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https://www.scribd.com/doc/101421029/SakuraiJJModernQuantumMechanicsAW1994802dpiT513s
09/12/2015
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Statementof the Problem
The approximation method we considerhere is timeindependent
perturbation theory\342\200\224sometimes known as the RayleighSchrodingerper
perturbation
theory.We considera timeindependentHamiltonian 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 fullpotential
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 fullstrength 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 fullstrength 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 Xplane
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 TwoStateProblem
Beforeweembark on a systematicpresentationof the basicmethod,
let us seehow the expansionin X
might indeedbe valid in the exactly
solubletwostateproblem we have encounteredmany times already. Sup
5.1.
TimeIndependent Perturbation Theory: Nondegenerate Case
287
posewehave a Hamiltonian that canbewritten as
f ?f2@>><2@>
+XK12l@>><2@)+XK212(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 spinorientationproblem,wherethe ana
analogue ofE.1.6)
is
=
V2l.
H=
o o#a= 0 ' a3 ai
aoa3 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 supposeXF12
issmall comparedwith the relevant energyscale,the
differenceof the energyeigenvaluesof the unperturbedproblem:
E.1.12)
We can then use
.
1 e2
\\/l +e
=l+ey+\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 XF12,
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 spinorientationproblem.
The readermight be led to believethat a perturbation expansion
alwaysexistsfor a sufficiently weak perturbation.Unfortunately this isnot
necessarilythe case.As an elementaryexample,considera onedimensional
probleminvolving a particleofmassm in a very weak squarewellpotential
of depth Vo (V=Vofor a
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 freeparticleHamiltonian and interpret result E.1.15)
as the energyshift
in the ground state from zero to XF2.Specifically,becauseE.1.15)
is
quadratic in F, we might betemptedto associatethis as the energyshift of
the ground state computedaccordingto secondorderperturbation 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 Xisincreasedfrom zero,
branch points are encounteredat
The condition for the convergenceof the seriesexpansion for the X =1
fullstrength caseis
@)_?@)
l
If this conditionisnot met, perturbation expansionE.1.14)
ismeaningless.
Seethe discussion on convergence following E.1.44),
under general remarks.
5.1.TimeIndependent 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
the right. Explicitly,
1
*,E
\342\200\236\302\273.'
17@) _ ff ^ ^ 17@) _ F@)
Also from E.1.22)
and E.1.23),
it isevident that
(XVbn)\\n) =
4>n(XV A
Jn>. 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^)+
^(XKAw)#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.132)
^(O)_
and similarly
1
1
1
E.1.33)
sowe have
E.134)
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.
TimeIndependent 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 X2term 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
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 twostate 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 firstorder
energy shift it is sufficient to evaluate the expectation value of V with
respectto the unperturbedkets.Second,it isevident from the expressionof
the secondorder
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 ^72/(^7@)
?,@))>while the energyof thejth level
goesup by the sameamount. Thisis a specialcaseof the nolevelcrossing
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 secondorderenergyshift is
negative.This means that the secondorderenergyshift is always negative
5.1.TimeIndependent 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 kineticenergy
operator(then this RayleighSchrodingerperturbationexpansionisjust 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).
Wavefunction 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 Becausen)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 secondorder
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 groundstate ket 0) in the
presenceof V and the groundstateenergyshift
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^jc20<\302\260>>
=
^.
2y2
5.1.TimeIndependent 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 groundstateket, 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 groundstatewave
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 oneelectronatom\342\200\224the
hydrogen
atom or a hydrogenlikeatom with onevalenceelectronoutsidethe closed
(sphericallysymmetrical)shell\342\200\224is
subjectedto a uniform electricfield in
the positivezdirection.
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
Eiftermsofordere31E3or 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.TimeIndependent Perturbation Theory: Nondegenerate Case
297
that followsfrom angular momentum (the WignerEckart theorem with
T^l0)and parity considerations.
Thereisanotherway to lookat the raselectionrule.In the presence
of F, the full
sphericalsymmetry of the Hamiltonian is destroyedby the
externalelectricfield that selectsthe positivezdirection,but V (hencethe
total H) isstill invariant under rotation around the zaxis;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 firstorder ket. Also, becausethe
secondorder
energyshift isobtained from the firstorderket [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=aE2.
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<*zl,0,0)
( ,
wherethe sum overk includesnot only all bound states \\n,l,m) (for n >1)
but alsothe positiveenergycontinuum 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 lzi,o,o>2=E
k *0
all k
=
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.TIMEINDEPENDENTPERTURBATIONTHEORY:THE
DEGENERATECASE
The perturbation method we developedin the previoussectionfails when
the unperturbed energyeigenketsare degenerate.The methodof the previ
previous
sectionassumesthat thereisa unique and welldefinedunperturbedket
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.TimeIndependent 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 offdiagonalmatrix
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 gfold 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 =
(EHo\\V)\\l)
=
(E?g>KV)P0\\l> + (EHoW)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) + (EHoXPx^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
EH0
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(EEg>)]= 0
E.2.9)
where V = matrix ofP0VP0with matrix elements(m@)Vm'@)).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 firstorder energy shifts and the correct
zerothordereigenkets.Notice that the zerothorderkets we obtain as
X \342\200\224\302\273
0arejust the linearcombinationsofthe variousm@))'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 firstorder 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 firstorder
5.2.TimeIndependent 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
PofO))Theeigenenergiesto first orderare E\\l) =
E$+ Xvr We assume
that the degeneracyiscompletelyresolvedsothat Efp E^ =
X(v, 
vj) are allnonzero.We cannow apply nondegenerate
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 Xterm just reproduces
E.2.11).
As for the X2term, 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 secondorder
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 gfold.
2.Diagonalize the perturbation matrix by solving, as usual, the
appropriatesecularequation.
3.Identify the roots of the secular equation with the firstorder
energyshifts; the basekets that diagonalizethe V matrix are the
correctzerothorderketsto 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 zdirection,the appropriate per
perturbation
operatorisgiven by
V =
\302\253E,
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 mvaluesmust 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.TimeIndependent Perturbation Theory: The Degenerate Case
303
Explicitly,
<2jK2/>,
m =
0>=
B/7,m =
E.2.19)
It issufficient to concentrateour attention on the upper lefthandcornerof
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 zerothorderketsthat
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 energylevel 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
Efor 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
SpinOrbitInteractionand 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 (spinindependent)
potential Vc(r) appropriate for the
valenceelectronisno longerof the pure Coulombform. Thisisbecausethe
electrostaticpotential
Vc(r)=
e
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
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 spinorbit(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
E3.4)
we suspecta spinorbitpotential VLS contribution to H as follows:
= ~
V'Beff
1
eS1
mec,
dVc
mec
x
XI7/(e)dr
1 1dVc
2 2
mzecz dr (LS).
E.3.5)
When this
expressioniscomparedwith the observedspinorbitinteraction,
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 tobeonehalfofE.3.5).
The correctquantummechanicalexplanation 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
E3.6)
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 zerothorderunperturbedketsto beused!
In degenerate perturbation theory, if the perturbation is already
diagonal in the representation we are using, all we need to do for the
firstorderenergyshift is to take the expectationvalue.Thewave function in
the twocomponentform isexplicitly written as
=
Rnl(r)Wr'\302\261lu'm
E3.8)
where \302\256}i=l\302\261ll2
is the spinangularfunction of Section3.7[seeC.7.64)].
For the firstorder 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 windependentidentity [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 groundstateconfiguration 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 finestructuresplitting,
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 finestructuresplit
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,finestructuresplittings 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 (oneelectron)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 positivezdirection(B=
2?z),
=
\\(ByxBxy)
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 magneticmomentinteraction
mec mec
<5320)
[')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
=
lBLz
E.3.23)
and
),
E.3.24)
we obtain forE.3.20)
SB=\342\200\224BSZ.
E.3.26)
mc z
v
7
The quadratic B2(.x2
+ >>2)is unimportant for a oneelectronatom; 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 LS
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 gfactorof
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 firstordershift 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
PaschenBack
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 zdirection.Weareleft
with cylindricalsymmetry only\342\200\224that is,invarianceunder rotation around
the zaxis.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 51
Almost good
J2 (orLS)
No good
J2(orLS)
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{ 4ms
can besatisfied in only one way.
In many elementarybooksthere are pictorialinterpretationsof the
weakfieldresultE.3.32)
and the strongfieldresult E.3.34),
but wedonot
bother with them here.We simply summarize our resultsin Table51,
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 mvalue\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,
37173).
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 RayleighSchrodingerper
perturbation
theoryisto calculatethe longrangeinteraction,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 zaxis)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
zaxis
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+r2ri r+r2
The lowestenergysolutionof Hoissimply the product of the groundstate
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 lowestorderr~3termin E.3.40)
correspondsto the interactionof two
electricdipoleserland er2separatedby r.Thehigherorderterms represent
higherordermultipole 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 firstorderperturbation energy matrix element
=0, sincethe ground state f/0@) wave function E.3.39)
has /,=0 (and
=0 for / and m # 0).The secondorderperturbation
^ v
will be nonvanishing. We immediately seethat this interaction varies as
1/r6;sinceEj\302\256>
E^\302\260\\
it is negative.This1/r6longrangeattractivevan
der Waals' potential is a generalproperty of the interaction betweentwo
atomsin their ground state.*
*Seethe treatment in SchiffA968), pages 261263,
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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