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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)

|(A nlm| B n l m |) V (|100

=

)|

2E1 En En

n,l,m

|100

n ,l ,m

Atypicaltermhereis

(A nlm| B n l m |) (xA xB ) (|100

|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

(A 100| B 100|) (xA xB + yA yB 2zA zB )

(|100

|100

Ryd.,sothisisaloweringofenergy.
2

Inmultiplyingout(xA xB + yA yB 2zA zB ) ,thecrosstermswillhaveexpectationvaluesof

zero.Thegroundstatewavefunctionissymmetrical,soallweneedis100| x2 |100 = a20,
wherea0 istheBohrradius.
Thisgives
E

(2)

6a
2E1

(
R

a0

usingE1 = e2 /2a0 .Bearinmindthatthisisanapproximation,butaprettygoodoneamore

accuratecalculationreplacesthe6by6.5.

Forcesbetweena1sHydrogenAtomanda2pHydrogenAtom
Withoneatominthe|100 andtheotherin|210 ,say,atypicalleadingordertermwouldbe
(

100|

210|) (

) (|100

|100

) = (

100|

|100

)(

210|

|100

(A 100| B 210|) (xA xB ) (|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 )

WebeginbyrepresentingV asan8 8matrixusingthesestatesasthebasis.First,notethatall

thediagonalelementsofthematrixarezeroinallofthem,werefindingtheaverageofx, yor
z

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

havekepttheunnecessarylabelsA, Btomakeclearwherethistermcomesfrom.(ThexA and

yAtermswillnotcontributeform = 0.)
Thisisnowastraightforwardintegraloverhydrogenwavefunctions.Thethree2 2matrices
havetheform
0
(
km /R

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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