SERCMolecularSimulationWorkshopandSymposium:May69,2009

DepartmentofChemicalEngineering,IndianInstituteofScience,Bangalore560012
1
StatisticalThermodynamics
LecturenotesbyDr.SudeepPunnathanam
Introduction
StatisticalMechanicsisthestudyofmacroscopicphenomenafromami
croscopicpointofview.StatisticalMechanicshelpsustounderstand,explainand
predictmacroscopicbehaviorofacollectionofentities(e.g.molecules)giventhe
microscopicbehavior(e.g.intermolecularinteractions).Thebranchofstatistical
mechanicsthatdealswithequilibriumthermodynamicsbehavior(e.g.pressure,
entropy,freeenergy)iscalledStatisticalThermodynamics.
Onlycertainproblemsinstatisticalthermodynamicsareexactlysolvable
(e.g.idealgas,Einsteincrystal,Isingmodelinoneandtwodimensions,etc.).
Computersimulationsprovideexactnumericalresultsforproblemsthatare
solublebyapproximatemethodsormightbequiteintractable.
Sincecomputersimulationsgiveexactresultsforagivenmodel,thesecan
beusedtotestthepredictionsoftheories.Historically,computersimulations
havebeenabletodiscriminatebetweenwellfoundedapproaches(integralequa
tiontheories)andideasthatareplausiblebutlesssuccessful(oldcelltheoriesof
liquids).Computersimulationresultscanalsobedirectlycomparedwithex
perimentalresults.Insuchcases,theresultscanhelpinvalidatingthemolecular
modelusedinthesimulations.Withagoodmodel,thesimulatorcanoffernew
informationaboutthesystem,whicharedifficultorimpossibletoaccessex
perimentallyandthusassistininterpretingnewexperimentalresults.

Figure1:Theconnectionbetweentheory,experimentsandcomputersimula
tions

SERCMolecularSimulationWorkshopandSymposium:May69,2009
DepartmentofChemicalEngineering,IndianInstituteofScience,Bangalore560012
2

ConceptofEnsembles
Thestateofamacroscopicsystemcanbespecifiedbyfewproperties.For
example,apureliquidcanbedescribedcompletelybyitmass,pressureand
temperature.However,foreachmacroscopicstate,thereexistalargenumberof
microscopicstatescorrespondingtoit.Forquantumsystems,eachmicroscopic
stateisdescribedbytheeigenfunctionobtainedbysolvingtheSchrodingerwave
equation.Forclassicalsystems,thepositionsandmomentaofallitsconstituent
moleculesdescribeeachmicroscopicstate.Anensembleofsystemsisacollection
ofvariousmicroscopicstatesofthesystemthatcorrespondtothesinglemacro
scopicstateofthesystemwhosepropertiesweareinvestigating.
Dependinguponthethermodynamicenvironmentofthesystem,wecan
createvariousrepresentativeensembles.Thecommonlyencounteredensembles
aregivenbelow

Typeofensemble Constantvari
ables
Description
Microcanonical N,V,E Isolatedsystem
Canonical N,V,T Closedisothermalsystem
Grandcanonical ,V,T Openisothermalsystem
Isothermalisobaric N,P,T Closedisothermalisobaricsystem

TimeaveragingversusEnsembleaveraging
Supposewewishtodetermineexperimentallythevalueofamechanical
property(e.g.pressure,energy)ofasystem.Letusdenotethispropertybythe
variableM.Ingeneral,theinstantaneousvalueofMwilldependonpositions,r
N
,
andmomenta,p
N
,oftheNparticlesofthesystem.Theexperimentallymeasured
valueisthetimeaveragedvalueofM(r
N
(t),p
N
(t)).

M
time
= lim

1

M r
N
t
( )
,p
N
t
( )
( )
dt
0

AnotherwayofdeterminingthevalueofMisthroughaveragingoverthe
varioussystemsintherepresentativeensemble.Thusweobtaintheensemble
averagedvalueofMgivenas

M
ens
= dr
N
dp
N
M r
N
,p
N
( )

r
N
,p
N
( )
,
where(r
N
,p
N
)istheprobabilitydensitydistributionoffindingasysteminthe
ensemblehavingaconfigurationwithmomentap
N
andpositionsr
N
.

Postulates
PostulateI:
ThelongtimeaverageofamechanicalvariableMinthethermodynamic
systemofinterestisequaltotheensembleaverageofM,inthelimitasthenumber
ofsystemsoftheensemblebecomeinfinitelylarge,providedthatthesystemsofthe
ensemblereplicatethethermodynamicstateandenvironmentoftheactualsystem
ofinterest.
SERCMolecularSimulationWorkshopandSymposium:May69,2009
DepartmentofChemicalEngineering,IndianInstituteofScience,Bangalore560012
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Thefirstpostulatetellsusthatwecanreplacethetimeaveragewithan
averageoverinstantaneousvaluesforallthesystemsintheensemble.Itapplies
toalltypesofensembles.Thusitisnotnecessarytofollowthetimeevolutionof
thesysteminordertoobtainthevaluesforvariousmechanicalproperties.How
ever,thepostulatebyitselfdoesnothelpustocalculatetheensembleaverages
sincenoinformationisavailableabouttheprobabilitydistributionofthevarious
microscopicstatesintheensemble.Suchinformationcanbeobtainedbytheap
plicationofthesecondpostulate.

PostulateII:
Inanensemblerepresentativeofanisolatedthermodynamicsystem,the
systemsoftheensemblearedistributeduniformly,thatis,withequalprobabilityor
frequency,overthepossiblequantumstatesconsistentwiththespecifiedvaluesof
N,VandE.
Thesecondpostulateappliesonlytothemicrocanonicalensemble.Itis
alsoknownaspostulateofequalaprioriprobability.Itstatesthattheprobabil
itydensityisuniforminthemicrocanonicalensemble.Theformofforother
ensemblescanbederivedfromtheabovetwopostulates.

ConnectiontoThermodynamics
GibbsEntropyFormula
TheGibbsEntropyformularelatestheentropyofasystemtotheprob
abilitydistributionofthemicrostates.Itcanbederivedfromtheabovetwopos
tulates.Herewepresentitwithoutproof.

S = k
B
Pr
( )
ln Pr
( ) [ ]

where

Pr
( )istheprobabilityoffindingthesysteminthemicrostate

and

k
B
is
theBoltzmannsconstant.
MicrocanonicalEnsemble
ConsideranisolatedsystemwithNparticlesoccupyingavolumeVwith
totalenergyhavingavalueofE.Letbethenumberofmicrostatescorrespond
ingtothissystem.isalsocalledthepartitionfunctionofthemicrocanonical
ensemble.FromtheGibbsentropyformula,wecanrelatethepartitionfunction
toentropyasfollows

Pr
( )
=
1

S = k
B
1

ln
1

=1

= k
B
ln
( )
1
T
=
S
E






N,V
= k
B
ln
E






N,V

T
=
S
N






E,V
= k
B
ln
N






E,V
P
T
=
S
V






N,E
= k
B
ln
V






N,E

SERCMolecularSimulationWorkshopandSymposium:May69,2009
DepartmentofChemicalEngineering,IndianInstituteofScience,Bangalore560012
4

Entropyofanidealgas
Inordertoobtaintheentropyofanidealgas,weconsider

Nnon
interactingparticlesinaboxandsolveforthewavefunctionusingtheSchrod
ingerequation.Intheclassicallimit,themicrocanonicalpartitionfunctionis
givenas


N,V, E
( )
=
1
h
3N
N!
dp
1
dp
N
dr
1
dr
N

such that
p
i
2
2m
= E
i=1
N

=
V
N
h
3N
N!
2mE
( )
3N / 2
3N /2
( )
!

Intheaboveequations

histhePlancksconstantand

N!indicatesthatallthe
particlesareidenticalandhenceindistinguishable.Fromtheaboveequation,we
canobtainexpressionsforvariousthermodynamicsquantitiesasfollows

S = k
B
ln
= Nk
B
5
2
+ ln
V
N
[
\
|

)
j +
3
2
ln
2E
3N
[
\
|

)
j + ln
2mE
( )
3/ 2
h
3
[
\
|
|

)
j
j
|
|
|
|
|
|
|
|
P
T
=
S
V
[
\
|

)
j
E,N
=
Nk
B
V
PV = Nk
B
T

T
=
S
N
[
\
|

)
j
E,V
= ln
h
3
2mk
B
T
( )
3/ 2
[
\
|
|

)
j
j
+ lnP
=
0
T
( )
+ k
B
TlnP

InderivingtheaboveequationsweusedtheStirlingsformulaforlarge

N

ln N!
( )
NlnN N

CanonicalEnsemble

Figure2:Aclosedsystemwithsurroundingsisolatedfromtheuniverse.Theto
talenergyofthesystemplussurroundingsisE.

ConsideraclosedsystemwithN
1
particlesoccupyingavolumeV
1
inter
actingwithsurroundingscontainingN
2
particlesandhavingvolumeV
2
.Weini
tiallyletthesystemplussurroundingsinteractwithaheatbathhavingatem
peratureT.Onceequilibriumisreached,boththesystemandthesurroundings
areremovedfromtheheatbathandinsulated.Theynowformanisolatedsys
temhavingatotalenergyE.Duringtheinteraction,thesystemcanhavedifferent
SERCMolecularSimulationWorkshopandSymposium:May69,2009
DepartmentofChemicalEngineering,IndianInstituteofScience,Bangalore560012
5
energiescorrespondingtovariousmicrostates.LetE

betheenergyofthesys
temcorrespondingtothemicrostate.Duetoconservationofenergy,thesur
roundingswillhaveenergy

E E

.Thenumberofmicrostatespossibleforthe
surroundingsisequalto

E E

( ).Sincethesystemplusthesurroundingsform
anisolatedsystem,fromthepostulateofequalaprioriprobabilitywehave

Pr
( )
E E

( )
wherePr()istheprobabilityoffindingthesysteminstate.Ifthesurroundings
aremuchlargerthatthesystem,

E >> E

,andwecanexpand

E E

( )ina
Taylorseries.


ln E E

( ) [ ]
= ln E
( ) [ ]
E

ln
E
+
= ln E
( ) [ ]

k
B
T
+
E E

( )
E
( )
exp
E

k
B
T






Pr
( )
exp
E

k
B
T






Pr
( )
=
exp E

/ k
B
T
( )
exp E

/ k
B
T
( )

Q N,V,T
( )
= exp E

/ k
B
T
( )

Intheaboveequation,

Q N,V,T
( )isknownasthepartitionfunctionofthe
canonicalensemble.Since

E

hasadegeneracy

E

( )

Q N,V,T
( )
= E
( )
exp E / k
B
T
( )
E

ThroughtheapplicationoftheGibbsentropyformulawecanrelatethepartition
function

QtotheHelmholtzfreeenergy

A N,V,T
( )asfollows

ln Pr
( )
=
E

k
B
T
ln Q
( )
S = k
B
Pr
E

k
B
T
ln Q
( )

=
Pr E

T
+ k
B
ln Q
( )
Pr

=
E
T
+ k
B
ln Q
( )
k
B
Tln Q
( )
= E TS = A N,V,T
( )

Intheclassicallimit,thecanonicalpartitionfunctionforasystemof

N
particlesisgivenas
SERCMolecularSimulationWorkshopandSymposium:May69,2009
DepartmentofChemicalEngineering,IndianInstituteofScience,Bangalore560012
6


Q N,V,T
( )
=
1

3N
N!
exp H p
N
,r
N
( )
/ k
B
T
[ ]
dp
N
dr
N

where

isthethermaldeBrogliewavelengthoftheparticleandisgivenas

=
h
2
2mk
B
T






1/ 2

H p
N
,r
N
( )
=
p
2
2m

+U r
N
( )
istheHamiltonianofthesystem.Thefirstandthesec
ondtermsdenotethekineticandpotentialenergiesoftheparticlesrespectively.
Foranidealgas,thecanonicalpartitionfunctioncanbeevaluatedexactlyandis
givenby

Q
ig
N,V,T
( )
=
V
N

3N
N!

Therestofthethermodynamicpropertiescanbederivedfromthepartition
functionasfollows.

A
ig
N,V,T
( )
= k
B
TlnQ= Nk
B
T ln N
3
/V
( )
1
[ ]
P
ig
=
A
V






N,T
=
Nk
B
T
V
U
ig
=
A/T
( )
1/T
( )






N,V
=
3
2
Nk
B
T
C
V
ig
=
U
T






N,V
=
3
2
Nk
B

ig
=
A
N






V,T
= k
B
Tln N
3
/V
( )
= k
B
Tln
3
/ k
B
T
( )
+ k
B
TlnP
=
0
T
( )
+ k
B
TlnP

Theensembleaveragesinthecanonicalensembleforamechanicalprop
erty,M,iscalculatedasfollows

M =
M

exp E

/ k
B
T
( )

Q N,V,T
( )

Intheclassicallimit,theaboveequationbecomes


M =
1

3N
N!
M p
N
,r
N
( )
exp H p
N
,r
N
( )
/ k
B
T
[ ]
dp
N
dr
N
Q N,V,T
( )

SERCMolecularSimulationWorkshopandSymposium:May69,2009
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7

GrandCanonicalEnsemble

Figure3:Anopensystemwithsurroundingsisolatedfromtheuniversecontain
ingatotalofNparticles.ThetotalenergyofthesystemplussurroundingsisE.

Consideranopensystemwithvolume

V
1
interactingwithasurrounding
ofvolume

V
2
.Letthetotalnumberofparticlesinthesystemplussurroundingbe
equalto

N.Initiallythesystemplussurroundingareincontactwithalargeheat
bathtillequilibriumisattained.Thentheyareremovedfromtheheatbathand
isolated.Let

Ebethetotalenergyofthesystemplussurroundingsand

Tbe
theirtemperature.Let

N

and

E

bethenumberofparticlesandtheenergyof
thesystemrespectivelyforthemicrostate

.Hencethesurroundingswillcon
tain

N N

particlesandhaveenergy

E E

.Fromthepostulateofequala
prioriprobabilitywehave

Pr
( )
E E

, N N

( )
Ifthesurroundingsaremuchlargerthanthesystemthenwecanexpand

E E

, N N

( ) inaTaylorseriesasfollows


ln E E

, N N

( ) [ ]
= ln E, N
( ) [ ]
E

ln
E






N,V
N

ln
E






E,V
+
= ln E, N
( ) [ ]

k
B
T
+
N

k
B
T
+
E E

, N N

( )
E, N
( )
exp
E

k
B
T






exp
N

k
B
T






Pr
( )
exp
E

k
B
T






exp
N

k
B
T






Pr
( )
=
exp E

/ k
B
T
( )
exp N

/ k
B
T
( )
exp E

/ k
B
T
( )
exp N

/ k
B
T
( )

,V,T
( )
= exp E

/ k
B
T
( )
exp N

/ k
B
T
( )

Intheaboveequation,

,V,T
( ) isknownasthepartitionfunctionofthe
grandcanonicalensemble.Since

E

hasadegeneracy

E

( )

,V,T
( )
= exp
N= 0

N / k
B
T
( )
E, N
( )
exp E / k
B
T
( )
E

SERCMolecularSimulationWorkshopandSymposium:May69,2009
DepartmentofChemicalEngineering,IndianInstituteofScience,Bangalore560012
8

,V,T
( ) isrelatedtothethermodynamicquantitiesasfollows

PV = k
B
Tln
( )

Theclassicalformofthepartitionfunctionisgivenas


,V,T
( )
=
exp N/ k
B
T
( )
h
3N
N!
N= 0

exp H p
N
,r
N
( ) ( )
dp
N
dr
N


Theensembleaveragesinthegrandcanonicalensembleforamechanicalprop
erty,M,iscalculatedasfollows

M =
M

exp N

/ k
B
T
( )
exp E

/ k
B
T
( )

,V,T
( )

Intheclassicallimit,theaboveequationbecomes


M =
1
,V,T
( )
exp N / k
B
T
( )

3N
N!
M p
N
,r
N
( )
exp H p
N
,r
N
( )
/ k
B
T
[ ]
dp
N
dr
N
N= 0

References
1. DonaldA.McQuarrie,StatisticalMechanics,UniversityScienceBooks,
2000
2. TerrellL.Hill,AnIntroductiontoStatisticalThermodynamics,DoverPubli
cations,1987
3. DavidChandler,IntroductiontoModernStatisticalMechanics,OxfordUni
versityPress,1987
4. DaanFrenkelandBerendSmit,UnderstandingMolecularSimulation,2
nd

Edition,AcademicPress,2001
5. M.P.AllenandD.J.Tildesley,ComputerSimulationofLiquids,OxfordUni
versityPress,1989