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VanderWaalsForcesbetweenAtoms
MichaelFowler
Introduction
TheperfectgasequationofstateP V = N kT ismanifestlyincapableofdescribingactualgasesat
lowtemperatures,sincetheyundergoadiscontinuouschangeofvolumeandbecomeliquids.In
the1870s,theDutchphysicistVanderWaalscameupwithanimprovement:agaslawthat
recognizedthemoleculesinteractedwitheachother.Heputintwoparameterstomimicthis
interaction.Thefirst,anattractiveintermolecularforceatlongdistances,helpsdrawthegas
togetherandthereforereducesthenecessaryoutsidepressuretocontainthegasinagivenvolume
thegasisalittlethinnernearthewalls.Theattractivelongrangeforcecanberepresentedbya
negativepotentialaN /V ongoingawayfromthewallsthemoleculesnearthewallsare
attractedinwards,thoseinthebulkareattractedequallyinalldirections,soeffectivelythelong
rangeattractionisequivalenttoapotentialwellextendingthroughoutthevolume,endingcloseto
thewalls.Consequently,thegasdensityN /V nearthewallsisdecreasedbyafactor
E/kT
aN /V kT
e
= e
1 aN /V kT .Therefore,thepressuremeasuredatthecontainingwall
isfromslightlydilutedgas,soP = (N /V ) kT becomesP = (N /V ) (1 aN /V kT ) kT ,or
2
.ThesecondparametervanderWaalsaddedwastotakeaccountof
thefinitemolecularvolume.Arealgascannotbecompressedindefinitelyitbecomesaliquid,for
allpracticalpurposesincompressible.HerepresentedthisbyreplacingthevolumeV with
V N b, N bisreferredtoastheexcludedvolume,roughlyspeakingthevolumeofthe
molecules.Puttinginthesetwotermsgiveshisfamousequation
(P + a(N /V ) )V = N kT
[P + a(
N
V
) ] (V N b) = N kT .
Thisrathercrudeapproximationdoesinfactgivesetsofisothermsrepresentingthebasicphysics
ofaphasetransitionquitewell.(Forfurtherdetails,andanenlighteningdiscussion,seefor
exampleAppendixDofThermalPhysics,byR.Baierlein.)
GroundStateHydrogenAtoms
OurinteresthereisinunderstandingthevanderWaalslongrangeattractiveforcebetween
electricallyneutralatomsandmoleculesinquantummechanicalterms.
Webeginwiththesimplestpossibleexample,twohydrogenatoms,bothinthegroundstate:
WelabeltheatomsAandB,thevectorsfromtheprotonstotheelectronpositionaredenotedby
r A
and
r B
respectively,and R isthevectorfromprotonAtoprotonB.
ThentheHamiltonianH
= H
+ V
,where
2m
2
A
2
B
rA
rB
andtheelectrostaticinteractionbetweenthetwoatoms
e
V =
e
+
R + r B r A
R + r B
R r A
.
ThegroundstateofH 0 isjusttheproductofthegroundstatesoftheatomsA, B,thatis,
|0 = |100
|100
Assumingnowthatthedistancebetweenthetwoatomsismuchgreaterthantheirsize,wecan
expandtheinteractionV inthesmallparametersrA /R, rB /R.Asonemightsuspectfromthe
diagramabove,theleadingordertermsintheelectrostaticenergyarejustthoseofadipoledipole
interaction:
V = e
1
r A r B
2
( r A ) ( r B )
= e
R
R
3( r A R )( r B R )
Takingnowthez-axisinthedirection R ,thisinteractionenergyis
2
V =
(xA xB + yA yB 2zA zB )
Nowthefirstordercorrectiontothegroundstateenergyofthetwoatomsystemfromthis
interactionisEn1 = n 0 H 1 n 0 ,wherehereH 1 = V andn 0 = |100A |100B .
BeginningwiththefirsttermxA xB inV
(A 100| B 100|) (xA xB ) (|100
|100
) = (A 100| xA |100
) (B 100| xB |100
isclearlyzerosincethegroundstatesaresphericallysymmetric.Similarly,theothertermsin
V arezerotofirstorder.
0
m
H
m
H
Recallthatthesecondorderenergycorrectionis
2
En
En Em
mn
Thatis,
(2)
)|
2E1 En En
n,l,m
|100
n ,l ,m
Atypicaltermhereis
|100
) = (A nlm| xA |100
) (B n l m | xB |100
sothesingleatommatrixelementsareexactlythosewediscussedfortheStarkeffect(aswewould
expectthisisanelectrostaticinteraction!).Asbefore,onlyl = 1, l = 1contribute.Tomakea
roughestimateofthesizeofE (2) ,wecanusethesametrickusedforthequadraticStarkeffect:
replacethedenominatorsbytheconstant2E1 (theothertermsarealotsmallerforthebound
states,andcontinuumstateshavesmalloverlaptermsinthenumerator).Thesumover
intermediatestatesn, l, m, n , l , mcanthenbetakentobecompletelyunrestricted,including
eventhegroundstate,giving
(|nlm
|n l m
) (A nlm| B n l m |) = I
n,l,m
n ,l ,m
theidentityoperator.Inthisapproximation,then,justasfortheStarkeffect,
E
(2)
whereE1
= 1
1
2E1
(|100
|100
Ryd.,sothisisaloweringofenergy.
2
(2)
6a
2E1
(
R
a0
Forcesbetweena1sHydrogenAtomanda2pHydrogenAtom
Withoneatominthe|100 andtheotherin|210 ,say,atypicalleadingordertermwouldbe
(
100|
210|) (
) (|100
|100
) = (
100|
|100
)(
210|
|100
|100
) = (A 100| xA |100
) (B 210| xB |100
andthisiscertainlyzero,asarealltheotherleadingterms.Baym(LecturesonQuantum
Mechanics)concludedfromthisthatthereisnoleadingorderenergycorrectionbetweentwo
hydrogenatomsifoneofthemisinthegroundstate.Thisisincorrect:thefirstexcitedstateofthe
twoatomsystem(withoutinteraction)isdegenerate,so,exactlyasforthe2Dsimpleharmonic
oscillatortreatedinthepreviouslecture,wemustdiagonalizetheperturbationinthesubspaceof
thesedegeneratefirstexcitedstates.(Forthissection,wefollowfairlycloselytheexcellent
treatmentinQuantumMechanics,byC.CohenTannoudjietal.)
Thespaceofthedegeneratefirstexcitedstatesofthetwononinteractingatomsisspannedbythe
productspacekets:
(|100
(|100
|200
|210
) , (|200
) , (|210
Thetask,then,istodiagonalizeV
subspace.
|100
|100
) , (|100
) , (|100
|211
|21 1
) , (|211
|100
) , (|21 1
),
|100
inthiseightdimensional
(xA xB + yA yB 2zA zB )
foroneoftheatomsinthegroundstate.Second,writingV
( r A r B 3zA zB )
,itis
evidentthatV isunchangedifthesystemisrotatedaroundthez-axis(thelinejoiningthetwo
protons).Thismeansthatthecommutator[V , Lz ] = 0,whereLz isthetotalangularmomentum
componentinthez-direction,soV willonlyhavenonzeromatrixelementsbetweenstateshaving
thesametotalLz .Third,fromparity(orWignerEckart)allmatrixelementsinthesubspace
spannedby(|100A |200B ) , (|200A |100B )mustbezero.
Thisreducesthenonzeropartofthe8 8matrixtoadirectproductofthree2 2matrices,
correspondingtothethreevaluesofLz = m.Forexample,them = 0subspaceisspannedby
(|100
|210 ) , (|210
|100 ).Thediagonalelementsofthe2 2 matrixarezero,
A
B
A
B
2
theoffdiagonalelementsareequalto 2e
(A 100| zA |210
) (B 210| zB |100
,wherewe
km /R
3
(followingthenotationofCohenTannoudji)wherekm
3
km /R ,
withcorrespondingeigenkets
0
2
andtheenergyeigenvaluesare
e a ,
(1/2 ) [(|100
|210
) (|210
|100
)]
Sofortwohydrogenatoms,oneinthegroundstateandoneinthefirstexcitedstate,thevander
Waalinteractionenergygoesas1/R3 ,muchmoreimportantthanthe1/R6 energyfortwo
hydrogenatomsinthegroundstate.Noticealsothatthe1/R3 canbepositiveornegative,
hydrogenatomsinthegroundstate.Noticealsothatthe1/R3 canbepositiveornegative,
dependingonwhethertheatomsareinanevenoranoddstatesotheatomssometimesrepel
eachother.
Finally,iftwoatomsareinitiallyinastate(|100A |210B ),notethatthisisnotaneigenstateof
theHamiltonianwhentheinteractionisincluded.Writingthestateasasumoftheevenandodd
states,whichhaveslightlydifferentphasefrequenciesfromtheenergydifference,wefindthe
excitationmovesbackandforthbetweenthetwoatomswithaperiodhR3 /2km=0 .
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