)
E o(2) --
(14.34)
E(2)
o
= _,\2a 2 mc2 (n
23
+ 2)! I:
k=O
2(2n +3 -k)! - (n + 2)!(n + 3 - k)! .
(n+2-k)!(n+1-k)
(14.35)
A feeling for the rate of convergence may be obtained by comparing the exact
second-order result for the case n = 1, where Fo(x) = -'\[amcxJn.J2,
versus the first two terms in the second-order expansion in this case, namely
Thus for n = 1 the first term is little over half the total second-order value which
also includes a contribution from the term
since there are also continuum states <I>k in this basis. As noted previously Eq. (14.5)
also automatically includes this contribution. For n = 3 however one obtains E~2) =
-42,780,\2a 2mc2 from Eq. (14.35), versus the first two second-order terms, Eq.
(14.34) rv -37, 883.15,\2a 2mc2 - 2, 432.74,\2a 2mc2, indicating that the convergence
improves with increasing n.
246 Chapter 14
EXAMPLE 14.15
but with
).. J2Otmcx/fi 1
- - dy'
2 2
).. exm ex
= (14.40)
2n
where hFo = )..2ex 2 me2 /4 is a constant in this case. This yields:
E~2) = (~olhFol~o) - E&l) (cJ>olFolcJ>o)
)..2 ex 2me2 3)..2ex2me2
=
4 8
)..2ex2me2
= (14.41)
8
Using Eq. (14.7) one also obtains
E~3) = (cJ>o lFohFol cJ>o) - 2E~2) (cJ>o lFo I cJ>o) - E~l) ( cJ>o IF~ I cJ>o)
3 3 3}
>. 3 ex 2 me2 { 16 + 16 - 8' = O.
In this case one can also trivially solve this problem exactly by writing the
Hamiltonian as
The Dalgarno-Lewis Technique 247
where a' = a(1 - A/2), which has exact ground-state energy:
in agreement with the result obtained by the Dalgarno-Lewis approach above, veri-
fying also that the choice a = 00 was the correct one. One may also write:
EXAMPLE 14.16
p2 1 2 2
Ho=-+-mw x (all x).
2m 2 '
CP1 (x) = {7} 3/4 ~/: exp ( - m;;2) , and E~l) = 0, from parity considerations.
as one can easily verify by substitution in Eq. (14.1), and by noting that
71 2
E1
(2)
= {CP11 hF1 ICP1} = -SA nw.
248 Chapter 14
EXAMPLE 14.17
p2
Ho= -+-mw x
1 2 2
and mw
h(x) = ).}iw { r;:x 2} .
2m 2
1
<P2(X) = ( 2";; )1/2 (mw)1/4
T [2 (mw)
r;:X2 - ] (mwx2)
1 exp -~ .
).[mw2 2 ]
F2(X) = -"2 r;:x - 2(mw/n)x2 -1 '
while
E2 exact = 2"5 nw .J1 + 2), rv nw [52" + 2").
5 5 2 + ....
- 4). ]
EXAMPLE 14.18
1
<P2(X) = ( 2";; )1/2 (mw)1/4
r;: [2 (mw)
r;:X2 - ]
1 exp
(mwx2)
---v;- .
The Da,lgarno-Lewis Technique 249
From parity considerations one concludes that E~l) is zero.
Evaluating Eq. (14.4) in turn yields:
F2 {x} = -..\
rmw x -
[VT 4~x
2 {mw/h}x 2 -1 '
1
a result which may be verified by substitution in Eq. {14.1}.
Hence in this case
(14.43)
+ [E(l)] 2 ""' hnihin _ E(2) ""' hnih in
n L...J .3 n L...J t.2 '
i"#n tn. i"#n m
I.e.
and
I.e.
(mIn).
250 Chapter 14
(One easily confirms that the operators Gn , and In are consistent for the diagonal
case (m = n). ) The equivalent integral expressions, analogous to Eq. (14.4) for Fn,
are:
IX <Pn~y)2 {21i~ l
and
In(x) = Y
[Fn«() - [Fn]nn] <Pn«()2d(} dy.
The first term in Eq. (14.43) for E~4) (assuming hij = hji ) can thus be written
Thus
By a similar manipulation the wave function to second order, Eq. (11.15) can be
cast in the form:
(14.45)
The Da.lgarno-Lewis Technique 251
EXAMPLE 14.19
Obtain the fourth-order contribution to the energy of the ground state of the
system with the Hamiltonian in Example 14.10, assuming the same decomposition
H=Ho+h.
After some calculating one finds:
(14.46)
while
Io(x) = 16~w [{ ~xr +9{ ~xr]· (14.47)
Using the expression for Fn(x) obtained in Example 14.10, one evaluates seven
additional straightforward integrals:
Three-dimensional Systems:
The difficulty with three-dimensional systems is that generally one cannot write
down a closed-form expression analogous to Eq. (14.4) for the three-dimensional
counterpart of Fn. One must therefore fall back on Eq. (14.1).
If
252 Chapter 14
and VCr) is purely central, then
UlO(r) = ame]
2VFIT-h-J
3
(amer)
rexp --h- ,
while
1 [2 Fame]5 2
IT-h-J r exp (amer)
1 2 2 1
U21(r) = "4V"3V --v;- , and t I
2 me-
= --a n2·
a
n
Suppose
h = 'xa 2me2 [a~ez] = 'xa2me2a~crYr}((),4».
This potential corresponds to the perturbation introduced by a constant Electric
Field Eo in the z direction since such a field is equivalent to a potential -zIEol. Find
E 10
(2)
•
For this h one can easily verify that
f 10l ( r ) = _A amer
Ii
(~
2h + 1)'
Tbe Dalgarno-Lewis Tecbnique 253
satisfies Eq. (14.48), where [' = 1, m' = O.
The first-order energy E~~) for (the ground state of) this system is zero due to
parity considerations. Hence
(2)
ElO = ( <1>100 IhFnlI' I<1>100 ) = - 27 >. 20: 2mc2.
1611"
This expression in turn is related to the first term in the second-order energy expan-
sion for El~). Thus:
EXAMPLE 14.21
Consider the same unperturbed Hamiltonian as in Example 14.20, i.e.:
V(r) = _ o:fie .
r
If
verify that
f 10l' ( r ) = ->. [o:mer]" (_1_~ ~)
fi I' + 1 .", + I' .
Note that Example 14.20 is just a special case of this result when 1'=1.
This result may be verified by direct substitution in Eq. (14.48) with m' = 0,
where, as in Example 14.20, El~) = 0, and
d
dr {lnu 10(r)} =
(1;:- - o:me)
-.",- .
254 Chapter 14
Here
=
>.2a-.2mc2(21' + 2)! (2l'2 + 51' + 2) (14.49)
22/'+471" (l' + 1)l' .
EXAMPLE 14.22
Given the unperturbed Hamiltonian
and
h= h >'1iwyrmw
V{3 T Z = >.1iwYo1 (0, <I»yrmw
T r.
· E(2)
H ence 0 b trun 00'
The relevant unperturbed ground state here is:
uoo(r) =
2
71"1/4
[mw]3/4
T rexp
(mwr2)
----v;- ,
while
(0)
Enl = ( 2n + 1+ 2"3) 1iw.
Whence it is easy to show E~~) = (<Pooolhl<pooo) = O.
One can easily verify:
fJo(r) = ->.J7 r.
Hence
E~~) = (<Pooo I>.J~w rYo1 (0, <1» 1iw ( ->'Yo1 (0, <I»J~w I
r) <Pooo)
= _ \ 231iw (14.50)
A 871" •
The Da,lgarno-Lewis Technique 255
Also direct evaluation confirms that:
= -f[;'\.
This expression in turn is related to the first term in the second-order energy
expansion for E~~). Thus:
_,\23nw = (cJ>ooolhlcJ>OlO) (cJ>01olhlcJ>ooo)
8~ -nw
= _,\23hw.
811"
Thus in this case only one term in the infinite series contributes to this sum, since
EXAMPLE 14.23
Consider the same unperturbed Hamiltonian as in Example 14.22, but let
If both the unperturbed potential V(r) and the perturbation h(r, B, </J) = h(r)
are central, the problem of obtaining F reduces essentially to the one-dimensional
case, since then Fn -+ fnl(r), and the commutator relation becomes
I.e.
[Un! (r ) d2fnl(r) + 2Unl(r)dfn!(r)] = 2m (h( )_E(1») ()
dr2 dr dr 1i2 r n! Un! r
If n' -# n
I.e"
(14.53)
EXAMPLE 14.24
If
H.o = (J;? + ~mw2r2 and h(r) = >'1iw {";;' r2},
2m 2 '
Evaluate E~~), where
u01(r) = Vf8{mw}5/4
3;I72 T (mwr2)
r2 exp --v;- , and
=
8>.1iw roo (2) 6 8>.1iw 15y'7r
31r 1 / 2 Jo exp -u u du = 31r 1/ 2 ~
The Dalgarno-Lewis Technique 257
Substituting in Eq. (14.52) and using the integrals given in Examples 14.10, 14.11
one obtains for this case :
Hence
E 01
(2) -
-
>.mw r 2) >.'hw {mw
JofOO ( -"2T T r 2} U 2 ()
lO r dr -
(1)
E01
>.mw r 2) U 2
JofOO ( -"2T ( )dr
lO r
The main results of this chapter are summarized in Tables 14.1, 14.2, 14.3 and
14.4.
References
1. A. Dalgarno and J. T. Lewis, Proc. Roy. Soc. A233 1955, p. 70.
2. C. Schwartz, Ann. Phys. 6 1959, p. 156.
3. L. B. W. Jolley, Summation of Series, Dover Publications (1961), p. 65.
4. 1. S. Gradshteyn and 1. M. Ryzhik, Tables of Integrals, Series and Products,
Fourth (English) Edition, prepared by A. Jeffrey Academic Press, New York
(1980), p. 7.
5. Op. Cit., p. 92.
6. Op. Cit., p. 306.
7. H. A. Mavromatis, Am. J. Phys. 59 (8), 1991, p. 738.
258 Cbapter 14
TABLE 14.1: One-Dimensional Systems
= 00 (Ixl > b)
The Dalgarno-Lewis Technique 259
TABLE 14.2: One-Dimensional Systems
14.20
xYo1 (O, </J)
(r 2:: 0) Anw [/¥ r)" Yci' (0, </J) 0 0 [' -~ [J¥ r)" Yd'(O, </J) 14.23
k == h - (cJ>nlhlcJ>n) (( cJ>nlhlcJ>n) = 0)
Fn == Fn - (cJ>n\FnlcJ>n) (( cJ>nIFnlcJ>n) = 0)
(N = 1 - (cJ>nlwn) = 1)
Wn = N [1 + Fn + ... J cJ>n
(N- 2 = 1 + (FJ) + ... _ (wnlw n) = 1)
En(3) = ( cJ>n\FnhFnlcJ>n
• •• )
(wnIOlwn) = N 2 ( (cJ>nIOIcJ>n)
(N- 2 = 1 + (1';) + ...)
+2 (cJ>nIOFnlcJ>n) + (cJ>nIFnOFnlcJ>n) + ...)
CHAPTER 15
L == r x p,
the major difference between classical and quantum mechanics is that whereas clas-
sically the vector product of L with itself is zero, i.e.
Lx L = 0,
in quantum mechanics
Lx L = iliL,
or the commutator:
(15.2)
(15.3)
since operating on Eq. (15.2) with Ly and on Eq. (15.3) with Lx and subtracting,
one obtains
(15.4)
(21+1)(l-m)! mi.
47r(l + m)l (-1) Pm ( cos 0) exp (zm1»,
(15.9)
pJ( cos 0) PI ( cos 0),
yields:
00 I [21r 1 00
S(cos O-cos 0') = L L Jo y::.I(O,1»Y~(O',1>') d1> = - L(2l+1)PI(cos O)PI(cos 0') .
1=0 m=-I 0 2 1=0
264 Cbapter 15
Moreover if ()J = 7rj2, defining u == cos(), in the range -1:::; u:::; 1 one obtains:
1
2 L:(21 + I)P1(u)P1(0)
00
c5(u) = . (15.10)
1=0
One notes that only even l's contribute to this infinite series since P1(0) is zero
for odd Z. The result of truncating the sum in Eq. (15.10) at [ = 12 is illustrated in
Figure 15.1, which looks very similar to Figures 2.1-4 .
6 (u)
-1.
EXAMPLE 15.1
Show that the delta function in Eq. (15.10) is properly normalized, i.e. that
f~1 c5( u) du = 1.
1 c5(u) du
-1
1 1 00
= - L:(21 + 1)
2 1=0
1 PI(U) du PI(O)
1
-1
1 00 2
= - L:(2Z + 1) -Z- c510 PI(O) = 1,
2 [=0 2 +1
where one uses the useful orthogonality property of Legendre polynomials namely
that
-1
1
1 P[(U)PI'(U) du = -2[2 c51l',
+1
and the fact that Po(u) = 1. One notes that no matter at what [ one truncates
the series in Eq. (15.10), the normalization condition is always satisfied by this
expression.
Angular Momentum and Coupled States 265
EXAMPLE 15.2
Consider '1/;(8, ¢» = N cos 28 sin ¢>.
Evaluate the normalization constant N and then expand this function in terms
of the complete set of spherical harmonics.
Firstly, to obtain N one evaluates:
{!f; 5
-cos20sin¢>
141r
= L L
00
1=0 m=-I
I
almY~(O,¢» , (15.11)
One notes that cos 20 sin </> is an odd function of 0, </> (since cos (2 {1r - O} ) sin (</> + 1r)
= - cos 20 sin </» so only odd-parity Y,!, functions can contribute to this integral. Since
the parity of the spherical harmonics (i.e. their behavior as x -+ -x, Y -+ -y, Z -+
-z, or equivalently 0 -+ 1r - 0, </> -+ </> + 1r) goes as (_1)1, this implies that one gets
contributions to aim when yl, y3 ... Additionally one can write
1 m Y;'(B, </»
I I
I 0 I 0 l/Vii
1 0 J3/(47r) cosB
1 ±1 -=fJ3/(81r) sinBexp(±i</»
this implies only spherical harmonics with m = ±1 contribute to this integral. Thus
the first non-zero contributions in Eq. (15.11) are a1±1.
From Table 15.1
3
-=f ( 87r
)1/2 V{T5 1 f"
14; 2i Jo (2 cos B-1) sin B dB
2 2
Thus
Example 15.2 involves an infinite sum. Sometimes however one only has a finite
number of terms in one's expansion.
EXAMPLE 15.3
Consider .,,(0, <1» = N sin 0 cos 20 sin <1>.
Evaluate the normalization constant N and then expand this function in terms
of the complete set of spherical harmonics.
Firstly, to obtain N one evaluates:
Thus to within a phase N = V105/(767r) . One also notes .,,(7r - 0, <I>+7r) = -.,,(0, <1»
i.e. only odd l's will contribute to this expansion. The sin <I> term further restricts
the expansion to m = ±1.
One notes here that with the help of Table 15.1 one can write:
(exp(i<l»~;XP(-i<l»)
a
.,,(0, <1» = NsinO(2cos 2 0-1)
The orbital angular momentum operator is a special case of the general class of
angular momentum operators:
J X J = inJ,
for which one can write, analogously to Eqs. (15.4), (15.5):
(15.12)
0, 1, 2, 3 ...
and for a given j, -j :::; mj :::; j where mj changes in integral steps.
J(1)xJ(2) = 0 = { J(2)xJ(1) }
(15.14)
which is the case say if J(l) operates on space 1, while J(2) operates on space 2, then
the sum of these two angular momenta the "total angular momentum operator"
Angular Momentum and Coupled States 269
EXAMPLE 15.4
Verify that J defined in Eq. (15.15) is an angular momentum operator if Eq.
(15.14) is satisfied.
Consider
since summing the k term of Eq. (15.14) including both orderings of coordinates 1,
and 2, yields the result:
J2 [¢Jl(I)¢i2(2)t (15.18)
J
Jz [¢i1(I)¢i2(2)t (15.19)
J
where
The j in this equation can have any value in integer steps between IiI - j21 ~ i ~
il + ja,
while mj = mh + mh, and the coupling coefficients (jIj2mitmj2Ijmj) are
270 Cbapter 15
TABLE 15.2
Wigner (or Clebsch-Gordan) Coupling Coefficients
J= m2 = 1/2 m2 = -1/2
j1 + 1/2 it+m+1/2
2i1+1
i1-m +1t.2
2it+1
TABLE 15.3
Wigner (or Clebsch-Gordan) Coupling Coefficients
J= m2 = 1 m2 =0 m2 =-1
(it-mHit- m+1)
j1 +1 (j1+m){j1+m+1)
2(it +1)(2it +1)
(j1-m+1l(it +m+1)
(2it +1)(it +1) 2(j1 +1)(2j1 +1)
J= m2 = ±3/2
i1 + 3/2 (il±m-1L2}(iI±m+1L2)(jI±m+3/2}
2UI +1)(2it +1)(2il +3)
3(jl±m-1L2)(jI±m+1L2}(jl=Fm +3L2}
i1 + 1/2 T 2il (2jl +1 )(2il +3)
i= m2 = ±1/2
iI'fm+1/2
i1 -1/2 - (i1 ± 3m - 1/2) 2(j1+1)(2il 1)(2il +1)
J= m2 =±2 m2 = ±1
j1 +2 (it±m-1l(j,±ml(j,±m+1)(j1±m+2}
4(j, +1)(2j, +1)(2j1 +3)(it +2)
(it -m+2l(j1 +m+2l(jdm+1}(j1 ±m}
(2i1 +1)(i1 +1)(2i1 +3)(i1 +2)
I (it±m-1)(j,±m)(j1±m+11(j1 'Fm+2)
j1 +1 =F 2j1 (i1 +1)(i1 +2){2j, +1) =F (j1 =F 2m + 2) (j,±m+1)(idm)
2it (2i1 +1)(i1 +1)(j1 +2)
3(h±m-1Hit±m)(j1'Fm+1Hj,'Fm+2) 3(i1'Fm+1Hh±m)
J1 2(2j, -1)it (j, +1)(2i1 +3) (1=F2m) 2(2i1-1)i1 (i1 +1)(2i1 +3)
j1 -1 (j1±m-1l(i1:Eml(h'Fm+1l(i1:Em+2} (j1:Em+1}(j,'Fm}
=F 2(j1- 1)j, (i1 +1)(2j1 +1) ±(it ± 2m -1) 2j1 (i1 -1)(2i1 +1)(j1 +1)
j1 - 2 (j1:Em-1l(j,:Eml(i1:Em+1l(i1:Em+2} - (i1:Em+1l(i1:Em)(i1'Fm-1)(i1±m-1)
4i1 (j, -1)(2i1-1)(2j, +1) i1 (i1 -1)(2j, -1)(2i1 +1)
J= m2 =0
3m 2-hU1 +1)
j1
V(2i1-1)il(i1 +1)(2il +3)
3(h-m)(h+m)
j1 -1 -m
(i1 1)il (2i1 +1)(i1 +1)
Some simple angular momentum coupling coefficients are given in Tables 15.2-5.
In some simple cases one may obtain the coupled wave functions and consequently
the corresponding coupling coefficients using symmetry arguments.
Consider for simplicity two eigenfunctions <p~231 (1) and <p~232 (2) each having angu-
lar momentum quantum number j= 1/2 and two possible projections mj = ±1/2.
Assume that they are eigenfunctions of two operators J(I), J(2) which satisfy Eq.
(15.14). There are two possible eigenfunctions for each ofthese two operators, namely
<p!~~(i) and <P~:/2(i), (i = 1, 2). One can thus construct four product states:
l/2( 1)<P1/2
<P1/2 l/2()2 , <P1/2
-1/2 (1) <P1/2
-1/2 () l/2()
2 , <P1/2 1 <P1/2 2 , <P1/2
-1/2 () l/2( 2).
-1/2 (1)<P1/2
The first two of these states are symmetric under interchange of particles 1 and 2,
whereas the third and fourth are neither symmetric nor antisymmetric under such an
interchange. Since J as defined in Eq. (15.15) commutes with the exchange operator
P12 (d. Example 12.5 and subsequent discussion) we should be able to, and in fact
can, immediately construct normalized symmetric and antisymmetric combinations
of these latter states as follows:
(15.21 )
Grouping states by symmetry alone one thus has three orthonormal symmetric
states :
If one operates on the symmetric states, Eq. (15.22) with the operator:
one obtains 1(1 + 1)n 2 times these states, while if one operates on Eq. (15.23) with this
operator one obtains 0=(0+1 )11.2, i.e. one has three symmetric states with quantum
number j=l, and one antisymmetric state with j = O. operating on these "coupled"
states with the operator Jz = {Jz(l) + Jz(2)} one obtains mj = n, 0, -n times the
wave functions respectively for the three states of Eq. (15.22) and 0 times the state of
Eq. (15.23). This justifies the notation for the wave functions in Eqs. (15.22), (15.23).
Thus instead of the four product states above one has obtained four equivalent states,
which however are eigenfunctions of the total angular momentum of this system, the
"triplet" ""L ""~, "":1>and the "singlet" ""g, i.e. 2 ® 2 = 3 + 1. One notes that in
all angular momentum couplings the total number of independent states remains the
same. Performing this calculation requires one use the result:
EXAMPLE 15.5
Consider two eigenfunctions cf>~. (1) and cf>~. (2) each having angular momentum
quantum number j= 1 and threel1possible prgjections mj = -1, 0, 1. Assume
that they are eigenfunctions of two operators J(l), J(2) which satisfy Eq. (15.14).
Construct the eigenstates of the total angular momentum J = J(l) + J(2).
There are three possible eigenfunctions for each of these two operators, namely
cf>W), cf>Mi) and cf>:l(i) , (i = 1, 2). One can thus construct nine product states:
~ {¢~(1)¢:1(2) - ¢:1(1)¢~(2)} ,
of which the first two eigenfunctions are symmetric while the third is antisymmetric.
To evaluate a, (3 one can operate on one of the two symmetric combinations with
the operator J2, using Eq. (15.24), (15.25) and (15.26):
1li~sym(1, 2) = ¢~(I)¢~(2),
1li~sym (1, 2) = ~ [¢H1)¢M2) + ¢MI)¢H2)]
1li~sym(1, 2) = ~ [2¢MI )¢M2) + {¢HI )¢~1 (2) + ¢~1 (1 )¢l(2) }]
1li:' lsym (1, 2) = ~ [¢:1(I)¢~(2) + ¢~(I)¢~l(2)]
1li:'2sym (I, 2) = ¢~1 (1 )¢:1 (2)
One thus notes for instance that the Wigner coefficient for
An ambiguity however arises as to the overall signs of the coupling coefficients. Thus
the wave function 1li8sym(I, 2) could equally well be written:
since this function is also normalized and orthogonal to both 1li~antisym(I, 2), and
1li~sym(I, 2). One must thus adopt and stick to a consistent convention.
An observant reader may have noticed that the component ¢MI )¢M2) is missing
from the 1li~antisym(I, 2) wave function. Its absence may be explained by arguing
Angular Momentum and Coupled States 277
that W5antisym(l, 2) is antisymmetric while the component <pMl) <pM2) is symmetric.
On a more technical level the coupling coefficient
(1 1 0 011 0) = O.
This is a consequence of the following three properties of the Wigner coefficients:
(15.27)
EXAMPLE 15.6
Consider two eigenfunctions <p~ )1 (1) and 'TJ~,{2J2 (2), the former having angular mo-
mentum quantum number j1= 1 and three possifile projections, mjl = -1, 0, 1, and
the latter angular momentum quantum number 12= 1/2 and two possible projections,
mh = -1/2, 1/2. Assume that they are eigenfunctions of two operators J(I), J(2)
which satisfy Eq. (15.14). Construct the eigenstates of the total angular momentum
J = J(I) + J(2).
There are three X two = six possible product functions which are eigenfunctions
of J2(1), J2(2) , Jz(I), J z(2):
These states are neither symmetric nor antisymmetric nor does one normally sym-
metrize or antisymmetrize these functions since j = 1 could refer to a Bose particle
while j = 1/2 may refer to a Fermi particle, or more likely the j = 1 refers to the
orbital angular momentum, while the j = 1/2 refers to the spin of a Fermi particle.
The first state above has maximum rhj = mil + mil = 3/2 projection and is
unique. It must therefore correspond to the state W~~~(I, 2).
278 Chapter 15
Thus:
W;~~(1, 2) = cfoi (1 )Tf~~~(2).
(15.28)
But L = L(I) + L(2). Operating with L on the l.h.s and with L(I) + L(2) on
the r.h.s. of Eq. (15.28) one obtains:
If
i.e.
If cfo~1(I)Tfi~~(2) + fa cfoMl)Tf~2/2(2)
i.e. :
W~12/2(1, 2) = .
= Ii v3cfo:l (1 )1]~~2(2) ,
1.e.
W~;/2(1, 2) = cfo~l (1 )Tf~12/2(2) ,
as expected by analogy with Eq. (15.28).
· d a quartet 0f states: .T,3/2
One h ast h uso b tame .T,3/2 .T.3/2 .T,3/2
'£3/2' '£1/2' '£-1/2' '£-3/2.
There remain a doublet of orthonormal states: W~~~, Wl};/2' the former of which must
be orthogonal to W~~~, and the latter orthogonal to W~12/2. These two states will auto-
matically be orthogonal to the other W3 / 2 states since they have different projections
mj. To within an arbitrary phase (hence the same ambiguity mentioned above about
the overall sign of the coupling coefficients which one must treat consistently) these
two states are:
(15.29)
Premultiplying Eq. (15.29) by 4>:'/> (1 )4>::/2 (2) and integrating using the assumed
3 1 32
(15.30)
EXAMPLE 15.7
Using complete set arguments obtain the inverse of Eq. (15.20) .
One can immediately write:
Premultiplying Eq. (15.31) by [¢i1 (1 )¢i2 (2)]~, and using the assumed orthonor-
. 3
mality of the [4>i1(1)4>12(2)];"'s one obtains:
3
(15.32)
(15.33)
where the (mj) in the sum implies there is really no sum over mj since mil +mj2 = mj'
EXAMPLE 15.8
Find orthogonality conditions satisfied by the Wigner Coefficients.
Starting with Eq. (15.20) and using the fact the functions involved are orthonor-
malone obtains:
280 Chapter 15
Thus:
L Uti2 m jl mh Ijmj )(jlhmj] mj2 Ij'mp) = 8j ,jl 8mj ,mjl . (15.34)
mil
(15.35)
One can consider next the case of three angular momentum operators, J(I), J(2),
J (3). If they operate on different spaces (for instance on the coordinates of particles 1,
2, and 3 respectively), then the total angular momentum is also an angular momentum
operator, namely:
J == J(I) + J(2) + J(3).
Formally the condition for J to be an angular momentum operator is that
in which case J X J = iliJ. One can then examine the problem of finding eigenfunctions
of J assuming one has eigenfunctions of J(I), J(2), J(3), namely ¢#.1' 'T/!;,2' ).,~3'
It is immediately clear that the order of the intermediate coupling is not unique
in this case. Thus one may couple these three eigenfunctions with three different
intermediate orderings:
The different functions which result may however be related to each other. Thus
using complete set arguments one can write:
They involve in all six angular momenta il. i2. i3. J12 • J 23 , J and are related to
the so called "6-j's"as follows:
In terms of U functions:
(15.37)
EXAMPLE 15.9
Obtain orthogonality relations for the U functions using complete set arguments.
Starting from Eq. (15.37) one has:
Hence:
:E U (jl i2 J i3i J12 J23 ) U (jl i2 J i3i J12 J~3) = DJ23, J~3 • (15.38)
J12
L U (it i2 J i3i J12 J23 ) U (jl i2 J iJi J~2 J23 ) = DJ12 , Jf2 • (15.39)
J23
EXAMPLE 15.10
Consider three angular momenta with eigenfunctions: cfJ.:.1, "'!;,2' )..~3' where il =
i2 = h = 1/2, coupled according to the intermediate coupling scheme [cfJl [.".12 )..ia j J23
Evaluate the recoupling matrix in Eq. (15.37) for this case.
1:.
282 Chapter 15
Using Tables 15.6-7:
TABLE 15.6
Non-vanishing U-Coefficients with one argument zero
2J12 + 1
(2j1 + 1)(2h + 1) ,
(2jl + 1) (2h + 1)
Angular Momentum and Coupled States 283
TABLE 15.7
U-Coefficients with one argument half
In some simple cases one can obtain the eigenfunctions of three angular momentum
operators by using symmetry arguments.
EXAMPLE 15.11
Consider for simplicity three eigenfunctions ¢i.:..n (1), ¢i~.n (2) and ¢i.:.D (3) each
having angular momentum quantum number il = i2 = h = 1/2 and two possible
projections mip mh, mh = ±1/2. Assume that they are eigenfunctions of three op-
erators J(l), J(2), and J(3), which satisfy Eq. (15.36). Construct the eigenfunctions
of the total angular momentum J = J(l) + J(2) + J(3) by symmetry arguments.
In this case since there are two possible eigenfunctions for each of these three
operators, namely <p~~~(i) and <p1};/2(i), (i = 1, 2, 3), one can thus construct eight
product states:
,1.1/2 ( ),1.1/2 ( ) 1/2 ( )
'I'±1/2 1 'I'±1/2 2 <P±1/2 3 .
If one operates on this state (or on the two other symmetric states above) with
.1,2 _
'I" -
-.!...
J2 [",1/2(1)",1/2
'1"1/2 '1"-1/2
(2) _ ",1/2 (1)",1/2(2)] ",1/2(3)
'I" -1/2 '1"1/2 '1"1/2 .
Finally for the third function with projection n/2 one can take a linear combination
of symmetric two-angular momentum functions Eq. (15.22) times eigenfunctions of
the third angular momentum operator which again result in an overall projection of
n/2:
1 [1/2() 1/2 ()
1fJ = a J2 <P1/2 1 <P -1/2 2
3
+ <P1/2
-1/2 1 <P1/2 2 <P1/2 3 + f3<P1/2 1 <P1/2 2 <P -1/2 3 .
( ) 1/2()] 1/2() 1/2( ) 1/2( ) 1/2 ( )
The constants a, f3 can be determined from the requirement the functions 1fJ1, 1fJ2,
and 1fJ3 are orthonormal. This implies:
Similarly one may obtain the three functions which have overall projection -n/2.
Thus there are four completely symmetric functions:
Angular Momentum and Coupled States 285
?jJ3/2
3/2 = </>~~~(1 )</>~~~(2)</>~~~(3)
?jJ3/2
1/2 = ~ [</>!~~(1 )</>!~~(2)</>~;/2(3) + </>!~~(1 )</>~12/2(2)</>!~~(3) + </>~12/2(1 )</>!~~(2)</>!~~(3)]
?jJ3/2
</>-1/2 1 '1'-1/2 2 '1'1/2 3 + '1'-1/2 1 '1'1/2 2 '1'-1/2 3 +
1 [1/2 ( )-1.1/2 ( )-I.1/2() -1.1/2 ( )-I.1/2( )-1.1/2 ( )
-1/2 v'3
.1. 1/ 2(1).1.1/ 2 (2).1.1/2 (3)]
'1'1/2 '1'-1/2 'I' -1/2
./,3/2
'1'-3/2 = </>~;/2(1 )</>~;/2(2)</>~;/2(3),
two wave functions antisymmetric under interchange of coordinates 1, and 2, but
with no definite symmetry under interchange of coordinates 1 or 2 with coordinate
3:
./,1/2
'1'1/2
= _1
v'2 [-1.1/2(1)-1.1/2
'1'1/2 '1'-1/2
(2) _ .1.1/ 2 (1)-1.1/2(2)] -1.1/ 2(3)
'I' -1/2 '1'1/2 '1'1/2
./,1/2 =
'1'1/2
1 [1/2() 1/2 ()
- .j6 1/2 ( ) 1/2()] 1/2() f2 1/2( ) 1/2( ) 1/2 ( )
</>1/2 1 </>-1/2 2 + </>-1/2 1 </>1/2 2 </>1/2 3 + V3</>1/2 1 </>1/2 2 </>-1/2 3
./,1/2
'1'-1/2
= .j6 1/2 ( )-I.1/2( )] -1.1/2 ( )
</>1/2 1 </>-1/2 2 + </>-1/2 1 '1'1/2 2 '1'-1/2 3 -
1 [1/2() 1/2 ()
[[</>1/2</>1/2] 1]
</>1/2
3/2 [ 0 ]1/2 , and the last two to
,while the next two to: [</>1/2</>1/2] </>1/2
[[</>1/2</>1/2] 1]
</>1/2
112
. Here one has the equivalence 20202 = + 2 + 2. 4
Of the more complicated recoupling coefficents: 9-j's, 12-j's, 15-j's, etc. in the lit-
erature, the most frequently encountered are the 9-j's. They arise when one considers
286 Chapter 15
four angular momentum operators J{I), J(2), J(3), J(4), which operate on different
spaces such that
J = J(I) + J(2) + J(3) + J(4),
is also an angular momentum operator (i.e. J x J = J).
An important case in point is if one has two particles with orbital and spin angular
momenta. Two convenient couplings are the j-j (intermediate) coupling scheme:
(15.40)
(15.41)
where as the names imply in the former case one couples the total individual angular
momenta to form the total angular momentum, and in the latter the total orbital
and spin angular momenta to form the total angular momentum.
To change the intermediate coupling one uses 9-j's. Thus
[[l112]L[8182]S]J =
M
L:
h, i2
A (~~L :~S ~~)
J
[[l18di1 [1282]hr
M
(15.42)
The A function in Eq. (15.42) is related to the 9-j (which as the name implies
involves nine angular momenta) as follows:
(15.43)
and in Table 15.8 the values of the A's are given for the simple case 81 = 82 = 1/2
(electrons, protons, etc.). The 9-j is a very symmetric quantity. Thus it is invariant
under reflection about either diagonal. Also, if one or more entries of a 9-j are zero
it simplifies. Thus:
{H c }
f
o
= Dei Dgh
{-1 )b+c+d+g
y'(2c+l){2g+1)
{a be}
e d 9
,
{ oad 0be}
e f
0
= Da.d Dbe Dc!
1
yi{2a+1)(2b+1){2c+l)
.
Angular Momentum and Coupled States 287
TABLE 15.8
A(
It 1/2
12
L S
1/2 h)
j coefficients for spin 1/2 particles
S=o S=l
L=J L = J-1
S=l S=l
L=J L= J+1
r
Hence,
1) ~ 82 i2 82 i2 }
S J S' J
(15.44)
Similarly one obtains:
L:{2i1+1)(2h+1)(2L+1)(2S+1){~:L
L,8
;:
S J
~:}{ ~~L ;~S
EXAMPLE 15.13
Consider two p (l = 1) spin 1/2 Fermions. Write the possible states inj-j coupling
and using Table 15.8 express these states in L-S coupling.
One uses for simplicity notation pj( i) here which stands for [1 1/2]; and 28+1 LJ
where L = 0 => S, L = 1 => P, L = 2 => D. In the j-j intermediate coupling scheme
one has:
[P3/2(1 )P3/2(2)] 0
[P3/2(1 )P3/2(2) r
[P3/2(1 )P3/2(2) r
[P3/2(1 )P3/2(2) r =
[P3/2(1)Pl/2(2)r =
[P3/2(1 )Pl/2(2)] 2
[Pl/2(1 )P3/2(2) r
[Pl/2(1 )P3/2(2) r
290 Chapter 15
EXAMPLE 15.14
Pick out the anti symmetric states (hence only acceptable states if the two particles
are identical) in Example 15.13.
In all one thus has 1+1+5+3+5=15 (acceptable) anti symmetric functions. The re-
maining 21 are (unacceptable) symmetric functions.
Schematically:
1
73 -ft,0 0 0
[Pl/2(1 )pl/2(2)] 0 ISO
r
[113/2(1 )P3/2(2)
-ft,
1
-73 0 0 0 3po
[P3/2(1)P3/2(2)] 2 0 0 0 A 1
73
3P2
~ {[P3/2(1)Pl/2(2)r - [Pl/2(1)P3/2(2)]2}
0 0 0 1 ID2
-73 -ft,
CHAPTER 16
But for the integral on the r.h.s. not to vanish, jl and h must be able to couple to
angular momentum zero, (with projection zero), i.e. form a scalar integrand. This
implies only the term j3 = jl survives and also that q + m2 = ml (since analogously
with Y,;:I(O, ¢) = (-l)mY~m(O, ¢), the complex conjugate of 'ljJt:. 1 , 'IjJ*!:.1 '" 'IjJ::ml as
concerns angular momentum coupling) . Thus
l(jll k,j2, ml, q, m2) = (kj2q m 21jlmd J 'IjJ*!:.1 [Tk'IjJh 1:1 dr.
Moreover the integral on the r.h.s. being a scalar, it should not depend on ml which
can therefore be dropped in writing down the result:
l(jll k,j2, mIl q, m2) = (kj2q m 2ljlml) J 'IjJ*it [Tk'IjJi2 t dr. (16.1 )
This is the famous Wigner-Eckart theorem. An almost obvious result, once one has
seen the derivation, it is basic in the evaluation of numerous matrix elements which
arise in Atomic, Molecular and Nuclear Physics. It is useful because it removes the
"geometry", i.e. the projections mIl q, m2 from the matrix element evaluation by
concentrating them in a Wigner coefficient which one can look up in tables (cf. Tables
t
15.2-5), and additionally one has merely to evaluate a single projection-independent
"reduced matrix element" f 'IjJ*it [Tk'IjJi2 dr in order to obtain the value of the in
292 Chapter 16
principle (2jl + 1)(2k + 1)(2h + 1) matrix elements I(h,k,h,ml,q,m2) (many of
which are zero however since I(jl,k,h,mhq,m2) = 0 unless q + m2 = ml) which
arise for a particular jl, k and h.
If the irreducible operator is for example the multipole operator:
(16.2)
this automatically behaves like a wave function. For a three-component vector oper-
ator, e.g. 5, Lor 1, one must choose combinations of the three components which
behave like an (irreducible) tensor of rank 1. This can be done by using the spherical
harmonics (d. Table 15.1) as prototypes, i.e. take
Jx+iJ
V2
y •
sInce y;(I}«(),A..)
1 '/' = - [If!] 1 . ()
-2 -1r -V2 -2r -1r V2 Y:
z,/, = - [If!](X+i
sm exp (.,A..)
EXAMPLE 16.1
Obtain the irreducible tensors which can be formed from the two vectors 1(1), and
1(2).
There are nine components here, and since the angular momentum operators
operate on different spaces they commute and one need not worry about the order in
which these combinations appear. In detail one has
A single scalar can be formed from these components, by analogy with rl·r2.
From the discussion immediately preceding Example 16.1 one sees that a three-
component irreducible tensor of rank one can be formed as follows:
Tensor Operators, and Evaluation of Matrix Elements 293
If a == i(l)xi(2),
,p~ C"
,p}
Cx + iCy
..;2
Cx -iCy
,p:l ..;2
Finally one forms an irreducible tensor of rank 2 by analogy with the five compoent
spherical harmonics of rank 2, Y,! (d. Table 15.1) or by recalling that
EXAMPLE 16.2
Evaluate the angular part of the matrix element
(11V12) = (21V11) ,
where
One notes that z = (z/r)r = r cos fJ = 2rV'lr/3 Yo1(fJ, </1) (d. Table 15.1), behaves
like an irreducible tensor operator of rank 1 and projection 0, i.e. can be treated like
a wave function 'l/JJ as concerns angular momentum coupling. Thus:
~C2v'i" (R2o(r) Irl R21 (r)) (1 ~omj I~mj) (Yo 0 ( fJ, </1) IYo1 (0, </1)1 Yo1(fJ, </1))
= ;;(_I)m j +1/2 (R20(r)lrIR21(r)).
EXAMPLE 16.3
Solve Example 16.2 using the Wigner-Eckart theorem.
Tensor Operators, and Evaluation of Matrix Elements 295
Using Eqs. (16.1), (15.37) and Table 15.6,
= U(l1~~jO~)(yO[ylylt)·
Using the results
i.e. one obtains (as one must) the same result as in Example 16.2.
EXAMPLE 16.4
Evaluate the matrix element
It is convenient here to use the following property of the spherical harmonics, namely:
(16.5)
(21' + 1)(2k + 1)
(16.6)
(21 + 1)47r
Finally then:
(21' + 1)(2k + 1)
(Y.!.I~kl y~,) = (kl'qm'llm) (kl'OO Ito)
(21 + 1)47r
EXAMPLE 16.5
Evaluate the matrix element
Tensor Operators, and Evaluation of Matrix Elements 297
As in Example 16.4 one writes:
)(
I", j"
(16.7)
For a particular j there are two possible values of [" with opposite parities, namely
[" = j + 1/2, or [" = j - 1/2 .
However for the reduced matrix element ([[" ~r [k [I' ~r'r) not to vanish, ["
must have the same parity as [' if k is even parity or opposite parity than l' if
k is odd parity. Hence in this case (since one is coupling [' to spin 1/2 ) only one
I" which, to simplify the notation at this point, one can calli, survives. This is not
the case however if one for instance couples [' to a spin 2 1. Thus in the spin =1 case
there are generally three possible values for I (cf. Example 16.6 for general spin S).
In the present case therefore
l.e.
/ [y, 1/2]i Iykl [Y" 1/2]i') = (kj'qm/ljm) (kj'O~ Ij~) (t/~0~ Ij'~) (2k + 1)(21' + 1)
\ X m q X m' (ItOt Ijt) (21 + 1 )411"
EXAMPLE 16.6
Evaluate (for arbitrary S) the matrix element:
Using the Wigner-Eckart Theorem, Eq. (16.1) and Eq. (15.37) one obtains:
M.E. = I
(kj'qm/ljm) ([IS]j [k [I'S]ir)
(21' + 1)(2k + 1)
= (kj'qm/!jm) U (kl'jSj Ij') (kl'OO I/O)
(21 + 1)411"
where one has also used Eq. (16.6).
If S = 1/2, comparison of this result with Example 16.5 implies
where
with analogous expressions for JJ Jf J: u and hence obtain the generalized Lande
formula:
Tensor Operators, and Evaluation of Matrix Elements 299
Applying the Wigner-Eckart theorem to the matrix element (W!..IA!I w!,..), one ob-
tains:
(16.9)
since
J . A -- J+A_1 +2 L1A+ + Jz Az -- - J11 A1-1 - J1-1 A11 + J.tOJ-'-O·
Ll1
If one inserts a complete set of states L:jll, mil Ij"m"} (i"m"l between the J's and A's
in Eq. (16.12) one obtains:
J(J. A) = -J: L:
j",m"
Ij"m"} (i"m"l A: 1 - J~l L:
j",m"
Ij"m"} (j"m"l A~
However any component of J1, the angular momentum operator cannot change the
angular momentum of a state. Thus only the term j" = j contributes to these sums.
Also matching the projections one has:
+(ljOmljm)(ljOmljm)} . (16.13)
+(ljOmljm)(ljOmljm)} . (16.14)
Equating Eqs. (16.11) and (16.15) and recalling that (w!..IJ . JI w!..) = (w!..1 J 2 Iw!..) =
j(j + 1)1i2 one finally obtains the generalized Lande formula.
EXAMPLE 16.8
With the help of the generalized Lande formula (d. Example 16.7) show that:
If
('11t,.;\ Jz(I) \'11t,.) = E timjl (j1i2mjl m j21 jmj)2, ('11t,.;\ Jz \'11t,.) = timj ,
m;l(mh)
Hence
=
ti 2 {j(j + 1) +h(j1 + 1) - h(h + I)}
2
Substituting one obtains finally (where this expression may be compared to Eq.
(15.34) ):
EXAMPLE 16.9
Evaluate the (possibly) off-diagonal matrix element (cf. Example 16.7 for the
diagonal case) in I and j :
(16.16)
If A only operates on the spin coordinates (e.g. if for instance Al = SI), with the
help of Eq. (15.37) one may write:
i.e.
(16.17)
x(-I)
1 .., /1
-3-3 \2 [A 11]1/2)
2 611' .
EXAMPLE 16.10
Evaluate the matrix element in Example 16.9 if A! = L!.
From Eq. (16.16):
For both these diagonal cases the result for ([I~J:I L~ I[I~]:) using the above
lh, if j=j'=1+1/2,
(21-1)(l+1)h if j=j'=1-1/2.
21 + 1 '
Finally for the two off-diagonal cases
1 . 1
U(llj~;lj') , if J., = 1 - -1 , J =
1
+-.
(l + 1)(21 + 1) 2 2
Thus
J·=I-~2'
and
r= r~ - d Ar
where r"2 an r = Ir'I '
and the 0"(1) and 0"(2) operate on the spins of two spin 1/2 particles, in terms of
irreducible tensors.
One notes:
Hence
A
(
ad
: f 0)
~ =6 ad 6be 6ef
J +2c + 1+
. (2a 1 )(2b 1) .
Hence:
Since, using Eq. (16.19)
If one writes Eq. (16.20) out in detail with the help of the Wigner coefficients:
S12 (f, u(l), u(2)) = 3 { [u 1(1)u 1 (2)]: [flfl]~2 - [u 1 (1)u 1 (2)]: [flfl]~1
+ [flfl]: - [ul(1)Ul(2)]~1 [flfl]:
[u 1 (1)u 1 (2)]: (16.21)
+ [ul(1)Ul(2)]~2 [flfl]: } .
306 Chapter 16
In order to operate with Eq. (16.21) one must write out the various terms in this
equation in a simpler form. Thus.
Yo
2(0.1..)
,'fJ = V[5
'i'(i;
3z -2
r2'
r2 Y,12(O,.I..) = _
'fJ V{15 x + iy ~,
8" r r
y;2(O, .1..) =
2 'fJ
J 15
3211"
(X + iy'\
r)
Similarly one obtains:
[f1f1]: = (1110121)f~f~ + (1101121)f~f~
1 AlAI 1 AlAI
..j2 rlrO + ..j2 rOrl
= 2 ~ (- Xr: ; ) ~ = - ~ iy ~ =
X fJ ~2(O, ¢» ,
and
Summarizing (where [rlfl]~ = [flrl]~M' a result which may be obtained using the
second property of Wigner coefficients noted in Eq. (15.27) ):
[flfl]: = fJ Yo 2 (O, ¢» .
The spin operators must also be simplified:
[a 1(1)a l (2)]:2 = (11 ± 1 ± 112 ± 2)a(1)i1a(2)i1
= ( ax (l) ± ia y (l)) ( a x (2) ± ia y (2))
1=..j2 1=..j2
1 2
= 2a±(1)a±(2) = 1i,2 S±(1)S±(2) ,
Tensor Operators, and Evaluation of Matrix Elements 307
where (cf. Eq. (15.25) )
hu ~-----------
S±=T' and S±X~.=hV(sTm8)(s±m8+1)X~.±1·
Similarly one obtains:
and
Summarizing
2 1 2
[
u1(1)u 1(2) ] ±2 = '2 u±(1)u±(2) = h2S±(1)S±(2)
[u 1 (1)u 1(2)]:1 = T~ {u±(1)uz(2) + uz(1)u±(2)} ,
2
= T h2 {S±(1)Sz(2) + Sz(1)S±(2)} , (16.23)
EXAMPLE 16.12
Given the tensor operator (cf. Example 16.11), evaluate the matrix element:
I = (~lx~1 SI21~IXO
= ~
ti 2
/967r5 V~3' ti2 (y} 1-v.21 Y,I)
2
I 0 I
1 {9&; f2 f5ti 2
= ti 2 VT V3' "2 V4; (2101111)(2100110)
~2 /9:7r ~ ~2 (f Jio (-fs) = -~.
EXAMPLE 16.13
Given the tensor operator (cf. Example 16.11), evaluate the matrix element:
EXAMPLE 16.14
Given the tensor operator (cf. Example 16.11), evaluate the matrix element:
=
fg6;{ V/23" 2"n2 (~11Yo21 ~1) + V/2(3" -n2) (Yo11 Yo21 Yo1) + V/23" 2"n2 (1 IYo2IY-l1)
3"1 n12 V5 Y- 1
= ~ 54 (-Is) [~] = -4 .
Comparing the results of Examples 16.12-14 one notes that the relative strength
of the tensor force in the three triplet P states 3 P2 , : 3 PI , : 2 Po , is as -2/5 : 2 :
-4 , where (3 R0,1,2 = [y1X1jO,l,2) .
310 Chapter 16
EXAMPLE 16.15
Given the tensor operator (d. Example 16.11), evaluate the matrix element:
Since its inception, the applications of Quantum Mechanics have been legion.
Starting with the one-electron hydrogen atom, the Schrodinger equation was success-
fully applied to many-electron atoms, molecules, solids, and nuclei, and has been able
to explain scattering phenomena, effects induced by electric and magnetic fields, spin
polarization etc. Moreover when Dirac's equation is used instead of Schrodinger's,
Quantum Mechanics successfully explains the spin and gyromagnetic ratio of the elec-
tron, the existence of particle-antiparticle pairs etc. These applications and related
problems are scattered through the literature. Given below are some applications of
Quantum Mechanics to Mathematics and Optics.
EXAMPLE 17.1
Consider the complete set for a particle in the one-dimensional oscillator well:
x 2 /2, x ~ 0,
v= {
00, x < o.
The complete discrete set for this potential is :
= f:
n=1,3 0
1 (>~(x)x(>n(x)dx 1 (>~(XI)XI(>l(x')dx'
00
0
00
= nt 3 [1 00
(>n(X)X(>l(x) dx f
(using Eq. (2.6), interchanging integration and summation, and dropping the * since
these (>(x)'s are all real).
Thus:
(17.1)
But
10 00
iPt(x)xiPt(x)dx =~, 1000
iP t (x)xiP 3 (x)dx = f[; ,
10'>0 iP 1(x)x(>s(x)dx = -J3~11" •
Thus
3 4 2 1
'2 = ;; + 311" + 3011" + ... ,
or
(17.2)
From Eq. (17.1) it is clear that this is a monotonic series, binding 11" from below.
EXAMPLE 17.2
Noting that I;' iPt(x)iPt(x)dx = Iooo iPt (x)(l/x) x iPt(x)dx = 1, use closure and
the complete set in Example 17.1 to get a second infinite-series expansion for 11".
(17.3)
where integrations and summations have been interchanged and complex conjugates
have been dropped since these iP's are real.
Evaluating
314 Chapter 17
10
(00 <I>1(X)~<I>5(X)dx
x
= J 3
0
1 1r
,
and also using the integrals listed in Example 17.1 one obtains:
1 =
=
J;J; -
4 2
;: - 31r - -10-7r - ••• ,
aa -J1~1r J3~1r
1
or
(17.4)
A careful examination of the nth term of this series shows that each term is
negative for n > 1, i.e. this series bounds 1r from above.
EXAMPLE 17.3
Use the complete basis for a two-dimensional harmonic oscillator
1 2
V ="2 P , P ~ 0,
(See Eq. (8.14) ), and a procedure similar to that used in Example 17.1 to get an
infinite monotonic series for 1/1r.
The simplest case one can examine involves n, m = o.
r'lr (00 <I>~(p, ¢»p2<I>oo(p, ¢»pd¢>d</> = 10{OO woo(p)lwoo(p)dp = 1.
10 10
Thus, using closure:
However, since p is a scalar, integrating over </>, </>' one finds that m = 0, i.e. that
(17.5)
Applications of Quantum Mechanics 315
Evaluating
and since Eq. (17.5) is a monotonic series this expansion bounds 1/7r from below.
EXAMPLE 17.4
With the complete set of Example 17.3 and the methods of Example 17.2 obtain
a second infinite series which bounds 1/7r from above.
Using the techniques of the previous three examples,
rOO woo(p)woo(p)dp =
io
1= f n
roo woo(p)pwno(p)dp roo Wno(P')!...woo(p')dp'.
io io p'
(17.7)
Evaluating
l o
co 1
woo(p)-woo(p)dp =
p
..ft , 1 woo(p)-wlO(p)dp
o
00 1
p
= -
..ft
2
,
1 00
o
1
woo(p)-w2o(p)dp = -
p
3..ft
8
.
Using in addition the integrals listed in Example 17.3 and substituting into Eq.
(17.7) one thus obtains:
(17.9)
Evaluating
Since, like Eq. (17.5), Eq. (17.9) involves a monotonic series, if truncated, Eq.
(17.10) yields a lower bound for 1/11". The series Eq. (17.10) however converges faster
than that of Eq. (17.6) as can be seen by inspection.
EXAMPLE 17.6
Show that a different, more quickly converging infinite series than Eq. (17.8)
results if one starts with n=O, m=l (rather than n=O, m=O) in Example 17.4.
Using the same techniques as the previous Examples one may write:
roo WOl(p)-pWOl(p)d
10
1 ft
p = """2 '
Applications of Quantum Mechanics 317
Using additionally the integrals listed in Example 17.5 and substituting into Eq.
(17.11) one thus obtains:
A careful examination of Eq. (17.12) shows that like Eq. (17.8) this series bounds
1/7r from above since all terms, other than the first, are negative. However the series
Eq. (17.12) converges to 1/7r faster than the series Eq. (17.8).
EXAMPLE 17.7
Use the complete basis for the three-dimensional harmonic oscillator
VCr) = r 2 /2 , r ~ 0, namely:
Unl(r) 1
Wnlm(r,lJ, ¢) = --Ym(O,
r
¢), n = 0,1,2 ... , 1 = 0, 1,2 ... , Iml = 0,1, 2... ~ 1,
( ) _{2r(n+l+3/2)}1/2 r'+1exp(-r2/2) F (
Unl r - n! r(1+3/2)
1 3
1 1 -n, + 2,r
2)
(see Eq. (8.13)), to obtain a similar series to that in Example 17.1 but which
converges more quickly than Eq. (17.2).
By the same arguments as were used in Examples 17.1, 17.3 one obtains:
(17.13)
°
Consider the case n = 0, 1 = 1. (The case n = 0, 1= gives identical expressions as
Example 17.1 since in this case there is no angular momentum term 1i, 21(l + 1)/2mr2
in the Hamiltonian and the potentials in these two examples become identical.)
Evaluating
['>Co
Jo uOl(r) ru n(r)dr = -v[32
45; ;
one may then substitute in Eq. (17.13) to obtain:
5 64 32 8
2 = 97r + 457r + 3157r··· ,
or
128 64 16
11" = 45 + 225 + 1575··· . (17.14)
318 Chapter 17
This series converges to 1r more quickly than Eq. (17.2) .
EXAMPLE 17.8
Use the same basis as in Example 17.7 to get a series similar to that of Example
17.2 but which converges more quickly than Eq. (17.4).
By the same type of arguments as are used in Examples 17.2, 17.4 one obtains:
(17.15)
Evaluating
1o
00 1
uOl(r)-uOl(r)dr
r
4
= 3y'-;
1r
1o
00 1
uOl(r)-un(r)dr
r
=
{f
-;
451r
Jor;,o uOl(r)~u21(r)dr
51r
r
= 13 2 ,
and using additionally the integrals given in Example 17.7, for the case n = 0, 1 = 1,
Eq. (17.15) yields:
8 4 {32{8 i8/2
1 = 3";; 3";; - V45;V 45; - V31[;; V35; ... '
or
32 16 4
1r = "'9 - 45 - 105···' (17.16)
a series which converges more quickly than Eq. (17.4).
One may note here that the leading terms of the series obtained in Examples
17.1-8 are all odd or even truncations of Wallis's3 expression for 1r
1r 2 x 2 x 4 x 4 x 6 x 6 x 8.. .
2' = 1 x 3 x 3 x 5 x 5 x 7 x 7... .
Other monotonic series for 1r, 1/1r whose leading terms are not a truncation of
the Wallis's expression may be obtained by using higher odd values of n (i.e. 3,5 ...
rather than 1) in Examples 1,2, or higher values of n, (i.e. 1,2,3 ... rather than 0 )
in Examples 3-8.
EXAMPLE 17.9
Consider the complete infinite square-well set over the range -1 < x < 1, namely:
while 1 cPt(x)lxlcPt(x)dx = -2 -
1
-1
1 2
2" '
71"
and
1 71"22
3"- =
(1'2- 71"22 )2 + (-71"22)2 + ( -(371")2
2)2 + ( -(371")2
2)2 + ( -(571")2
2)2 + ...
I.e.
or
(17.18)
a standard result4 •
EXAMPLE 17.10
Consider the complete infinite square-well set over the range -1 < x < 1, namely:
1 <Pt(x)x cl>t(x)dx
-1
1
2
1
= - - '2 '
3
2
7r
while
m = 1,2, 3 ....
Thus
1 1
-1
<Pt(x) x <Pi(x)dx = '2
7r 1
1 25
23 2 ' etc.
7r
2 {~2 _ 2} = 210 C1 ~2 3)4 + (3 ~25)4 + (5 !27)4 .. -} . (17.20)
one obtains
210 { 7 X 12 19 X 22 39 X 32 }
7r
2
= ""3 (1 X 3)5 + (3 X 5)5 + (5 X 7)5 ... , (17.21)
10 { 23 X 12 83 X 22 183 X 3 2 }
7r
4 = 2 (1 X 3)5 + (3 X 5)5 + (5 X 7)5 ... . (17.22)
of the Nth order fluctuations (where the operators chosen are such that (wlxlw) =
(wlplw) = 0). It turns out that 5 the state W which minimizes this product in the
case (WlxNIW) = (WlpNlw) can be found by solving the eigenvalue equation:
EXAMPLE 17.11
In the case N = 2 find the state "if! which minimizes U2 and the corresponding
second-order fluctuation.
In the case N = 2 Eq. (17.23) reduces to the well-known oscillator problem with
solutions "if! = <pn(x) (c.f. Eq. (2.12) with b = 1) in the coordinate representation,
while
EXAMPLE 17.12
For the general case N = 4, 6... find (UN )min. if one assumes the solutions of
Eq. (17.23) are the same states as those which arise for N = 2, i.e. the functions in
Example 17.11.
Premultiplying both sides of Eq. (17.23) by <Po and integrating over x, one obtains
But
1 ~
00
<Pox N <Podx = 100
~
<PoPN <podx ;;;;r (N
.1
= VW -2+-1) .
Thus
A = _1 r
N ft (N 2+ 1) = (U N
)l/~
mm. ' (17.24)
under this assumption for the wave function. (Example 17.11 is a special case of this
expression with N = 2, in which case A2 = (11ft) r (3/2) = 112).
If
N=4, A4 = _l_r (~) = _1_~~y7r = ~, etc.
ft 2 ..fo22 4
Using the duplication formula
(N -I)!!
AN = 2N/ 2 •
EXAMPLE 17.13
Show that the operator
only connects oscillator states which are diagonal, or differ by 4 or more quanta.
For diagonal states there are non-zero matrix elements. Thus in Example 17.12
one obtains (q>oIOIq>o) = (N -1)!!/2 N / 2 • Similarly one obtains
Obviously the operator 0 does not connect states which differ by an odd number
(1, 3, 5... ) of quanta since, like q>n, 0 has definite (even) parity.
Consider next states which differ by 2 quanta, in particular:
if N = 2.
But
If N = 6,
Applications of Quantum Mechanics 323
and so on for higher even powers of N. Thus generally
Thus the operator 0 connects diagonal elements and off-diagonal elements which
differ by 4 quanta.
EXAMPLE 17.14
Solve the eigenvalue problem, Eq. (17.23), for
o = ~ (pN + x N) N = 2, 4, 6 ... ,
{q;oIOIq;o} - AN (q;oIOIq;4)
{q;4101q;o} {q;4101q;4} - AN
equals zero. Otherwise the two linear equations above for 0:, f3 will be singular. This
determinant condition yields a quadratic equation for AN.
324 Chapter 17
Substituting into this equation the values of
obtained in Example 17.13 and noting that all these quantities are real (hence
(cJ>oIOIcJ>4) = (cJ>4101cJ>o) ), the equation can be solved for A, and after some algebra
one obtains:
where
f(N) == (N 4 + 4N3 + 20N 2 + 32N + 48) ,
and
g(N) == (N 3 + 2N2 + 4N + 3).
This complicated expression simplifies as N ---t 00 in which case:
(N -I)!! {8 9(N)}
Aground ---t 2N/2 f(N) ,
where the term in the braces and hence also Aground goes to zero as N ---t 00.
One may generalize Eq. (17.23), to include odd positive integer as well as non-
integer values of N (where N > -1), by considering the eigenvalue equation:
(17.26)
(17.27)
where as above AN = (UN )1/2. These expressions and the corresponding results
reduce to those obtained previously, if N = 2, 4, ....
EXAMPLE 17.15
Obtain AN = (UN )1/2 for general positive N if one assumes \]i = cJ>o(x), the
simple-harmonic oscillator ground-state wave function (d. Example 17.11).
Firstly
2 10
00
{)/4 exp ( - x;) } x {1r~/4 exp ( - ~2) }dx
N = J,r 10 x (-x )dx
00
N exp 2
= J,rr ( 1) .
N;
The evaluation of I~oo W"'p,N wdp, is easiest done in momentum space (d. Chapter
3) which is an acceptable procedure since the values of matrix elements are indepen-
dent of the basis representation used to evaluate them. Solving for c}o(x) using Eq.
(3.1) one obtains
c}o(p) = 1r1/4 (p2)
1
exp -"2 .
Hence by analogy with the above result:
1 w", INwd
00
-00
p p-
__
1
y1r (N 2+ 1) '
t:;
r and 1 (N- 2+ -1) .
>'N = .,fir
Thus for general N > -1 one merely gets an analytic continuation of the result given
in Eq. (17.24) which was derived for positive, even integer values of N.
References
1. H. A. Mavromatis, J. Approx. Theory 60 1990, pp. 1-10.
Yukawa potential 94
Zero-order 159
-order eigenfunctions 175
-order energy 211
Kluwer Texts in the Mathematical Sciences
1. A.A. Harms and D.R. Wyman: Mathematics and Physics of Neutron Radiography.
1986 ISBN 90-277-2191-2
2. H.A. Mavromatis: Exercises in Quantum Mechanics. A Collection of Illustrative
Problems and Their Solutions. 1987 ISBN 90-277-2288-9
3. V.I. Kukulin, V.M. Krasnopol'sky and J. Horacek: Theory of Resonances. Principles
and Applications. 1989 ISBN 90-277-2364-8
4. M. Anderson and Todd Fell: Lattice-Ordered Groups. An Introduction. 1988
ISBN 90-277-2643-4
5. J. Avery: Hyperspherical Harmonics. Applications in Quantum Theory. 1989
ISBN 0-7923-0165-X
6. H.A. Mavromatis: Exercises in Quantum Mechanics. A Collection of Illustrative
Problems and Their Solutions. Second Revised Edition. 1992 ISBN 0-7923-1557-X