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Sakurai J.J. Modern Quantum Mechanics (AW, 1994)(802dpi)(T)(513s)

Sakurai J.J. Modern Quantum Mechanics (AW, 1994)(802dpi)(T)(513s)

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Sections

Statementof the Problem

The approximation method we considerhere is time-independent
perturbation theory\342\200\224sometimes known as the Rayleigh-Schrodingerper-
perturbation

theory.We considera time-independentHamiltonian H suchthat
it can besplit into two parts, namely,

E.1.1)

285

286

Approximation Methods

where the V=0 problemisassumedto have beensolvedin the sensethat
both the exactenergyeigenkets\\n@)) and the exactenergyeigenvaluesE^0)
are known:

H0\\n^)=

E^\\n((\302\273).

E.1.2)

We are required to find approximateeigenketsand eigenvaluesfor the full
Hamiltonian problem

(H0+ V)\\n) =

En\\n)9

E.1.3)

where V isknown as the perturbation; it is not, in general,the full-potential
operator.Forexample, supposewe considerthe hydrogen atom in an
external electricor magnetic field. The unperturbed Hamiltonian Ho is
taken to bethe kinetic energy p2/2mand the Coulombpotentialdue to the
presenceof the proton nucleus \342\200\224

e2/r.Onlythat part of the potentialdue
to the interaction with the external E or B field is representedby the
perturbation V.

InsteadofE.1.3)

it iscustomary to solve

(H0+ \\V)\\n) =

En\\n)9

E.1.4)

where X is a continuous real parameter.This parameter is introduced to
keeptrack of the number of times the perturbationenters.At the end of the
calculationwe may set X ->1to get backto the full-strength case.In other
words,we assumethat the strength of the perturbation can becontrolled.
The parameter X can be visualizedto vary continuously from 0 to 1,the

X =0casecorrespondingto the unperturbedproblemand X =1correspond-

corresponding

to the full-strength problemofE.1.3).

In physicalsituations wherethis
approximationmethodisapplicable,we expectto seea smoothtransition of

|w\302\260>

into \\n) and E$\302\273

into En as X is \"dialed\" from 0 to 1.
The method restson the expansionof the energy eigenvaluesand
energyeigenketsin powerof X. This means that we implicitly assumethe
analyticity of the energyeigenvaluesand eigenketsin a complex X-plane
around X =0.Of course,if our method isto beof practicalinterest,good
approximationscan better beobtainedby taking only one or two terms in
the expansion.

The Two-StateProblem

Beforeweembark on a systematicpresentationof the basicmethod,
let us seehow the expansionin X

might indeedbe valid in the exactly
solubletwo-stateproblem we have encounteredmany times already. Sup-

5.1.

Time-Independent Perturbation Theory: Nondegenerate Case

287

posewehave a Hamiltonian that canbewritten as

f ?f|2@>><2@>|

+XK12|l@>><2@)|+XK21|2(O)>A(O)|,

E.1.5)

where |l@))and |2@))are the energyeigenketsfor the X =0 problem,and
we considerthe caseVn =

V22 =0.In this representation the H may be

representedby a squarematrix asfollows:

H=

xk12

21 z

E.1.6)

wherewe have usedthe basisformedby the unperturbedenergyeigenkets.
The V matrix must, of course,beHermitian; let us solvethe casewhen

Vl2

and V2l are real:

Vn =

Vl*2,

V2l =

V2*;

E.1.7)

hence,by Hermiticity

E.1.8)

This can alwaysbedoneby adjusting the phaseof |2@))relative to that of
|l@)).The problemof obtaining the energyeigenvalueshere is completely
analogousto that of solving the spin-orientationproblem,wherethe ana-

analogue ofE.1.6)

is

=

V2l.

H=

o o#a= 0 ' a3 ai

ao-a3 E.1.9)

where we assumea =

(ax,0,a3) is small and ao,ava3are all real.The

eigenvaluesfor this problemare known to bejust

E.1.10)

By analogythe correspondingeigenvaluesfor E.1.6)

are

E

X2F12 E.1.11)

Let us supposeX|F12|

issmall comparedwith the relevant energyscale,the
differenceof the energyeigenvaluesof the unperturbedproblem:

E.1.12)

We can then use

.

1 e2

\\/l +e

=l+-e-y+\342\200\242\342\200\242\342\200\242

E.1.13)

to obtain the expansion of the energy eigenvaluesin the presenceof

288

Approximation Methods

perturbation X|F12|,

namely,

E.1.14)

(?f -

Theseare expressionsthat we can readily obtain using the general for-

formalism to bedevelopedshortly. It isalsopossibleto write down the energy
eigenketsin

analogywith the spin-orientationproblem.
The readermight be led to believethat a perturbation expansion
alwaysexistsfor a sufficiently weak perturbation.Unfortunately this isnot
necessarilythe case.As an elementaryexample,considera one-dimensional
probleminvolving a particleofmassm in a very weak square-wellpotential
of depth Vo (V=-Vofor -a a). This problem
admits one bound stateof energy,

E = -Bma2/h2)\\XV\\2, X >0 for attraction. E.1.15)

We might regardthe squarewell as a very weak perturbationto beaddedto
the free-particleHamiltonian and interpret result E.1.15)

as the energyshift
in the ground state from zero to |XF|2.Specifically,becauseE.1.15)

is
quadratic in F, we might betemptedto associatethis as the energyshift of
the ground state computedaccordingto second-orderperturbation theory.
However,this view isfalsebecauseif this werethe case,the system would
alsoadmit an E <0 state for a repulsivepotential casewith X negative,
which would besheernonsense.
Let us now examinethe radius of convergenceof seriesexpansion

E.1.14).

If wegobackto the exactexpressionofE.1.11)

and regardit as a
function of a complexvariableX, we seethat as |X|isincreasedfrom zero,
branch points are encounteredat

The condition for the convergenceof the seriesexpansion for the X =1
full-strength caseis

@)_?@)

l

If this conditionisnot met, perturbation expansionE.1.14)

ismeaningless.

Seethe discussion on convergence following E.1.44),

under general remarks.

5.1.Time-Independent Perturbation Theory: Nondegenerate Case

289

Formal Developmentof Perturbation Expansion

We now state in morepreciseterms the basicproblemwe wish to
solve.Supposewe know completelyand exactlythe energyeigenketsand
energyeigenvaluesof

E.1.18)

The set {|n@))}is completein the sensethat the closurerelation 1=

LJh@))(h@)|

holds.Furthermore, we assumehere that the energyspectrum
isnondegenerate;in the next sectionwe will relaxthis assumption.We are
interestedin obtaining the energyeigenvaluesand eigenketsfor the problem
definedby E.1.4).

To beconsistentwith E.1.18)

we shouldwrite E.1.4)
as

(H0+XV)\\n)x =

E^\\n)x

E.1.19)

to denotethe fact that the energyeigenvaluesE^X) and energyeigenkets

\\n)x are functionsof the continuousparameter A; however,we will

usually

dispensewith this correctbut morecumbersomenotation.
As the continuousparameterA isincreasedfrom zero,we expectthe
energy eigenvalueEn for the nth eigenketto depart from its unperturbed
value E^\302\260\\

sowedefinethe energyshift for the nih levelas follows:

E.1.20)

The basicSchrodingerequationto besolved(approximately)is

{)?

E.1.21)

We may be tempted to invert the operator Ef\302\256

\342\200\224

Ho; however,in general,

the inverse operator l/(?w@)\342\200\224

HQ)is ill defined becauseit may act on

|\302\253@)). Fortunately in our case(XV\342\200\224

Aw)|w) hasno componentalong|\302\253@)),
as can easilybe seenby multiplying both sidesofE.1.21)

by (\302\253@)| on the

left:

E.1.22)

Supposewedefinethe complementaryprojectionoperator

E.1.23)

n

The inverseoperator l/(?w@)-Ho)iswell definedwhen it multiplies n on
the right. Explicitly,

1

*,-E

\342\200\236\302\273.'

)<*m|. E.1-24)

17@) _ ff ^ ^ 17@) _ F@)

Also from E.1.22)

and E.1.23),

it isevident that

(XV-bn)\\n) =

4>n(XV- A

J|n>. E.1.25)

290

Approximation Methods

We may thereforebetemptedto rewrite E.1.21)

as

However,this cannotbecorrectbecauseas X ->0,we must have \\n) ->

\\n@))

and A^->0.Nevertheless,even for X =?

0, we can always add to \\n) a

solution to the homogeneousequation E.1.18),

namely, cn\\n@)), so a

suitablefinal form is

\\n) =

cn(X)\\n^)+

^(XK-Aw)|#i>, E.1.27)

where

\\imcn(X)=l.

E.1.28)

Notethat

E.1.29)

For reasonswe will seelater, it is convenient to depart from the
usual normalizationconvention

(n\\n)=l.

E.1.30)

Rather, we set

E.1.31)

even for X #0.We can always do this if we are not worried about the
overallnormalizationbecausethe only effectof setting cn #1isto introduce
a common multiplicative factor.Thus, if desired,we can always normalize
the ket at the very end of the calculation.It isalsocustomaryto write

E.1-32)

^(O)_

and similarly

1

1

1

E.1.33)

sowe have

E.1-34)

We alsonote from E.1.22)

and E.1.31)

that

)-

E.1.35)

Everything dependson the two equations in

E.1.34)

and E.1.35).

Our basicstrategy is to expand \\n) and A^ in the powersof X and then

5.1.

Time-Independent Perturbation Theory: Nondegenerate Case

291

match the appropriate coefficients.This is justified becauseE.1.34)

and

E.1.35)

are identitieswhich hold for all valuesof X between0 and 1.We

beginby writing

n

n ' '*

\342\200\224n

Substituting E.1.36)

into E.1.35)

and equating the coefficientof various

powersof X, we obtain

0(X2):

E.1.37)

so to evaluate the energyshift up to orderX^ it is sufficient to know

|\302\253>

only up to orderX^\021. We now lookat E.1.34);

when it isexpandedusing

E.1.36),

we get

X

(\\nw) +X\\n{1)) +

\342\200\242\342\200\242\342\200\242)\342\200\242

E.1.38)

Equating the coefficientof powersof X, we have

0(X):

n **0

wherewehaveused^A^I/7^)=0.Armed with

\\n(l)), it isnow profitable

for us to go backto our earlierexpressionfor A(^ [seeE.1.37)]:

E.1.40)

Knowing A(^\\ we can work out the X2-term in ket equationE.1.38)

also

using E.1.39)

asfollows:

0(X2): |kB))= *\"

V

E^H

E.1.41)

292

Approximation Methods

Clearly,we can continuein this fashion as long as we wish. Our operator
method isvery compact;it isnot necessaryto write down the indiceseach
time. Of course,to do practical calculationswe must useat the end the
explicitform of n as given by E.1.23).
To seehow all this works, we write down the explicitexpansionfor

the energyshift

A =Z7

n

n

\342\200\224n

W I2

^( 142)

where

Vnk =

(n@)\\V\\k@)) *(n\\V\\k),

E.1.43)

that is, the matrix elementsare taken with respectto unperturbed kets.
Noticethat when we apply the expansion to the two-state problem we
recoverthe earlierexpressionE.1.14).

The expansionfor the perturbed ket

goesas follows:

Vkn

n

p@) _ p@)

+ x-

1^ rnrXkn

^n ^k ) I

-\".

E.1.44)

Equation E.1.44)

says that the nth levelis no longer proportional to the
unperturbed ket \\n@)) but acquirescomponentsalong other unperturbed
energy kets;stated another way, the perturbation V mixesvarious unper-

unperturbed

energyeigenkets.
A few generalremarks are in order.First, to obtain the first-order
energy shift it is sufficient to evaluate the expectation value of V with
respectto the unperturbedkets.Second,it isevident from the expressionof
the second-order

energy shift E.1.42)

that two energy levels,say the zth
leveland the jthlevel,when connectedby V tend to repeleachother; the
lowerone,say the /th level,tendsto get depressedas a result of mixing with
the higher jth levelby |^7|2/(^7@)

-?,@))>while the energyof thejth level
goesup by the sameamount. Thisis a specialcaseof the no-levelcrossing
theorem,which statesthat apairofenergylevelsconnectedby perturbation
donot crossas the strength of the perturbation is varied.
Supposethereismorethan onepairof levelswith appreciablematrix

elementsbut the ket |\302\253),

whoseenergywe are concernedwith, refersto the

ground state; then eachterm in E.1.42)

for the second-orderenergyshift is
negative.This means that the second-orderenergyshift is always negative

5.1.Time-Independent Perturbation Theory: Nondegenerate Case

293

for the ground state; the loweststate tends to get evenloweras a result of

mixing.

It is clearthat perturbation expansionsE.1.42)

and E.1.44)

will

convergeif |Ff//(jE/0)\342\200\224

?/0))|issufficiently \"

small.\" A morespecificcrite-

criterion

can be given for the casein which

Ho is simply the kinetic-energy
operator(then this Rayleigh-Schrodingerperturbationexpansionisjust the
Born series):At an energy Eo<0, the Born seriesconvergesif and only if
neither Ho+ V nor Ho\342\200\224

V has bound states of energy E

Newton1982,

p.233).

Wave-function Renormalization

We are in a positionto look at the normalization of the perturbed
ket.Recallingthe normalization conventionwe use,E.1.31),

weseethat the
perturbedket \\n) isnot normalizedin the usual manner.We can renormal-
ize the perturbedket by defining

E.1.45)

where Zn issimply a constant with

js/(n\\n)N = 1.Multiplying (ai@)| on the

left we obtain [becauseofE.1.31)]

ZY2 =

(n^\\n)N.

E.1.46)

What isthe physicalmeaningof Znl Because|n)N satisfiesthe usual nor-

normalization

requirementE.1.30),

Zn canberegardedas the probabilityfor
the perturbedenergy eigenstateto be found in the correspondingunper-

unperturbed

energy eigenstate.Noting

N(n\\n)N =

Zn(n\\n)=\\,

E.1.47)

we have

\021

=

(n\\n) =

+0(X3),

E.1.48a)

so up to order X2, we get for the probabilityof the perturbed state to be
found in the correspondingunperturbedstate

\342\200\2247-

E.1.48b)

The secondterm in E.1.48b)

is to be understood as the probability for

294

Approximation Methods

\"leakage\"to states other than

|/7@)).Notice that

Zn is lessthan 1,as

expectedon the basisof the probabilityinterpretationfor Z.
It isalsoamusing to note from E.1.42)

that to orderX2, Z isrelated

to the derivativeof En with respectto E^0) as follows:

E.1.49)

We understand, of course,that in taking the partial derivative of En with
respectto E^\302\260\\

wemust regardthe matrix elementsof V as fixed quantities.

Result E.1.49)

is actually quite generaland not restricted to second-order

perturbation theory.

Elementary Examples

To illustrate the perturbationmethodwehave developed,let us look
at two examples.The first oneconcernsa simpleharmonicoscillatorwhose
unperturbed Hamiltonian isthe usual one:

\\

E.1.50)

2m 2

Supposethe spring constant k

\342\200\224

moo2 ischangedslightly. We may represent

the modificationby addingan extrapotential

V={emu2x2,

E.1.51)

where \342\202\254

isa dimensionlessparametersuchthat e<^1.From a certainpoint
of view this is the silliestproblemin the world to which to apply perturba-

perturbation

theory; the exactsolution isimmediately obtainedjust by changing to

as follows:

eco,

E.1.52)

yet this is an instructive examplebecauseit affordsa comparisonbetween
the perturbation approximationand the exactapproach.
We are concernedhere with the new ground-state ket |0) in the
presenceof V and the ground-stateenergyshift

Ao:
^ 0)

and

A =v + Y L1MJ

+

\342\200\242\342\200\242\342\200\242

E 1 53b^

K ^0 0

/c

The relevantmatrix elementsare(seeProblem5 in this chapter)

em^

>

=

^ E.1.54)

?mwM

<2^|jc2|0<\302\260>>

=

^-.

2y2

5.1.Time-Independent Perturbation Theory: Nondegenerate Case

295

All other matrix elementsof form Vk0 vanish. Noting that the nonvanishing
energydenominatorsin E.1.53a)

and E.1.53b)

are \342\200\2242hco,

we can combine

everything to obtain

E.1.55a)

and

A = F -F@)=

f

E.1.55b)

Noticethat asa result ofperturbation,the ground-stateket, when expanded
in terms of original unperturbed energy eigenkets (|^@))},acquires a
component along the secondexcited state. The absenceof a component
along the first excitedstateisnot surprising becauseour total Hisinvariant
under parity; hence, an energy eigenstate is expectedto be a parity
eigenstate.

A comparisonwith the exact method can easilybe made for the

energyshift asfollows:

hco

~2

hco

E.1.56)

in completeagreementwith E.1.55b).

As for the perturbed ket, we lookat
the changein the wave function. In the absenceof V the ground-statewave
function is

1 -x2/2x20

771/4

E.1.57)

where

h

mco

E.1.58)

Substitution E.1.52)

leadsto

x

o

0

1/4'

E.1.59)

hence,

1

1/4

1 1

1/8

\\

I/O

e) exp x

2xo A+e)1/2

-x2/2x20

771/4,/JC

-x2/2xl

.1/4

]__ 1^
8 4 V2

JC

0

E.1.60)

296

Approximation Methods

where we have used

(x2@))= 1

2V2(x

1 1 1

1

x '

\\

x0

-x2f2xl

2l

2 + 4

E.1.61)

2V2tt1/4
and H2(x/x0)isa Hermitepolynomialof order2.
As another illustration of nondegenerate

perturbation theory, we

discussthe quadratic Starkeffect. A one-electronatom\342\200\224the

hydrogen

atom or a hydrogenlikeatom with onevalenceelectronoutsidethe closed
(sphericallysymmetrical)shell\342\200\224is

subjectedto a uniform electricfield in

the positivez-direction.

The HamiltonianHis split into two parts,

. V0(r) and V = -eE z (e<0 for the electron).

2m

E.1.62)

[Editor'sNote:Sincethe perturbation V

\342\200\224>

\342\200\224

ocas z

\342\200\224>

\342\200\224

o\302\260,

particles
bound by Hocan,of course,escapenow, and all formerly bound states
acquire a finite lifetime. However,we can still formally useperturbation
theoryto calculatethe shift in the energy.(Theimaginary part ofthis shift,
which we shall ignorehere,would give us the lifetimeof the state or the

width of the correspondingresonance.)]

It is assumedthat the energy eigenketsand the energy spectrum for the
unperturbed problem(Hoonly) are completelyknown.The electronspin
turns out to be irrelevant in this problem,and we assumethat with

spin

degrees

offreedomignored,noenergylevelisdegenerate.

Thisassumption
doesnot holdfor n ?^1levelsof the hydrogenatoms, where Vo is the pure
Coulombpotential; wewill treat suchcaseslater.The energyshift isgiven

by

2

^^\342\200\224

____

0 E zkk

zkj

E.1.63)

where we have usedk rather than n to avoidconfusionwith the principal

quantum number n.With no degeneracy,
eigenstate;

hence,

zkk =

0,

is espectedto be a parity

E.1.64)

aswesawin Section4.2.Physicallyspeaking,there can beno linear Stark
effect, that is, there is no term in the energy shift proportional to |E
becausethe atom possesses

a vanishing permanent electricdipole,sothe

energyshift isquadraticin

|E|iftermsofordere31E|3or higher areignored.

Letus now lookat

zkj, which

appearsin

E.1.63),

where k (ory) is
the collectiveindexthat standsfor (ai,/,m) and {nf,/',m').First, werecall
the selectionrule [seeC.10.39)]

'/'= /

\302\261

1

(n',I'm'z n,Im) = 0 unless

m = m

E.1.65)

5.1.Time-Independent Perturbation Theory: Nondegenerate Case

297

that followsfrom angular momentum (the Wigner-Eckart theorem with
T^l0)and parity considerations.
Thereisanotherway to lookat the ra-selectionrule.In the presence

of F, the full

sphericalsymmetry of the Hamiltonian is destroyedby the
externalelectricfield that selectsthe positivez-direction,but V (hencethe
total H) isstill invariant under rotation around the z-axis;in other words,
we still have a cylindricalsymmetry. Formally this is reflectedby the fact
that

[F,Lz]=0.

E.1.66)

This means that

Lz is still a goodquantum number evenin the presenceof
V. As a result, the perturbation can be written as a superposition of
eigenketsof Lzwith the samem \342\200\224

m =0 in our case.Thisstatement istrue
for all orders, in particular, for the first-order ket. Also, becausethe

second-order

energyshift isobtained from the first-orderket [seeE.1.40)],
we can understand why only the m =0 terms contributeto the sum.
Thepolarizabilitya of an atom isdefinedin terms of the energyshift
of the atomic state as follows:

A=-|a|E|2.

E.1.67)

Let us considerthe specialcaseof the ground state of the hydrogen atom.
Even though the spectrumof the hydrogen atom isdegeneratefor excited
states,the ground state (with spin ignored)is nondegenerate,so the for-
formalism of nondegenerateperturbation theory can be applied.The ground
state |0@))isdenotedin the (/?,/, m) notation by A,0,0),so

?

y l<*|z|l,0,0)|

( ,

wherethe sum overk includesnot only all bound states \\n,l,m) (for n >1)
but alsothe positive-energycontinuum statesof hydrogen.
There are many ways to estimateapproximatelyor evaluateexactly

the sum in E.1.68)

with various degreesof sophistication.We presenthere
the simplestof all the approaches.Supposethe denominatorin E.1.68)

were

constant.Then wecouldobtain the sum by considering
E l|z|i,o,o>|2=E

k *0

all k

=

, E.1.69)

where we have usedthe completenessrelation in the last step.But we can
easilyevaluate(z2)for the ground state as follows:

E.1.70)

and using the explicitform for the wave function we obtain

where a0 stands for the Bohr radius.Unfortunately the expressionfor

298

Approximation Methods

polarizabilitya involves the energy denominatorthat dependson E?\302\260\\

but

we know that the inequality

2

@) i

/7@)>_ 17@) , ZT(O)_
@)>_ 17@)

k

\342\200\224

^0

e
2a0

E.1.71)

holdsfor everyenergydenominatorin E.1.68).

As a result, we can obtain
an upperlimit for the polarizability of the ground state of the hydrogen
atom, namely,

16tf

/

.

E.1.72)

It turns out that we can evaluateexactlythe sum in E.1.68)

using a method

due to A. Dalgarno and J.T. Lewis(Merzbacher1970,

424, for example),

which alsoagreeswith the experimentallymeasuredvalue.Thisgives

9a3

^ 43.

E.1.73)

We obtain the same result (without using perturbation theory) by solving
the Schrodingerequationexactlyusing paraboliccoordinates.

5.2.TIME-INDEPENDENTPERTURBATIONTHEORY:THE
DEGENERATECASE

The perturbation method we developedin the previoussectionfails when
the unperturbed energyeigenketsare degenerate.The methodof the previ-

previous

sectionassumesthat thereisa unique and well-definedunperturbedket
of energyEr\\0) which the perturbedket approachesas X ->0.With degener-

degeneracy

present,however,any linear combinationof unperturbed ketshas the
same unperturbed energy;in sucha caseit isnot a priori obviousto what
linear combinationof the unperturbed ketsthe perturbed ket isreducedin
the limit X

\342\200\224>

0.Herespecifyingjust the energyeigenvalueis not enough;
some other observable is neededto complete the picture.To be more
specific,with degeneracywe can take as our baseketssimultaneouseigen-

eigenkets of Ho and someother observableA, and we can continuelabelingthe

unperturbed energyeigenketby |/c@)),wherek now symbolizesa collective
indexthat standsfor both the energy eigenvalueand the A eigenvalue.
When the perturbation operator V doesnot commutewith A, the zeroth-
order eigenketsfor H (including the perturbation) are in fact not A
eigenkets.

From a morepracticalpoint of view, a blind applicationof formulas

like E.1.42)

and E.1.44)

obviously runs into difficulty because

Vnk

E.2.1)

_ 17@)

becomessingular if

Vnk is nonvanishing and E^0) and E[0)are equal.We
must modify the method of the previoussection to accommodatesuch a
situation.

5.2.Time-Independent Perturbation Theory: The Degenerate Case

299

Whenever thereisdegeneracywe are free to chooseour baseset of
unperturbed kets.We should,by all means,exploitthis freedom.Intuitively
we suspectthat the catastropheof vanishing denominatorsmay beavoided
by choosingour baseketsin sucha way that V has no off-diagonalmatrix
elements (suchas Vnk =0 in E.2.1)).

In other words, we should usethe
linear combinationsof the degenerateunperturbedketsthat diagonalizeH
in the subspacespannedby the degenerateunperturbedkets.Thisisindeed
the correctprocedureto use.
Supposethere is a g-fold degeneracybefore the perturbation V is
switchedon.This means that there are g different eigenketsall with the
sameunperturbed energy E$\\ Let us denote these ketsby {\\m@))}. In
general,the perturbationremovesthe degeneracyin the sensethat therewill
be g perturbedeigenketsall with different energies.

Let them form a set

{|/>}.

As X

goesto zero |/>-*

|/@)>,and various |/@)> are eigenketsof Ho
all with the sameenergyEf?\\ However,the set |/@)>neednot coincidewith
{|m@))}even though the two setsof unperturbed eigenketsspan the same
degeneratesubspace,which we callD.We can write

=

2

where the sum isover the energyeigenketsin the degeneratesubspace.
Beforeexpandingin X, there isa rearrangement of the Schrodinger
equation that will make it much easierto carry out the expansion.

LetPo

be a projectionoperatoronto the spacedefined by {|m@))}.

We define

Pi= 1\342\200\224

Poto bethe projectiononto the remaining states.We shallthen
write the Schrodingerequation for the states|/> as
0 =

(E-Ho-\\V)\\l)

=

(E-?g>-KV)P0\\l> + (E-Ho-W)P1\\[). E.2.2)

We nextseparateE.2.2)

into two equationsby projectingfrom the left on

E.2.2)

with Poand Pu

(E-?g>-\\P0V)P0\\t) -XPoVP^t)= 0

E.2.3)

-\\PiVPo\\t) + (E-Ho-XPx^Pxl/)= 0. E.2.4)

We can solveE.2.4)

in the Px subspacebecausePX{E -//0-\\PXVP^)
isnot singular in this subspacesinceEisclosetoE$and the eigenvalues
ofP1H0P1

areall different from E$.Hencewe can write

l

E-H0-
orwritten out explicitlyto orderX when |/) isexpandedas|/) =

|/@)) +

300

Approximation Methods

To calculatePoI),we substitute E.2.5)

into E.2.3)

to obtain

lE- o

=0. E.2.7)

Although there is a term of orderX2 in

E.2.7)that resultsfrom the sub-

substitution, weshallfind that it

producesa term oforderX in the state P0\\l).
To orderX we obtain the equation for the energiesto orderX and eigen-
functions to orderzero,

E.2.8)

(E-?g>-\\PoVPo)(Po\\l(O))) = 0.
This is an equation in the gdimensionaldegeneratesubspaceand clearly
means that the eigenvectorsare just the eigenvectorsof the g x gmatrix
P0VP0and the eigenvaluesEA) are just the rootsof the secularequation

det[V-(E-Eg>)]= 0

E.2.9)

where V = matrix ofP0VP0with matrix elements(m@)|V|m'@)).Explicitly
in matrix form we have

V

\\

\\2

\\ :

\\

B@)

/ \\

\\

\\

E.2.10)

The rootsdeterminethe eigenvaluesA^x)\342\200\224there aregaltogether\342\200\224and

by

substituting them into E.2.10),

wecan solvefor (m@)|/@)) foreach/ up to
an overallnormalizationconstant.Thusby solving the eigenvalueproblem,
we obtain in onestrokeboth the first-order energy shifts and the correct
zeroth-ordereigenkets.Notice that the zeroth-orderkets we obtain as

X \342\200\224\302\273

0arejust the linearcombinationsofthe various|m@))'sthat

diagonalize

the perturbation V, the diagonal elementsimmediately giving the first-
ordershift

A/(D = y

E.2.11)

Note alsothat if the degeneratesubspacewerethe wholespace,wewould
have solved the problemexactlyin this manner. The presenceof unper-

unperturbed \"distant\" eigenketsnot belongingto the degeneratesubspacewill
show up only in

higher orders\342\200\224first

orderand higher for the energyei-

eigenkets and secondorderand higher for the energy eigenvalues.
ExpressionE.2.11)

looksjust likethe first-order energy shift

[see

E.1.37)]

in the nondegenerate

caseexceptthat herewehaveto makesure
that the baseketsusedare such that V doesnot have nonvanishing off-
diagonalmatrix elementsin the subspacespannedby the degenerateun-
unperturbed eigenkets.If the V

operatorisalready diagonalin the baseket
representationweare using, wecanimmediatelywrite down the first-order

5.2.Time-Independent Perturbation Theory: The Degenerate Case

301

shift by taking the expectationvalue of V, just as in the nondegenerate

case.

Let us now lookat E.2.7).

To be safe we keepall terms in the

g x geffectiveHamiltonian that appearsin

E.2.7)to orderX2

although

we want

P0\\l) only to orderX. We find

=0. E.2.12)

Letus callthe eigenvaluesoftheg xgmatrix PqVPqVi andthe eigenvectors
Po|f|O))-Theeigenenergiesto first orderare E\\l) =

E$+ Xvr We assume

that the degeneracyiscompletelyresolvedsothat Efp -E^ =

X(v, -

vj) are allnon-zero.We cannow apply non-degenerate

perturbation theory

E.1.39)

to the g x gdimensionalHamiltonian that appearsin

E.2.12).

The resulting correctionto the eigenvectorsPo\\^)is

=

2

Vj

~~

V

'

,F(U)

or more explicitly

-2 22

vj ~

vi k*D

1

M. E.2.14)

?

Thus, although the third term in the effectiveHamiltonianthat

appearsin

E.2.12)

isoforderX2, it isdividedby energy denominators of orderX in
forming the correctionto the eigenvector,

which then givesterms oforder

X in the vector. If we addtogether E.2.6)

andE.2.14),

we get the eigen-

eigenvector accurate to orderX.

As in the nondegeneratecase,it is convenient to adopt the nor-

normalization convention(/@)|/)=1.We then have, from E.2.3)

andE.2.4),

\\(fO)\\V\\t) =

A/ =

XA/A) + X2Af2) +

\342\200\242\342\200\242\342\200\242. The X-term just reproduces

E.2.11).

As for the X2-term, weobtain AzB) =

=

{f^V^f^)

+ {/^M/yP).Sincethe vectors

Po|//O)>are eigenvectorsof V, the cor-

correction to the vector, E.2.14),

givesno contribution to the second-order

energy shift, sowe find

using E.2.6)

Vkl

E.2.15)

Our procedureworksprovided that there isno degeneracyin the
rootsof secularequation E.2.9).

Otherwisewe still have an ambiguity as
to which linear contribution of the degenerateunperturbed ketsthe per-

perturbed kets are reducedin the limit X

\342\200\224>

0.Put in another way, if our
method isto work,the degeneracyshouldberemoved completelyin first
order.A challengefortheexperts:

Howmust weproceedifthe degeneracy
isnot removed in first order,that is, if someof the rootsof the secular
equation are equal?(SeeProblem 12of this

chapter.)

302

Approximation Methods

Let us now summarize the basicprocedureof degenerateperturba-

perturbation

theory:

1.Identify degenerateunperturbedeigenketsand construct the per-
perturbation matrix V, a g X

g matrix if the degeneracyis g-fold.
2.Diagonalize the perturbation matrix by solving, as usual, the
appropriatesecularequation.
3.Identify the roots of the secular equation with the first-order
energyshifts; the basekets that diagonalizethe V matrix are the
correctzeroth-orderketsto which the perturbedketsapproachin
the limit X ->0.
4. For higher ordersuse the formulas of the correspondingnonde-
generateperturbation theory exceptin the summations, wherewe
excludeall contributionsfrom the unperturbedketsin the degen-

degenerate

subspaceD.

Linear StarkEffect

As an exampleof degenerateperturbation theory, let us study the
effectof a uniform electricfield on excitedstatesof the hydrogen atom. As
is well known, in the Schrodingertheory with a pure Coulomb potential
with no spin dependence,the bound state energy of the hydrogen atom
dependsonly on the principalquantum number n.Thisleadsto degeneracy
for all but the ground state becausethe allowedvaluesof / for a given n
satisfy

/rm ^ 4 _x

J

0

E.2.16)

To be specific,for the n =2 level,thereis an / =0 state called2s and three
1=1(m =

\302\2611,0) states called2/?, all with the sameenergy, -e2/$a0.

As

we apply a uniform electricfield in the z-direction,the appropriate per-

perturbation

operatorisgiven by

V =

-\302\253|E|,

E.2.17)

which we must now diagonalize.Beforewe evaluate the matrix elements

in detail using the usual (nlm) basis,let us note that the perturbation

E.2.17)

has nonvanishing matrix elementsonly betweenstatesofopposite
parity, that is,between1=1and / = 0 in ourcase.Furthermore, in order
for the matrix elementto benonvanishing, the m-valuesmust bethe same
becausez behaveslikea sphericaltensorof rank onewith

sphericalcom-

component {magneticquantum number) zero.Sothe only nonvanishing matrix
elementsare betweenIs(m = 0 necessarily)and2pwith m = 0.Thus
2s

I

\302\260

Bp,m=

0\\V\\2

0
0

<2s

s)

2p m-

\\V\\2p, m

0
0
0

=0

=

0)

2/7 m =1

0
0
0
0

2p m =-\\

0
0
0
0

E.2.18)

5.2.Time-Independent Perturbation Theory: The Degenerate Case

303

Explicitly,

<2j|K|2/>,

m =

0>=

B/7,m =

E.2.19)

It issufficient to concentrateour attention on the upper left-handcornerof
the squarematrix. It then looksvery much like the ox matrix, and wecan
immediatelywrite down the answer\342\200\224for

the energyshifts we get

V(\302\2611}

=

\302\261

3ea0E

E.2.20)

where the subscripts\302\261

refer to the zeroth-orderketsthat

diagonalizeV:

\302\261)

= 1

,m=0)

\302\261

=

0\302\273.

E.2.21)

Schematicallythe energy levelsare asshown in

Figure5.1.
Notice that the shift islinear in the appliedelectricfield strength,
hencethe term the linear Stark effect. One way we can visualize the
existenceof this effectisto note that the energyeigenketsE.2.21)

are not

parity eigenstatesand are therefore allowedto have nonvanishing electric
permanent dipolemoments, aswe can easilyseeby explicitlyevaluating
(z).Quitegenerally,foran energystate that wecanwrite asasuperposition
ofoppositeparity states,it ispermissibleto haveanonvanishing permanent
electricdipolemoment, which

givesriseto the linear Starkeffect.

An

interestingquestioncan now be asked.If we look at the \"real\"
hydrogen atom, the 25 leveland 2p levelare not really degenerate.Due to
the spinorbit force,2p3/2isseparatedfrom

2pl/2,

aswe will show in the

next section,and eventhe degeneracybetweenthe

2sl/2and

2pl/2levels

that persistsin the singleparticle Diractheory is removedby quantum
electrodynamics effects(the Lamb shift). We might therefore ask, Is it
realistic to apply degenerateperturbation theory to this problem?A com-

comparison with the exactresult showsthat if the perturbationmatrix elements

3lellf la0

31elIE la0

i

A2s. m=0>-l2p,m=0\302\273

No changefor I2p,m=\302\2611>

(I2s.m=0>+\\2p,m=0\302\273

FIGURE 5.1.Schematic energy-level diagram for the linear Stark effect asan example of

degenerate perturbation theory.

304

Approximation Methods

are much largerwhen comparedto the Lambshift splitting, then the energy
shift is linear in

|E|for all practical purposesand the formalism of
degenerateperturbationtheory is applicable.On the oppositeextreme,if the
perturbation matrix elementsare small compared to the Lamb shift split-

splitting,

then the energy shift is quadratic and we can apply nondegenerate
perturbation theory; seeProblem13of this chapter.Thisincidentally shows
that the formalism of degenerateperturbation theory isstill useful when the
energylevelsare almostdegeneratecomparedto the energyscaledefinedby
the perturbation matrix element. In intermediate caseswe must work
harder;it is safer to attempt to diagonalizethe Hamiltonian exactlyin the
spacespannedby all the nearbylevels.

5.3.HYDROGENLIKEATOMS:FINE STRUCTUREAND THE
ZEEMAN EFFECT

Spin-OrbitInteractionand Fine Structure

In this sectionwe study the atomiclevelsofhydrogenlike atoms,that
is, atoms with one valenceelectronoutside the closedshell.Alkali atoms
such assodium(Na) and potassium(K) belongto this category.
The central (spin-independent)

potential Vc(r) appropriate for the
valenceelectronisno longerof the pure Coulombform. Thisisbecausethe
electrostaticpotential (r)that appearsin

Vc(r)=

e(r)

E.3.1)

is no longer duejust to the nucleusof electriccharge \\e\\Z\\ we must take
into account the cloudof negatively chargedelectronsin the inner shells.A
preciseform of (r)doesnot concernus here.We simply remark that the
degeneracycharacteristicsof the pure Coulombpotential are now removed
in sucha way that the higher / statesliehigher for a given n.Physically this
arisesfrom the fact that the higher / states are more susceptibleto the
repulsiondueto the electroncloud.
Insteadof studying the detailsof Fc.(r),which determinesthe gross
structureofhydrogenlikeatoms,wediscussthe effectof the spin-orbit(L*S)
interaction that gives riseto fine structure. We can understandthe existence
of this interactionin a qualitative fashion as follows.Becauseof the central
forcepart E.3.1),

the valenceelectronexperiencesthe electricfield

E.3.2)

But whenevera moving chargeissubjectedto an electricfield, it \"feels\" an
effectivemagneticfield given by

(^)

E.3.3)

5.3.Hydrogenlike Atoms: Fine Structure and the Zeeman Effect

305

Becausethe electronhas a magneticmoment |igiven by

mec

E-3.4)

we suspecta spin-orbitpotential VLS contribution to H as follows:

= ~

V-'Beff

1

eS1
mec,

dVc

mec

x
XI7/(-e)dr

1 1dVc
2 2
mzecz dr (L-S).

E.3.5)

When this

expressioniscomparedwith the observedspin-orbitinteraction,
it is seento have the correctsign,but the magnitude turns out to betoo
large by a factor of two. Thereis a classicalexplanation for this dueto
spin precession{Thomasprecessionafter L.H.Thomas),but weshall not
bother with that

(Jackson1975,for example).We simply treat the spin-
orbit interactionphenomenologicallyandtake VLS tobeone-halfofE.3.5).
The correctquantum-mechanicalexplanation for this

discrepancymust
await the Dirac (relativistic) theory of the electron(Sakurai1967,for
instance).

We are now in a positionto apply perturbation theory to hydrogenic
atoms using VLS as the perturbation (V of Sections5.1and 5.2).The
unperturbed Hamiltonian Ho is taken to be

E-3.6)

where the central potential Vc is no longerof the pure Coulombform for
alkali atoms.With just Howe have freedomin

choosingthe basekets:

Set1: TheeigenketsofL2,LT,S2,S,.

Set2: TheeigenketsofL2,S2,

J2,Jz.

Without

VLS (orHLS)eithersetis satisfactoryin the sensethat the basekets

are alsoenergyeigenkets.With

HLSaddedit is far superiorto use set 2 of

E.3.7)becauseL*Sdoesnot commute with

Lz and S2, while it does
commutewith J2and Jz.Rememberthe cardinalrule:Chooseunperturbed
ketsthat diagonalizethe perturbation. You have to be either a fool or a
masochistto usethe Lz,Szeigenkets[set1ofE.3.7)]

as the baseketsfor this
problem;if we proceededto apply blindly the method of degenerate
perturbation theory starting with set1as our basekets,we would beforced
to diagonalizethe VLS(HLS)matrix written in the Lz,S2representation.The

306

Approximation Methods

resultsof this, after a lot of hard algebra,give us just the J2,/.eigenketsas
the zeroth-orderunperturbedketsto beused!
In degenerate perturbation theory, if the perturbation is already
diagonal in the representation we are using, all we need to do for the
first-orderenergyshift is to take the expectationvalue.Thewave function in
the two-componentform isexplicitly written as
=

Rnl(r)Wr'\302\261lu'm

E-3.8)

where \302\256}i=l\302\261ll2

is the spin-angularfunction of Section3.7[seeC.7.64)].

For the first-order shift, we obtain

\302\246

, ,I

1 II dV\\

tf_f

/

\\

J l+

2

nlj

2my\\r dr

jn, 2 \\[-(/+1)]/

1

J

2

1 dV \\

/\342\200\242<\302\273

i dV

-^A ^

Rnl\302\261^Rnlr2dr

E.3.9)

^ r.1 J0 r
wherewe haveusedthe w-independentidentity [seeC.7.65)]

2

2

2
hz =hLi l
2 \\-(/+l)

E.3.10)

EquationE.3.9)

isknown as Lande'sinterval rule.
To be specific,considera sodium atom. From standard atomic
spectroscopynotation, the ground-stateconfiguration is

(lsJBs)\\2pNCs). E.3.11)

The inner 10electronscan bevisualizedto form a sphericallysymmetrical
electroncloud.We are interestedin the excitationof the eleventh electron
from 3s to a possiblehigher state.Thenearestpossibilityis excitationto 3p.
Becausethe centralpotentialisno longerof the pure Coulombform, 3sand
3/7 are now split.The fine structure brought about by VLS refersto evena
finer split within 3/?,between

3pl/2and

3/?3/2,wherethe subscriptrefersto
j.Experimentally,we observetwo closelyseparatedyellow lines\342\200\224known

as

the sodium D lines\342\200\224one

at 5896A, the other at 5890A; seeFigure 5.2.

Noticethat

3p3/2lieshigher becausethe radialintegral in E.3.9)

ispositive.

To appreciatethe order of magnitude of the fine-structuresplitting,

let us note that for Z ^

f\\

-^

E.3.12)

dr / , a3
I nl UQ

5.3.Hydrogenlike Atoms: Fine Structure and the Zeeman Effect

307

Doubletor \"Fine\"

structure

3P:3/2

1/2

/\\=5890A

/\\=5896A

FIGURE 5.2. Schematic diagram of 35 and 3>p lines. The 3s and 3p degeneracy is lifted
becauseVc(r) is now the screened Coulomb potential due to coreelectrons rather than pure
Coulombic; Vrs then removes the

3px/1 an<^

3P3/2 degeneracy.

just on the basisof dimensionalconsiderations.

Sothe fine-structuresplit-

splitting is of order(e2/al)(h/mecJ,

which is to be comparedwith Balmer

splittings of ordere2/a0.

It isuseful to recallhere that the classicalradius
of the electron, the Compton wavelength of the electron, and the Bohr
radius are related in the following way:

H

mec :ao::l:137:(l37J, E.3.13)

wherewe haveused

hc 137'

E.3.14)

Typically,fine-structuresplittings are then related to typical Balmersplit-

splittings

via

~3

m;c

e
a

2 \\

1

137

E.3.15)

which explainsthe origin of the term fine structure. There are other effects
of similar ordersof magnitude. Specifically,the relativisticmasscorrection
arisingfrom the expansion

2c2 r

\342\200\224

2m^ 8m

E.3.16)

is of the sameorder.

The ZeemanEffect

We now discusshydrogen or hydrogenlike (one-electron)atomsin a
uniform magneticfield\342\200\224the Zeemaneffect,sometimescalledthe anomalous
Zeeman effect with the electron spin taken into account. Recall that a

308

Approximation Methods

uniform magneticfield B isderivablefrom a vectorpotential

E.3.17)

ForBin the positivez-direction(B=

2?z),

=

-\\(Byx-Bxy)

E.3.18)

sufficeswhere B standsfor |B|.Apart from the spin term, the interaction
Hamiltonian isgeneratedby the substitution

p->p~\342\200\224.

E.3.19)

We thereforehave

Because

To this we may addthe spin magnetic-momentinteraction

mec mec

<5-3-20)

[')l,E.3.21)

?

it islegitimateto replacep*A by A*p whenever

VA(x)=0,

E.3.22)

which is the casefor the vectorpotentialofE.3.18).

Noting

=

l|B|Lz

E.3.23)

and

),

E.3.24)

we obtain forE.3.20)

S-B=\342\200\224|B|SZ.

E.3.26)

mc z

v

7

The quadratic |B|2(.x2

+ >>2)is unimportant for a one-electronatom; the
analogousterm isimportant for the ground state of the helium atom where
?(tot> an(j ^(tot) j3Otj1 yanigh j^readermay come backto this problem
when he or shecomputesdiamagneticsusceptibilities

in Problems18and19

of this chapter.

5.3.Hydrogenlike Atoms: Fine Structure and the Zeeman Effect

309

To summarize,omitting the quadraticterm, the total Hamiltonian is
made up of the following threeterms:

0

2m

IIr C~\"~

LS

2c2

2m2ec

dVc(r)

dr L-S

E.3.27a)

E.3.27b)

_ -111
2mec(L2+2SZ).

E.3.27c)

Noticethe factor 2 in front of Sz;this reflectsthe fact that the g-factorof
the electronis2.

SupposeHB is treated as a small perturbation. We can study the
effectof HB using the eigenketsof HQ+ HLS\342\200\224the J2,/,eigenkets\342\200\224as

our

basekets.Noting

,

E.3.28)

the first-ordershift canbewritten as

-e\\B

2mec +

E.3.29)

The expectationvalue of Jz immediately gives mh. As for (Sz),we first
recall

1

2/+1

x

_1

2'

2/+1 =m + \342\200\224

2/-

E.3.30)

The expectationvalue of Szcan then easilybecomputed:

2

B/+1)

-

___

i

mh

E.3.31)

In this manner we obtain Lande'sformula for the energyshift (dueto B
field),

-ehB

2mecm 1\302\261

1

B/

E.3.32)

We seethat the energy shift of E.3.32)

is proportional to m. To
understand the physical origin for this, we presentanother method for

310

Approximation Methods

deriving E.3.31).

We recall that the expectationvalue of Sz can also be
obtainedusing the projectiontheoremofSection3.10.

We get[seeC.10.45)]

mh

j=l\302\261l/2,m

i=l\302\261

1/2

m

1/2

= mh

mh

E.3.33)

which isin

completeagreement with

E.3.31).

In the foregoingdiscussionthe magneticfield is treated as a small
perturbation. We now considerthe oppositeextreme\342\200\224the

Paschen-Back

limit\342\200\224with

a magneticfield so intense that the effectof HB is far more
important than that of HLS,which we later add as a small perturbation.
With

Ho+ HB only, the goodquantum numbers are Lz and Sz.Even J2is
no goodbecausesphericalsymmetry iscompletelydestroyedby the strong
Bfield that selectsa particulardirectionin space,the z-direction.Weareleft
with cylindricalsymmetry only\342\200\224that is,invarianceunder rotation around
the z-axis.Sothe LZ,SZ eigenkets\\l,s =

\\,mhms)are to be usedas our
basekets.The effectof the main term HBcan easilybecomputed:

~e\\B\\

2mec

E.3.34)

The 2B/+1)degeneracyin

m{ and ms we originally had with

Ho [see
E.3.27a)]is now reducedby HB to states with the same (m7) +Bm5),
namely, (m/)+(l)and (ra/ +2)+(\342\200\224

1).Clearlywemust evaluatethe expec-

expectation valueof L*Swith respectto \\mhms)\\

i/n

=

h2mtms,

E.3.35)

wherewehaveused

E.3.36)

Hence,

=h2m,ms I1dVc

\\nLS/m,m,

2mzecz \\ r dr

E.3.37)

5.3.Hydrogenlike Atoms: Fine Structure and the Zeeman Effect

311

WeakB

Strong B

Dominant interaction

HB

TABLE 5-1

Almost good

J2 (orL-S)

No good

J2(orL-S)

Always good

L2,S2,/Z

*Theexception is the stretched configuration, for example, p3/2 with m = +\\. Here

Lz and Sz areboth good; this is because magnetic quantum number 72, m =

m{ 4-ms

can besatisfied in only one way.

In many elementarybooksthere are pictorialinterpretationsof the
weak-fieldresultE.3.32)

and the strong-fieldresult E.3.34),

but wedonot

bother with them here.We simply summarize our resultsin Table5-1,

where

weak and strong B fieldsare \"calibrated\" by comparingtheir magnitudes
ehB/2mecwith

(l/137Je2/^o-

I*1^stable almost good simply means
goodto the extent that the lessdominant interactioncouldbeignored.
Specifically,let us look at the level schemeof a p electron 1=1
(/?3/2,Pi/2)-In the weak Bcasethe energyshifts arelinearin B,with slopes
determinedby

m 1+ 1

2/+1

As we now increaseB,mixing becomes

possiblebetweenstateswith the

same m-value\342\200\224for

example,

p3/2with m =

\302\2615

and pl/2 with m - \302\2615;

in this connectionnote the operatorLz + 2SZthat

appearsin HB[E.3.27c)]

is a rank 1tensoroperatorT^=^with

sphericalcomponent q =0.In the

intermediate B region simpleformulas likeE.3.32)

and E.3.34)

for the

expectationvaluesare not possible;

it isreallynecessaryto diagonalizethe

appropriate2x2matrix (Gottfried 1966,

371-73).

In the strong B limit

the energy shifts areagain proportional to |fi|;asweseein

E.3.34),

the

slopesare determinedby m{ + 2ms.

Van derWaals'Interaction

An important, nice application of the Rayleigh-Schrodingerper-

perturbation

theoryisto calculatethe long-rangeinteraction,or van derWaals9
force,betweentwo hydrogen atomsin their ground states.It iseasyto show
that the energy betweenthe two atoms for large separation r is attractive
and variesasr~6.

Considerthe two protons of the hydrogen atoms to befixed at a
distancer (along the z-axis)with

xx the vector from the first proton to its
electronand r2 the vectorfrom the secondproton to its electron;seeFigure

312

Approximation Methods

r 2

z-axis

FIGURE 5.3. Two hydrogen atoms with their protons (+)separated by a fixed distance r
and their electrons (-)at displacements r, from them.

5.3.

Then the Hamiltonian Hcanbewritten as

H=H0

2

2

2

2

r |r+r2-ri| |r+r2

The lowest-energysolutionof Hoissimply the product of the ground-state
wavefunctionsof the noninteracting hydrogen atoms

E.3.39)

Now for large r (:\302\273 the Bohr radius a0)expandthe perturbation V in
powersof r,/r to obtain

2

/ 1 \\

E.3.40)

~3
The lowest-orderr~3-termin E.3.40)

correspondsto the interactionof two
electricdipoleserland er2separatedby r.Thehigher-orderterms represent
higher-ordermultipole interactions, and thus every term in V involves
sphericalharmonics

Y\342\204\242

with

/\342\200\242

>0 for each hydrogen atom. Hence,for

eachterm in E.3.40)

the first-orderperturbation energy matrix element
=0, sincethe ground state f/0@) wave function E.3.39)

has /,=0 (and

=0 for / and m # 0).The second-orderperturbation

^ v

will be nonvanishing. We immediately seethat this interaction varies as
1/r6;sinceEj\302\256>

E^\302\260\\

it is negative.This1/r6long-rangeattractivevan
der Waals' potential is a generalproperty of the interaction betweentwo
atomsin their ground state.*

*Seethe treatment in SchiffA968), pages 261-263,

which givesalower and upper bound on

the magnitude ofthe van der Waals' potential from E.3.41)

and from avariational calculation.

Also note the first footnote on page 263 of Schiff concerning retardation effects.

5.4.Variational Methods

313

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