Non-degenerate
Perturbation Theory
oo
Ir 1 - -r.,1
r<
47r "'"' }. ( )}' ( " )
= "'"'
L...J t+T 21+1 L...J 1.m
l,m r2
l=O r>
m=-l
r,
'
where
r1
= (0, ip) ,
r2
= (O', iy')
by
a) expanding in spherical harmonics.
b) realizing that i,.(i) is the potential for a unit charge located at ?, and comparing the two solutions.
Solution
We begin with Poissor.'s equation for the potential~ due lo a unit point charge
(12.1.l)
(12.1.2)
12.1 .
EXPANSJO.V OF
l/lf"1 - f21
233
Now, we also solve this differential equation in spherical coordinates. for this
purpose we write
w(r) = L:a1,m(r)}im(O.;p).
(12.l.3)
I ,m
~) =
c5(r-
_;.c5(r - r 1 )
r~
(12.IA)
Im
where
r=
(0, 'P)
;I
= (9 1 I ;p')
(12. l.5)
l d2
l (l + 1)
I
I
,
,.
1
+t
cf!
r-
r'
from r 1
-d
.,[ra1,rn(r)]dr= -} 1 ~m(r 1 ).
'
(12. l.6)
c to r 1 + c we get in the
(12. l.7)
I _
da1,m
rlu1 ,m
1I r
r'+
d ,.
r' -t
( :,)
lm 7
(12. l.8)
'
1\1.m rn
with
11
=I or
11
= -(I+ l}
(12.1.9)
so we have that
a1 ,m(r)=
1\1 m
{
n1,m
'
r1
r-11+1)
r
r
< r'
> ,.1
(12. 1.10)
lier<> we have alrendy imposC'd tlw bo1111dary conditions that tlll' solution has
to be finite at ,. = O and has to vanish for 1 -t oo. The solution also ha:> lo
be continuous ;1t 1' = r' and to .satisfy tlw condition or discontinuity in the first
derivatiw . Imposing th~e two conditions WP get
,1
I \ 1,rn I'
= I/1 , rn r 1- (l +I )
(12 .1.ll}
or
1(21+1)
B1 ,m
= "'"' ,.
(12.1.12)
rvnAYll;!;ff. Jj!.
as well as
A1 m
lr,(l-l)] =
(12.1.13)
Thus,
___
l ___
l_y; (r')
A1,m 21 + 1 r'(l+l) l,m
.
{12.1.14)
So finally we get:
lr--r-- 1=4rr
r < r'
r > r'
(12.1.15)
12.2
In the equation for the rth order correction to the state Im}
(Ol(mln}(r) =
E~O) ~ E~)
- E~3 ) (Ol(mjn}(r- 3 )
[<o>(mlH' -
... -
m ::j:. n
(12.2.16)
jn}(2)
~
m,r;tn
(E(O)
- E(O))
(E(O)
- E(O))
n
m
n
r
- L
m;tn
~
2
E~o) - E~?l)
m;tn
(12.2.l i)
E~o) - E~)f
Solution
We start with the equation (12.2.16) for the rth order correction to a state,
namely
(Ol(mln}(r)
= E~o) _1 E~>
- E~3 ) (O)(mjn)Cr- 3 )
... -
E~r-l) (Ol(mln)Pl)
m-:/; n
(12.2.18)
J2.3.
235
(12.2.19)
En -Em
E~o) - E~)
(O)(mlH' - El ln)(O}
E~o) ~ E~)
n
0
(O)(mlH'ln)< >
m-/: n
(12.2.20)
we find , a fter writing everything out, the desired result, namely equation (12.2.17).
12 .3
Solution
a) Here
p2
H = 2m
.,
+ -kx+ -,\x2
> 1,\1.
(12.3.2 1)
=~ .
(12.3.22)
We now define
n2
= k + ,\ ,
w2
= !:_
0'2
m
rn
m
The exact energy eigenvalues are given by
(12.3.23)
If we now expand this in a binomial series in ,\ to get the corrections due to the
perturbation we find
(n
+ 1/2)/iw [ 1 + 2:
(n
+ ;-)/iw
+ (n +
2
2 -
;.,:
+ ...]
1
,\
1
,\ 2
- ) I i - - (n +-)Ii--+ ....
2 :.!mw
:.! 8rn2w3
( 12.3.24)
236
E~o)
= (n + 1/2)/iw
(12.3.25)
= ,\ (Ol(n!H'ln)(O)
~ (Ol(nl.z:21n)(O)
2
>.Ii
?
- - (Ol(nja 2 +at-+ 2a1a + ljn)(o)
4mw
>.Ii
- ( n + 1/2) .
2mw
(12.3.26)
So this result agrees with the exact result to this order. Next we have
(2) _
E,l - ,\
I:
1( 0 l(nlH'ls)(O)l 2
E(O) -
a;tn
( 12.3.27)
E(O)
,\ (Ol(nlH'ls) 10l =
~ (O>(nja2 + a 12 +
2mw
2a1a + lls)(o)
(12.3.28)
So,
12)
"
4m2w2
( 12.3.29)
Then,
(2)
n
ft,\
[ (n
16m 2w 3
+ 2)( n + 1) + --'----'n (n - I ) ]
-2
I)
/i,\2- ( n+-8m2w3
2
( 12.3.30)
\ I
H =Ho+ AH
p2
l
l
= -2m
+ -k.r+ -k -krJ
2
2
?
,\ [
(12.3.31)
H = J/o +.AH"= -
2m
1 p2
k 2m
(12.3.32)
I.All!"<
lfn
for
I.Al< k
<12.~:m
12.4.
237
JJ '
<
(12.3.34)
fl" .
Therefore, the pnturbat1on herics is boundrd by the perturbation hcries for fl"
as Jong ru; I.XI< k. On thr olhrr hand, thr rth order term for the pertur bation
series for H" is
(>./knn
+ 1/2)/i,.,.; 1>(nln)lr-l
(>./kr(n + 1/2)/i,.,.;or,t .
(12.3.35)
From this we see that we can bound the perturbation serirs for H' by a convergent resu lt if l>.I < k. In fart,
r:I
+ l/'2)h..J
(,\/k)(11
12.4
(12.3.36)
a) Find the approximate ground htate energy to second order for the Hamiltonian
2
p
1 .,
I 4
= -2m
+ -kr
+ ->..r
2
4
>0
Solution
a) The Hamiltonian is
,,2
fl = Ho+ >.H' = -
2111
+ -k:c2 + -,\.r-t .
( 12.4 .37)
(l2A.:J8)
~ ~ ....... .e. .
(12.4.39)
The second order perturbation correction is given by
..\2 E~2l
,\2
16
= -
I (Ol(Olx41n)(O)l2
n;t O
,\2
liw( l /2 - n - 1/2)
16
2mw
n/iw
n;tO
2
= __
1_ (~)""" (v'4!c5n,4 + 6J2on,2)
16/iw
2mw
~
rt
(12.4.40)
b) The wavefunction correct to order ..\ is given by
m;tn
But, for m
f: 0 we
E(O) O
( 12.4.41)
E(O)
m
have
(12.4.42)
Therefore,
IO) =
IO)(O) -
IO)(O) -
~-h[12J212)< 0l + 2/614)<0>] .
16 4m 2w 3
12.5
1/4 Ax 4
2mw
2riw
41lw
( 12.4.43)
Brillouin-Wigner Perturbation
Repeat part a of the problem above (problem 12.4) using Brillouin-Wigner perturbatio n theory.
12.6.
239
TWO-LEVEL SYSTEM
Solution
To first order the calculation is t.he same as for Rayleigh-Schrooinger perturbation theory. ln second order the appropriate formula is
).2 E(2)
= ).2
'' (Ol(Olx"IO)COl
4 L...,
n;o!O
(12.5.44)
E(O)
n
0 -
(-li-) L
2
).2 el2l = A
0
4
2mw
0
< l(Ol(at
+ a) 4 IO)(o)
Eo - E~O)
n;o!O
2
(-Ii-)
J4ic5,.,4 + n/26n,2 + /2c5n,2
4 2m..J
Eo -
= ). 2
E~o)
= )_2 ( fl. )2 [
v'4f
4 2mw Eo - (4 + l/2)fiw + Eo -
3J2
(2 + l/2)fiw
{12.5.45)
~liw
- ) + ). 2 e<02
2
+ 4~). (-li
2m..J
2
E0 =
>
(12.5.46)
After substituting this in the equation above and rearranging we get the following equation for Eo.
Eo = A2
~!i..J
- ~). (-"-)
2
4
2mw
(-h-)
2mw
2
[
E0
v'4f
+ Eo (4 + 1/2)/iw
3
J2
(2 + l/2)fiw
(12.5.47)
12.6
Two-level System
where
Ho= (
E1
O
H' = (
-ia
ia )
0
240
Solut ion
The Hamiltonian is as always
II = Ho+ >.Fl'
(12.6.48)
where
0 )
2
'
H' -- ( -i>.a
(12.6.19)
Exact solutions
The eigenvalues are given by
det (
E1 - E
-i>.a
i>.a )
E2 - E
=O
( 12.6.50)
Ed =
E+
2(1
+ E2) +
l
2(2 - l~'i)
>.2 a 2
E2 - 1
E_
( 12.6.5:q
This result shows that
( 12.6.51)
so that the two r.nergy levels are 'r<pelll'd'' by the prrturbat1on. This rf'.sult i:-.
quilc gen<>ral.
The cigenv<'clors arc oft he form
( 12.6.5!))
where
(I :!.6.56)
12.6.
24 1
TWO-LEVEL SYSTEM
so t hat
a= E
-i>.a
(12.6.57)
lh.
E :I:
1-
-i>.a )
lJ' = A::1: ( E1 - E::1:
(12.6.58)
IA:1:I =
(12.6.59)
Now, to later compare with the perturbation theory we let>. -t 0 and find that
>.2a2
E1 - E+ -t
-(E2 - Ei) - - - F2 -E1
(12.6.60)
>.2 0 2
A+ -t
(2
>.a .
( 12.6.61)
1/1+ -t (
E;~ E1
_ -t (
,la.. )
(12.6.62)
E,-I, 1
Perturbation Theory
The 0th order c-igenvalucs nncl eigenvectors arc
E1< 0 l
= E1
D2<0 l
= E2
( 12.6.6:3)
a11d
r (O) _
V1
l )
( 12.6.64)
H'l,llioi)
(12.6.65)
'f.J
/~-i(O)
E1-~ E2 ( ~)
0
,.,(1)
..,. 2
ti\Ol(JiJ\Ol, fl'~)~O))
0
2! > -
1:
E2 (
~)
(12.6.66)
242
1/Ji
( 1)
-i.Xa ( 0 )
- E2
1
+ E1
;I., )
( E2-E1
1/12
O)
i.Xa
( 1)
1 + E 2 - E1
0
( E:is, ) .
(12.6.67)
E(2J
2
J2
a2
~ ""-----'~
E(O) - E(o)
n;i!I
n;t2
J(
E1 -
1/J~o)' H'l/J~o) J2
E2(0) -
E2
a2
=--
E(10)
E2 -
( 12.6.68)
E1
E_
(12.6.69)
E+
These results again coincide with those obtained by expanding the exact solu tions in powers of .X.
12. 7
Approximate SHO
11 < 1 .
= -klxl2+c
2
2klxl
2+
<=
2kx - 2k(x -
Also,
where
c = 0.5772 l6 ... =Euler's constant.
2kx
In I.xi
12.8.
243
Solution
Using the fir:;t hint and writing, as suggested.
c << 1
(12.7.70)
Eo =
2.hw +
( 12. 7. 71)
2k<(Ol.r ln l.rlO)
where
w
= k /m
(12.7.72)
and IO) is the corresponding simple harmonic oscillator ground state. Thus. we
need to evaluate
(Ol.r 2 In1.rlO) =
Vw
e-(mw/li)rl
dz .
( 12.7.73)
-oo
00
ft4 -3/2
.,
a-or x-lnl.rld.r=-
(1-l/2(c+ln(4o))J
(12.7.74)
12.8
Two-dimensional SHO
.,
.,
lk1 - k21>2>.
b) u~e perturbation theory to find to order >. 2 the energy of all the levels and
com pare with the exact solution to this order.
Solution
T he Hamiltonian /I is
-2
/I= I:_+
2m
I
2
"
2m
l
2
( l '2.8. 76)
p.. 2
/I = -2
+ -rm.11
2
2 .,
.r
,, 2
'
+ _11_
+ -m...i22Y2
+ mo2 ry
2m
2
(12.8.77)
where
w1
= kifm
w2
= k2/m
a- 2
= >./m.
(12.8.78)
a) Exact Solution
We now rotate the axes to remove the cross term.
X cos8+Ysin8
;c
= -XsinO+YcosO
(12.8.79)
Then,
2V
m
wr [X
w~ [X 2 sin 2 0 + Y 2 cos 2 8 -
:o sin 28)
o [-X sin20+Yzsin20+2XYcos28)
(12.8.80)
= 0.
(12.8.81)
p;
.,
.,
2m
2m
+ Py = Px + ~ .
2m
2m
( 12.8.82)
So,
p2.
H= ~
2m
p2.
2m
.,
., .,
2
+ _>_ + -mn-x
+ -mn-y1
2
(12.8.8:3)
where
w 21 cos') ()
=
n~
. ') ()
+ w2') sin
-
w, +w2
wi + Wj., -w2.,
I (
")
. 28
a- 2 s111
l /( .,
., .,
4
- 2V
w2-wi)-+4o
04
as o ~ 0 .
.,
w2 -
o4
w, -;.u2
2
.,
as o
wi)2 + fa4
0 .
(12.8.84)
l/2)1if22.
(12.8 85)
e,.,,n) =
(111
+ l/2)hf2, + (n2 +
So, to lowest order in >., for later comparison with perturbation theory, we have
(111
(12.8.86)
J2.8.
245
TWO-DIMENSIONAL SHO
b) Perturbation Theory
The Hamiltonian Ho represents two uncoupled SHO's. The energy <'igcnvalurs
are
( 12.8.87)
Also, the cigcnkets may be writte11
(12.8.88)
The first order correction lo the energy is zero since
( l2.8.89)
Jn second order we get
(12.8.90)
ow,
(Ol(n1, 112l.rylm1, m2)(0J
11
(Ol(n 1. 1121.,
~(al
.::m yW1w2
I
[ (Ol(n1,n2 lv'(m1+l)(m2+l)Jm1+l ,m2+ l)< 0 >
~
= -2IiITI yW1W2
+
+
+
(0)(111.
112l~J1111
Ii
I
[
:-;---- ~ v(m1
.::111 yWJW:?
+
+
+ l)lm1
(Ol(111,112IJmi(m2
+ l)(O)
1)< 0 >]
- l,1112
I, 1112 -
J(1111
,111
(12.8.91)
This is I he sanw r<'sull that \\"<'obtained by cxpa11ding the exact solut io11.
246
12.9
a -elfl
- IEI
and for harmonically bound electrons takes the form
- __..:.:__
o - 47r2m
L v~ fj- v2
j
Here, fj a re dimensionless constants called the "oscillator strengths" . In quantum mechanics these are defined by
47rm
fj
he v3olm;ol3 2
47rm E3 - Eo I _
3he2
h
erjo 12
:~ (Ej -
Eo}lf}ol
For N uncoupled electrons one then has the Kuhn-Thomas-Reiche sum rule
L li = N.
j
pi
H = 2m
+ V(r)
a) Show that
(En - Eo)rno
= - miii (nlPlO) .
together with the results of part a) to prove that for a single C'lectron
~2m(En-Eo)
3h2
J2. 9.
247
Solution
We start with the llarniltonian
pi
= 2m + V(Jl
( 12.9.93)
Then.
ih
-(nlPrlk) =
( 12.9.94)
/l] . Therefore.
(111[.r, ll]lk)
(12.995)
Hence, we have
iii
-(OIPrlk) = ( f:1t
m
- /~o)(Olrlk)
( 12.9.96)
--(klPrlO)
rn
It then
follow~
= (Ek -
Eo)(kl.rlO) .
(12.9.97)
that
L(Ek - Eo)(Ol.rlk)(kl.rlO)
=-
I: -(OIPrlk)(kl.rlO}
,11
>-
ih
-(OlprxlO}
L(E1c - Eo)(Ol.rlk}(kl.rlO)
L: ~(01.rlk}(klPrlO)
-ih
( 12.9.98)
111
Similarly.
L (Ek - Ho)lxkol2
k
"
le
1h
= - -(OlrPrlO)
m
(I 2.9 .99)
Therefore,
L(E1c - Eo)lrkol 2 =
"
ih
2(0lpz.r
- EPrlO)
m
/j2
'>~
(12 .9.100)
248
L
k
2m
-(Ek - Eo)l.rxol- = 1 .
112
(12.9.101)
[Jenee, since all three directions r , y: arc equivalent we have for a single <'lectron
that
21
"'
~ (Ek -
~ 3h-
( 12.9.102)
For N independent (uncoupled) electrons we therefore find the Kuhn-Thoma'>Reiche sum rule
L
x
~~(Ex -
Eo)[l.rkol + 1Yxol
+ l:kal 2 ] = L
Ix
=N
(12.9.IO:l)
12.10
Solution
The unperturbed energy for the ground state i::;
(0)
E1
h27T2
(12.10.104)
= 2ml,2 .
1/Jo =
ff
sin(u/ l)
(12.10.105 )
( 12.10.106)
ie
1L
4eEL
(12.10.107)
E1 =
h27r2
--+
-e.t:L
2m2
4
(12.10.108)
12.11.
249
POSI T RONIUM
Positroniun1
12.11
A -
=--,?bi S2
1-
Solut ion
a) The Hamiltonian for the:-e four lewls, in the absence of a magrwtic field, is
as giv<>n
A II 0 = - fi'l
St
(12.11.109)
S2
Is. m)
where
t hen, 111 tl'rrns of the spin :.talcs for the cl<>ctron and positron, r<sprct1vely, we
have
11.
I)
p,o)
(
) _ ( ~[I H)
I tt)
+I H)J )
11.-1)
I H)
(12.11.110)
~[I t !) - 11 t)J
IO, O)
Also. sine<
- s;i
,\,
W<' M'e
1 [(J>
.n]
= 2
..,, + s2- )"- - ,.,i
- ~2
(12.11.111)
11=~
0
010
2 ( 0
0 0 0
Thercfon~. I he
~!:,-=
j)
(12.11.112)
A
[1-(-3)]=2A=8.2x 10--1 e\ .
2
(12.11.113)
250
So, we have
A=4.lx10- 4 eV.
(12.11.114)
A - s2
H =Ho - - B- = --si
h2
eh B- (+ -u1 2mc
- )
u2
(12.11.115)
where iii are the Pauli matrices and the index 1 refers to the electron and the
index 2 refers to t he positron. Calling
eB
--=w
2mc
we find t hat in the representation already used we get that
- -. B
= liw
0 0
0 0
0 0
0 0 )
2 0
0 0
0 2
0 0
(12.11.116)
The eigenvalues of the total Hamiltonian are therefore (listed in the order in
which the states a re listed in (12.11.110))
A/2 , A/2 + 2/iw , A/'l. , A/2 - 2/"iw.
12.12
Solution
The unperturbed Hamiltonian is
(12 12.117)
Ho= 2J .
The energy eigenvalues are
E _ l(l +l)h 2
I -
2/
(12.12.118)
-P E =
-PEcosO .
(12.12.119)
12.13.
251
The effect of this perturbation is to produce (in lowest order) a change in energy
E1(l)
= -PE(lmlcosOllm)
(12.12.120)
(12.12.121)
lrn
(12.12.122)
=1
Llm = 0
J.
}'10
and Yoo=
we get
(001 cos Ol 10} = ( 101cos0100)
= J3 .
(12.12.123)
So, finally
(12.12.124)
12.13
252
Solution
For any op<rator A the matrix element of the time derivative of the operator i~
given by
( 12 .13 .125)
wher<' /l is the total Hamiltonian. Applying this to the opPrator
-/i(nl[d. l/]lm}
-~ (<nldlllm)- {nllldim)j
-h(Em -
J we find
En)dnm.
(12.13.126)
""
1 1
"' -- - - Inn .
1'"
d~im ;r,nn]
d - dd
(12.13.127)
d we get
= Lqj(nl[ii , llJlm)
,,
1h
L 'li(nl -.M;J-lm}
( 12 1:J 128)
So.
iii
qj [ (pj)nrn
]
2 ~"
~~ ;\[
(cl),,.,.
- (d)nm
(pj)m11
m
Ill
,,2~
-q-'>
~\I
J
as r<quir<>d.
(12.13.129)
12.14.
253
12.14
= N (~~~'.?
L riqr, Im)
Solution
lf we first write out the double commutator explicitly we find
Ii L
eiir, II Le-iiir
L:e-iqr 11
e-iq ;:,,]
eqr, Le-'F - L
L cq ;:, H ' L
cqr, -
(12 .14.t:W)
ext, we take the diagonal matrix elements (in the energy representation) of
this expression and insert a complete set of intermediate :;tales.
L
m
+ (nl
Em { (n
254
(12.14.131)
j
:i .L [Pj
eiq ;:,
jk
= -2 (fiq)2
2M ik
-2 (liq)2 N
2M
.
(12.14.132)
12 .15
Solut ion
The unperturbed ground state of the two bosons is
(12.15.134)
with energy
1
Eo = 2 x ;:liw = liw
12.1 6.
255
Here
mw)l/4
0 (x) = ( 7rh
2
exp -
mw 2)
hx
Also, the wavefunction 1,c>(x 1, x2) is already properly symmetrized. The energy
shift D. E d ue to the perturbation is given to lowest order by
D..E =
(l/J, Vintt/J)
2
2)
Vo ( -mw) 1/2
e-11~ r,+:r,
e- 0 ( r,-:r, ), dx1dx2 . (12.15.136)
211/i
_ 00
Joo .. (
X1+2'2
2
(12.15.137)
= Vo
6.E
c:~f' 1: e-
211/i
mw + 2o-h
211/i
mw + 2crli
1/2
+ r 2 /2))
dRdr
(..!!!!__) 1/2
2mw
1/2
(12.15.138)
12.1 6
111
a) Find the ground state energy correct to first order in Vo for the case of the
singlet spin state.
b) Find the ground state energy correct to first order in \'o for the case of the
t riplet spin state.
Solution
a) In lhe singlet case, the spin wavefunction is antisymmetric and the space
wavefunction is therefore symmetric in the interchange of the two coordinates.
Thus, this cai;e is identical to the case of two bosons discussed in problem 12.15.
b) In the tripl<'t ca:,e the spin waverunction is symnwtric so the space wavefunction must be antisymmetric. This forces one of I he particles to be in the
first excited state. Th1>refore, the unperturbed spatial wavefunction for the
ground state of the two fermions is
~{r1 . .r2)
J2 [0(.z:i)i(.r2) -
01(.z:t)oo(x2)]
(12.16.139)
with energy
Eo
= ~h..J
+ ~h..J
= 2fi..J
2
2
Ile re
mw)
(-2Tfh
0(.r)
t/4
rn...,
exp - - . r2
2/i
= V~
h.ro(.r)
i(.r)
( 12.16.140)
1:
The energy shift ~ E due to the perturbation is now givC'n to lowest order by
i~o
j.
e-o(r,-r,)
[5(.ri)oi(.r2)
+ I(.ti}5(.r2)
2o(xi)t(r2)1(.rt)<t>o(.r2)] dx1d.r.2
(12.16.141)
(12.16.142)
The Jacobian of this transformation is again 1. Therefore,
flE
=
=
=
12.17
Vo
j"
mw 3/2 (
\0271'(-)
'l1rh
\o r;h (
v~
c-or>
exp (- mw (2R2 +
Ji
-CV
rrh )'1
-2m..,;
mw
mw+2o!i
)3/2
r2
/2))
r2
dR d1
3 2
l (
2Tfn
) 1
271' mw + 2o h
(12.16.113;
2
=-~of
2
12.17
A l:1VA
Solu tion
If we take the electric field pointing in the .r-dir('('tion then the perturbation is
(12.17.144)
I'= -er .
The p roblem is no". for all practical purpos<'s, orw-dimensional. The ground
st ate wavefunclion is
+ rcff'rs
(..!. + b2~ + ~)
E+ - h2rr2
o,o.o - 8m
(12.17.145)
a2
(12.17 146)
c2
(t:ri.o.o. \I vcl,o,o) = 0 .
(12.17. M7)
~
n;tO
( ~,+
o,o.o \ft'-n.o.o )( !,.,'n,o.o
r:+
- -n,o.o
~o,o,o
v ~ +o.o.o )
( 12. 17 . l48)
where we have includ<>d only the non-vanishing matrix elements and the su perscri pt "-" refers lo parity
-1.
~;; 0 0
I
'
= (abc)-
1 2
as well a.-;
2 2
,_
[~
n ,0,0
/i rr ('111
I
l )
=
8m -+-+a:?
b2 c2
(12 .17.150)
11
1
= -
-I
2a
xsin((n
+ l/2)rr.r/a) dx + ;I
2n
., ( ., Tl )"
= (-l)n+l:l2a
rr- 4n- - 1 -
12.17. l.5)
1
Also,
+
fi2rr2
.,
Ea o o - Eno o = - ., (I - 4n)
8 111a-
( 12. 17.152)
~ E = _ 8HJ2 c 2 ma 4 ~
2
7rG
h2
n
~ (4n2 - 1)5
(12.17.153)
258
After equating this to the expression for the energy shift in terms of the polarizability we find that the polarizability is given by
00
4096 e2 ma 4
a=
n2
7~ n:J
L (4n2- l)S
12.18
( 12.17 .154)
= roA l/ 3 where
ro = 1.2 x 10- 13 cm
and A is the atomic number of the nucleus. Thus, the potential energy experienced by an electron near a nucleus is not simply
Ze 2
V(r) = - - .
r
If we assume that the charge density in the nucleus is constant then we have
instead the potential energy
r~
(12.18.155)
r?. R
a) Use perturbation theory to calculate the i:;otope shift, that is the dependence on A of the K-electron {ls state) for an atom with Z protons and atomic
number A.
b) Use this result lo compute the energy splitting for the K-electron between
the heaviest lead (Z = 82) isotope A
214 and the lightest A= 195.
Neglect the presence of the other electrons.
Solut ion
a) The unperturbed Ham iltonian is
p2
ze2
Ho=---.
2m
r
(12.18.156)
The perturbation is
H'
( ze2)
V(r) Ze
--r-
2
[
R2JiY
0
;!
2
+ fl]
r
R
r?. R
(12.18.157)
E~o) = - ~ Ze
2 a/Z
(12.18.158)
12. 18.
259
r-vrs;r
(2z)3/2
a
-Zr/o
( 12.18.159)
( 12.18.160)
Thus,
(1)
0
(2z)3 ze2R }{ R
~
2
e-2Zr/a
[~ - ~
2R 2
R]
dr .
r
r2
(12.18.161)
We now let
2ZR
a
2Zr
a
n=--
(12. 18.162)
z=-
Then,
(12.18.163)
= 2Zro
--j
\1 /3
"
,i/3
( 12.18.164 )
"')'.'t
/ ~oCll
l Ze 2 1_ 113 [ 12A-2/3
=-- . x 12 a/Z /
2
-r:-i'''"
12 A-2/3
( 12
b) If we tak1: Z
82 and A
values we find that
12
+ -:yA-1/3
+ :l)]
.( 1)
l! 0 (A= 195) =
3 + "f A1/3
Ze
2l a/Z
x 9.91 x
-3
10
(12.18. 165)
Substituting these
(12.18.166)
Similarly, for Z = 82 and A= 214 we get that a= 0.245 . Thus, repeating the
calculation we find that in this case
x 1.08 x 10- 2
(12.18.167)
2-; = l:l.6
e\'
the energy difference in energy of the 1, electrons between the two isotopes is
.:lE =
Zc 2
-- x 9.4 x 10- 4
2a 1Z
= 86
eV
( 12.18.168)
260
12.19
= Jc
2 ji 2
+ m 2 c4 -
mc 2
::::
-2
-2) 2
l (
!!._ - - -2 !!._
2m
2mc
2m
(12.19.169)
Use the last term as a perturbation to calculate the first order correction to the
energy levels of a hydrogenic atom.
Hi nt: The fo llowing expectation values for a hydrogenic atom may be useful
(l/r)
(I /r
n2
a/Z
1
n3(l
(12.19.170)
+ 1/2) (a/Z)2
Solution
To save labour we use the fact that
p2
l Ze 2 1
Ze 2
= E-\f=- - - - -2 + 2m
2 (a/Z) n
r
(12.19.171)
1 ((I2(a/Z)
Ze
2
- 2mc 2
1
n2 -
2 4
2
ze2) )
-1-
2 4
I [l Z e
1
Z e l
- - -2 - - -2 - --- 1 r
2mc 4 (a/Z) n 4
(a/Z) n2 ( / )
2
Z e" [1
- 2mc 2 4
12 .20
z2e"
mc2
(z)
(z)
;
2
[ 3
8n 4
(z)
n" - ;
i
+ Z 2 e2 ( 1I r 2 )]
(z)
n" + ;
1
]
n3(2/ + 1)
1
]
n3(/ + 1/2)
(12.19.172)
e2 [- -
RJ r1 r2 -
z1 .:2
261
where R is the separation of the centres of the two hydrogen atoms and rj =
(x 1 ,y 1,.:t) and r2 = (r 2 ,y2 ,.::!) are r<>spc>ctively the coordinates of the electrons
associated with atom l and 2. Using perturbation tlH'ory calculate the interaction energy of two widely Sl'parated hydrogen atoms. As an approximation for
the unperturbed cnergie.-; use
Solution
The total Hamiltonian for the two hydrogen atoms is
II = JI0 I
+ H02 + \
(12.20.li3)
i=l.2.
(12.20.174)
where
_.,
z.,
2m
r,
_ p; Jefl o. - - -
(12.20.175)
En=----;;
ao n-
(12.20.176)
T o lowest order this energy shift. is
E< 1 > =
('-1( 1,2)1\'lt>'(l,2})
f2
(12.20.177)
~
x
(~1(1,2)1Vln1,l1,m1)ln2,/2,m 2 )
n, n 2 ;1!1
(n1,/1,mtl(n2,/2,m21\'li.(J,2))
l
.,
, (1!(1,2)1V-1~(1,2})
(12.20.178}
Here we have usl'd the indicated approximation to go to the second line and the
completeness relation to obtain the last line. Thest> matrix C'lc1111'11ts are now
262
easy to evaluate using the symmetry of the ground state wavefunction. In fact
the only non-zero matrix elements are
(12.20.179)
But,
(ilr?li) =
--
41
00
3
ao o
e-2r/ao r4
dr
3ao2 .
(12 20.180)
3
(2)-~
- 2E1R6
( 12.20.181)
Bibliography
(12.l] R.Jackiw, Phys.Rev. 157, 1220, i( 1967) .
(12.2] A.Z. Capri, Nonrelatmst1c Quan/um Mechanics 3rd edition, World Scientific Publishing Co. Pte. Ltd., chapter 12. (2002) .
Chapter 13
D egenerate Perturbation
Theory
13.1
V'
= -eE r = -ef.:: .
Solution
We first write out the n = 2 levels for the hydrogen atom in units such that
length is scaled by the Bohr radius.
- r/2) e-r/ 2
v12,o.o
- --(1
1/12,1,0
1 r e -r/?- cos 0
---
v2,1,1
vs;
v'321r
-re-r/2 sinOc 1
v16<G
1
- --re-r/ 2 sinee.-
~1 2,1.-1
(13.1.1)
v'641r
111
-3
el:a (
-3
0 0 )
0 0 0
~ ~ ~
t,'1 2 ,o,o
and
t,'2, 1 ,o.
264
Here we have restored the usual units so that the Bohr radius a is no longer of
unit length. The eigenvalues of this matrix are +ct:a, -ea, 0, 0. Therefore
the degeneracy of two of the states is lifted in first order and the new energies
0
a re E~o} + ea, E~O) - ea, E~ >, and E~o} where
2
E(O} 2
_:..___
13.2
(13.1.2)
2a
= >.xy
is applied, find the change in the energy of the first excited state to first nontrivial order.
Solution
The eigenfunctions for the particle in the box are given by
I/Jn
. mrx . k1ry
= -a2 Siil
- - Siil a
a
0 $ x, y
5a.
(13.2 .3)
En,k
= -
., (n2ma-
+ k-).
(13.'2..t)
This shows that the ground state with n = k = 1 is the only nondegenerate stale.
All other states are dearly degenerate. The first excited state is two-fold d<'generate. The two degenerate states are ll, 2}(0} and 1'2, t)< 0l. The perturbation
Hamiltonian in the degenerate subspace has matrix elements <0 l(i, Jlxyli, J)(O).
When this is written out we get
H'
= (
1la
9 .. 1
91'" )
lli
a
2
(13.2.5)
'
l
a [2-
16 ]
(13.2.6)
9rr2
and
~ ( ~)
Thus, instead of
(13.2.7)
p, 2)( 0
and j2,
J) (O)
we begin with
(1:3.2.8)
13.2.
265
and
(13.2.9)
in our perturbation calculation. The first order correction is given by .>. times
the eigenvalues above. The second order terms are given by
( 13.2.10)
Now,
2J2
-.,a-
(1.ryin, k}(O)
la [.
0
-21Ty
d.x dy Sill -1TX Sill
a
a
. '21T .r . rry]
n1T .x . k1Ty
sill -sill ry sin - s i n .
a
a
a
a
(13.2.11)
But,
21a
a-
1
-;;
la
la [
(n
+ m) 7r
1
= -;;
a-
717rJ' .
1111TJ:
.rd.r Sill - - Sill - -
d [
;c .r cos
a- o
J:
(n - m)u
(n
- cos
a
(n - m)rr
+ m)7r.r]
a
d. (n - m)u
Sill
a
(n+m)7r.r]
d.
Sill - ' - - - - -
l
(11 - m)rra
l
(11+111)7ra
la . (
la . ( +
1:>111
n - m) 7r.r d
Sill
11
.r
m )7r..r d.r
a
wc>
find
(1.rvln, k}(OJ
q_!_2 .,411111 .,
(13 2 12)
.,
rr (n- - m-)-
(13 2.13)
Sub::.tituling this in the sum for the perturbation sf'fies we have the desired
result.
266
13 .3
H'
= >.(a!ata1a1 + a~a~a2a2)
on the second excited states and to first order on the third excited states. What
are the effects on the ground state and first excited states?
Solution
In this case we have
Ho= !iw (a!a1
+a~a2)
(13.3 .14)
(13.3 .15)
and
( 13.3.16)
This shows that all states except the ground state are degenerate.
second excited state we have three degenerate states:
For the
All have the same unperturbed energy 2h..u. Jn this degenerate subspace, the
perturbation Hamiltonian is
(13.3.17)
The eigenvalues are
2>., 0 , -2>. .
The corresponding eigenvectors are respectively
~(~)
( 13.3.18)
267
lt/12.+)
ll/J2,o)
lt/12.-)
Therefore, writing r ==
+1, 0, -1
= 2hw + r2,\ +
(13.3.19)
we find
n1+n~;t2
I (Ol(n1. n2IH'll/J2,r)l 2
2hw - ( n1 + n2 )Iiw
(13.3.20)
131O) (O) 12, l)(O) 11. 2)<0 > 10. 3)< 0 >
I
( 13.3.21)
0, , 0,
Ji2,\,
and,
-/i2,\.
Not all the degeneracies a re lifted. f'or this reason we only compute to first
order in ,\, To this order the eigenvalues are
E3,r
= 3hw + rv'l2>.
( 13.3.22)
where r = 0, 0, 1.
13.4
= ,\((a!a2 + a;at)].
A2
= -a1
sin 0 + a2 cos8
and choosing fJ appropriately. Do this and compare with the perturbation result.
268
Solution
a) Again we have
(13.4.23)
We fi rst solve for lhe eigenvalues to second order in A, then we solve the problem
exactly and compare. For n1 + n2 = 2 (second excited state) we have the three
degenerate st ates:
12, O)(o) , Il, 1)(O) , and IO. 2)<0 >.
T he perturbation Ha m iltonian in this degenerate subspace is
(13.4.2-1)
The eigenvalues arc: 2A , 0 , -2A. The corresponding eigenvectors arc respect ively
I/,/?, )
1/2 )
I I,/?,
1/2
1/2
-l~v'2
-1/,/?,
(13.4.25)
1/2
ltc12 +) =
!12 O)(O)
2'
=
li.2,-)
_I 12 O)(o) - _I IO 2)(0)
v'2 '
v'2
!12 0)(0) - _I II
2 '
V:J'
J)(O)
+ !10
2'
2)(0).
( 13.4.26)
This yields:
= 21t..v + r2A
(13.4.27)
Since If' does nol change the sum over n 1 + n 2 there is no second order contribution. T he third exc:itccl states are:
j3,\
0
0
( 13.4.28)
13.4.
:u . -:l>. . A , -A.
269
The corresponding
1/./2 )
-../3/2
2 ( ../3/2
-1/./2
1/../1 )
1 ./3/2
2 ( ../3/2
I I .,/2
/3/2 )
1 -1/./2
2 ( -1/./2 .
/3/2
./3/2
)
1/../2
2 ( -1/./2
-/3/2
(13.4.29)
We could now again compute the new ba..;i:-. \'ectors and go on to :second order,
but becau:.c> [11 0 , ll')
0 there is no second order contribution. Thu:;, correct
to second order the energies art>
E2 = 3fiw 3A 3hw A .
(134.30)
b) \Ve next examine the exact solution. for this purpose we make the principal
axis transformation
-<11 sin
0 + a2 ros 0 .
(13.4.31)
Ho
a1,
al.
a2.
a~.
= h.1o1(ula1 + o~a2)
/1,W( r\ I A+ [JIB)
(13.4.32)
and
f/ 1
(AlsinO+B'co:sO)(AcosO-BsinO)]
+ Bl A) co:s 20)
( 13.4 .:3:3)
A) JJ1 8 .
(I :J.'l.:M)
= \\
270
13.5
Find to order ,\2 the energy of the ground state and first excited state. Compare
your answer with the exact solution obtained in problem 12.8c.
Solution
In this case k 1 ~ k2 and all levels except the ground state are almost degenerate.
Thus, for the fi rst two excited states we need to use degenerate perturbation
theory.
Ground state: n1 = n2 = 0
( 13.5.36)
and
E(l)
- 0
0,0 -
( 13.5.37)
while
( 13.5.38)
where we have
(13.5.39)
Thus, we get
>.2 n2
,(2) -
Eo o - - -----,
4m 2 w1w2 h(w1 + w2)
( 13.5.40)
Wl -W2
k1 - k2
= ---
(13.5.41)
J1
Pr
+ Py2
2m
= 0, n 2
= 1 ; n = 1 , =0
1
2
+ -2 k 1r + -k
2 y + >.xy .
2
n2
( 13.5.42)
Our perturbation is
H' = >.xy = ?h>. (a1 +al)(a2
m1.J
+a~).
(13.5.43)
13.5.
271
E~> =
h)..
2mJw1w2
(13.5.45)
( 13.5.48)
Bu t,
2m
~
~ [<o, ll(at + ai)(a~ + a 2 )1n 1 , n 2 )
w.,..i2 v2
(13.5.49)
So, for n 1
+ n 2 f::
(13.5.50)
(l/1IH'ln1. 2)
= 2 m~ (c5n, ,1c5n,,2 On
,2c5n 2 ,i]
(13.5.51)
v nAr i.eft
l;J.
>.. ti
- 4m2w 1w2
Wt
i
+w2
1 ]
+2w1
(13.5.52)
and
(13.5.53)
Again, if we set w 1 = w2 1 we find that the results agree to order >.. 2 with the
exact results obtained in problem 12.8a.
13.6
E = E(y/a, .r/a, 0)
is applied to this particle. Find the energy of the ground state and first excited
states correct to order 11.
Solution
for a box with sides (a, a, b) the <>nergy eigcn::.tates for a particle in this box arc
r( o)
Vn m r
'
2.J'i
. (11rr.z:) . (mrry) (''rrz)
/i' sin - - Siil - - Siil avb
(I :1.6.51)
m
a-.,
-
where n.
Since b
111,
<<
(I :l.6 .5fi)
state; are dPgenerate and their energy is given by E\~J.. = E~~l, 1 Thus, the
ground stale perturbation is given by taking the expectation value of the pnturb111g potPntial which is given by
e
a
-e<f> = -.ry.
( 13.6 .fi6)
The resu It is
cf.
-(1.1.
a
(0)
J , J,J
=
=
!l.rvlt.1, 1)
41 . ., (71'.r)
c
--;;
a a-
eEa
4
s111
.r d.c
r ., ('211'y)
Jo
sin
--;-
y dy
(l~.6.57)
13. 7.
273
f or the fi r:-.t excited states we nN'd to diagonalize the perturbation in the degenerate sub:-.pacP. T hus, we have to evaluate
e
.
_ r .
.
-(I. 2, !lr.yp, 2, 1) - -(:.! , l , l!r.1112.1, I}
a
a
41
(rr.r)
7 .r d.r 1/J . ., (2rry)
Q
rf. a
= -;
2
.,
O Sill-
O Sill-
ydy
1.a
4
(l:l .6.58)
as w<'ll as
rf.
1.
41 (".r)
7 .
4
ef.
~a:?
Sin
1
4
(2;;-r)
--;;--
Siil
dz
O Siil
(T.'/) . ('lrry)
7 y dy
-;:--
256
r f . a -4
8l
rr
Siii
(13.6.59)
2t1 ;,:;. ) .
Ill..,.
(13.6.60)
"
~ 8215:"]
( 13.6.61)
13. 7
Ho =
,,2
-'lni
on - a
<
r <n
-
Dp
= {/(x} E C
1/(-a) = -/(a)}
Find t hi' :-.hi ft in energy of all I ht en<'rgy levels to first nontrivial order due to
a perlu rbat ion
>.H' = >..r .
Hi nt: T iu ugensolutions for Jl0 arl' giv<n in (l:l.l] and are
/u(r)
..
F:.n
..
/~ - { n+l )
u-,,""'
:;---:;(n
;,ma-
1/ '2)
(1~ . 7 . 6'2)
vnArnn! lJ.
Solution
The eigenfunctions of the unperturbed Hamiltonian are, as in [13.l], given by
~ ei1r(n+l/2):r/o
fn(x) =
= 0, 1, 2, ...
v2a
(13.7.64)
En =
1T2 h2
E-(n+l)
= - 2 (n + 1/2) .
2ma
(13.7.65)
This shows that every eigenvalue is two-fold degenerate. We thus need to diagonalize the perturbation Hamiltonian in the degenerate subspace::.. This means
we have to evaluate the matrix elements
(/n,Xfn)
= U-(n+l).Xf-{n+l)) = 0
(13.7 66)
as well as
Un. xf-{n+l)) =
U-(n+l) x/n)r
= 7r( 2na+ l)
( 13. 7 .67)
The energy corrections are now given by the eigenvalues of the matrix
(2 >.a ) ( 01 01 ) .
n
+l
( 13. 7 .68)
1T
>.a
(13.7.69)
(2n+l)11"
Thus, all the degeneracies are lifted and the energies corresponding to En and
E-{n+l) are
1T2h2
>.a
- - ( n + 1/2)- - - 2ma2
(2n + 1)11"
13.8
2
21
a) What are the energies of the lowest and first excited states?
b) A perturbation
H'
eB
= g-L:r
Mc
(13.7.70)
13.8.
275
Solution
We have
Ho
2
= 21
'
eB
= g Mc
Lr .
(13.8.71)
HoYi,m =
l(/+l )h2
2I
Yi,m
( 13.8. 72)
Lr= 2"(L+
+ L)
(13.8.73)
(13.8.74)
since
(13.8.75)
For the first excited state's we have to diagonalize the matrix with matrix
elements
(Y1 m, LrF1,m)
= ~ [)'2 -
m(m
1)6m',m-l ] . {13.8.76)
I ( 0 1 0)
V2
(13.8.77)
I 0 l
0 l 0
fi:?
I
1.
li 2
eB
--gr \le
( 13.8. 78)
Et
'1 2
eB
= -1(1 + l) + g-rnh
'
I
Al e
m
(13.8.79)
276
13.9
Find the energy correct to order ..\2 for the second excited state of the Hamiltonian
H =Ho+ ..\H'
where
l
l
2( 2
2)
2mw
x +y
and
H' =
xpy.
Solution
The energy levels of the second excited stale are 12. 0) , ll. l) , IO. 2). They all
have the same energy 3hw. We now diagonalize the perturbation part of the
Hamiltonian in the degenerate subspace. To do this we use
x=
vth
+ ai)
~(a 1
iv. r;;r;:;;
22
Py=
-(a2 - a2)
{13.9.80)
Then,
\ h[
t
t t
t
)
"\If' ='"2a1a
2 +a 1a 2 - a 1a2-a 1a2.
(13.9.81)
1 0 )
0 l
-1 0
(13 .9.82)
v'6
1. )
1 ( 1 )
~ll
../2
'
1 (
v'6
-=-~l
(13.9.83)
.
Thus, the new ba:;is states wc use for starting the perturbation computation arc
It/I+> = ~(l2,o)+2ill,l)-I0,2))
lt,'.>o)
v'6c12,o}-2ip,1)-I0,2}) .
(13.9.84)
13.10.
PASCllEN-BACK EFFECT
277
\Ve now have to compute the terms H'l\.1+), H'ltbo) , and H'lv-) which do not
co ntain terms 111, m) with n + m = '2. T hen we have (arter omitting the terms
with n + rn = 2)
>.(ri. mlH'l}
= -i v6
1-
and
(I 3 .9.86)
so that
2
(>./1) [
- - -'}. - +(:l-!i
-'}.- +:J-5
-16- +3-1
-4-]
16/i...; (3-5)
t>. 2 Ji
( 1:U).8/)
>.2/i
(1:\.9.88)
--::;-
Yes. t his prohlcrn c:u1 be . . ohed exactly since the total Hamiltonian is quadratic
in thr. annihilation and creation oper:1tors.
13.10
Paschen-Back Effect
Cak ulat< (to fir::.t order) tlw splitting of 1111 11,/ lr.wls for I= O, I of l h< nergy
levC'ls of tl11~ \'iilrnre rlc-ctron of an nllrnli 11to111 in a strong 11111g11t'ti1 field. For
Wrak fic lcls this is I he ze,.111n11 dfed . !"or 11111gnet ic field.., so strong I hat their
E'ffcct is greater than the spin-orhit split ting t hf' rc...ult is known as I ht P;lsclwnBack f'ffoct .
llinl : for the Paschr.n-Back effect it may be conwnicnt to Usf' some of the
results of prohl"m 17 7 .
Solution
We t ak<' I hc> 111ap,11rtic field 10 point i11 t lic> :-direct ion. In that cas<' t h1 ll a111ilto11inn for t 111 \"al11w<' elc?Ct run i. .
/i'!.
II=:;--+ V(r)
Liii
I d\I -
+ -.
-., ---J,. :i 2111c- r c1r
eH
-(!,,
'lmc
. . .,
+ :l.),) .
(J:U0.89)
( t:U0.90)
~ . v
vnAYJ,t:;H.
we have the weak field or Zeeman effect. In that case it is convenient to choose
states of good j, mj and this situation is solved in general in problem 17 .10.
On the other hand if
l 1 dV eB
13/2, 3/2)
13/2, 1/2)
13/2, - 1/2)
13/2, -3/2)
ll /2, 1/2)
ll/2, -1/2)
=
=
=
=
1
y13ll,
-1)11/2, 1/2) +
I
11. -1)11/2, 1/2) - .fill,
O}ll/2, -1/2) . (13.10 .92)
13/2, 3/2)
1
13/2, 1/2) + ./311/2,
1/2}
II. O)II/2,-1/2) =
ll, -1)11/2, -1/2)
1
13/2, -1/2) + J31I/2,
-1/2)
1
v'313/2,
-1/2)-
311/2, -1/2)
13/2, -3/2) .
(13.l0.9:l)
( J 3.10.94)
eB
2mc
Cn,I
(13.10.95)
279
PASCHEN-BACK EFFECT
the result is
Cn,l
Cn,l
+ 2fiw
+ fiw
0
0
Cn,l -
fiw
Cn,l -
2/iw
+ fiw
<n,I + fiw
Cn,l
(13.10.96)
L S=~(P-l2-S1).
(13.10.97)
Ii =
3/2, 3/2)
h2
2[3/2(3/2+ 1)-1(1+1)-3/1]
fj2
(13.10.98)
,,2
2[1/2(1/2 + l) - O- :J/4)
=0
(l:U0.99)
This leaves only four states to consider. These split into two pairs: those with
mj
1/2 and those with mj -1/2. Thus, we can consider them separately.
However, LSis not diagonal in this representation. In fact we find that
L = ~ (
For mJ
L,
L+
L_ )
-L,
(13.10.100)
(;' ( ~
~)
(13.10.101)
~ov
The energy corrections are just the eigenvalues of this matrix. These are easily
found to be
1
2(nt
and
(nl .
mj
../2.
../2. )
(13.10.lO:l)
and
C'nl
lnt/2 -
Jr/
2...v 2
ln/
(13.10 106)
J3.11.
281
This shows that the term with the+ sign corresponds to the case m1 = 0, m,
1/2 and the term with the - sign corresponds to m1 = 1, m, = -1/2.
Similarly, for mi= - 1/2 we find the eigenvalues
lnt/(hN)
13.11
m1
= 0,
m,
hw + lnt
<;t
(13.10.107)
sign corresponds
Using the results of problem l 0. 11 and 11.22 calculate the energy 1:>hift in the
hydrogen atom energy lcv<'ls (fine structure) <lu<' to a weak electric field.
Solution
We have the weak perturbation
V(T)
= e::
(13.11 108)
whe re we have chosen the electric field to poi11t in the ::-direction Also, from
problem 11.'2'2 we have that the unperturbed normalized hydrogen atom wavefun ctions are
Rn .j-1f2(r)
J2l+l
Rn,J+l/2(r)
Ill n,1,j=l-1/2,m
J2l+l
(
Ji (-Jt
)
)
(13.11.109)
m + 1/2 }'i,m-1/2
+ tn + lf:H'j m+1/2
( 13.11.110)
t.J1
Wn ,lj=l-1/2,m
l/12
(13.11.111)
282
The energy levels in the unperturbed hydrogen atom are labc>lled by n, j. Under
the perturbation the orbital angular momentum no longer commutes with the
Hamiltonian and thus, I is no longer a good quantum number However , the zcomponent of the total angular momentum J 2 , namely m, continues to be a good
quantum number. Thus, the matrix P)ements of the perturbation Hamilt onian
V between stales with different m vanish. The diagonal matrix elements of \'
also vanish
( '11n,l,j=I+1/2.m VIit n,1,j=I+ 1/2,m)
(~~1.VlJit)=O
(t,12. V1P2) = 0
(13.11.l IL)
Vi:i =
\'21
ef
2 JjU + l)
lc:-:i
r 3 Rn
(r)R
.,(r) dr
O
,J-1/2
n,J+I/.
[JU+ m)(; -
+ 1)
-JU- m)(j + m + 1)
j Y/_
j Y/_
(13.11.113)
To perform th<' angular integral ion we use that
cos O YI m (0, <;i)
(l+m+ 1)(1-m+l),
(21 + 1)(21+3)
}i+l ,m (O, ip)
(L + m)(l - m)
(21 - 1)(2/ + 1) Yt-i .m(O, <p)
(13.11.111)
Vi2 =
Vii
el:
= 2 JiU
+ l)
l oo
0
m
X--::===
Jj(i + 1)
3
1
Rn,j-1/2(r)Rn,j+lf2(r) dr
(13.11.115)
fo
00
3
r Rn,j-1f2(r)Rn,j+112(r) dr
(13. 11116)
and may be evaluated using the generating function as in problem 10.11 to yield
-~nJn2 -
(j + L/2)2 .
283
BIBLIOGRA PHY
3 nJn2
Vi2 =Vii= -4
(j + 1/2)2m f'
j(j + 1
e
( 13.11.117)
v= (
~1
Vi2
)
0
(13.11.118)
(13.11.119)
Finally we see that for a fixed value of n all tnms of the fine structure, except
the term with j = n - 1/2. are split into 2j + 1 equidistant levels corresponding
to m = - j,. . , j The term with j = n - 1/2 is not split at all since I ha:; a
fixed value I = j - 1/2
n - l and is not degenerate as regards the quantum
number I.
Bibliography
[13.1] A.Z. Capri, .Vonrelatmstic Quantum Jfechamcs 3rd edition, World Scientific Publishing Co. Pte. Ltd., section 6.8, (2002) .