5.

60 Spring 2008 Lecture #28 page 1

MODEL SYSTEMS
StartingwithQMenergylevelsformoleculartranslation,rotation,&vibration,
solveforqandQ,&allthethermodynamics,forthesedegreesoffreedom.
Theresultsarethefundamentalsofmolecularstatisticalmechanics.
WellderivetheresultsforaclassicalmodelthatmapsontoQMvibrations.
Thenwellcomparetoresults(given,notderived)fortranslationandrotation.
Double-stranded polymer model
Eachmonomerinonestrandinteractswithamonomerintheotherstrand.
Interactionenergyforeachmonomerpairisc
0
.
Thestrandscanunzipfromoneend,rupturingtheinteractionsoftheend
monomers,thenthenextones,thenthenext,andsoon.Eachruptured
interactionraisestheenergybyc
0
.Thethreelowestenergystatesandthe
energylevelsareillustratedbelow.

Configurational
energylevelsc
conf

nc
0
9c
0

8c
0

7c
0

6c
0


5c
0

4c
0

3c
0

2c
0

c
0

0








0 c
0
2c
0
Nondegenerateevenlyspacedlevels,separatedbyenergyc
0
:c=nc
0
(n=integer)
5.60 Spring 2008 Lecture #28 page 2
Foraverylongpolymer,thereisalargenumberoflevels.Thenwecanextend
thesumoverstatesinq
conf
toinfinitybecausethehighestenergiesaremuch
biggerthankTanyway(sothecorrespondingtermsinthesumarenegligible).

q
conf
=

e
c
n
kT n
0
kT
= 1+ e
c
0
kT 2
0
~

e
c
+ e
c kT 3
0
+ e
c kT
+
n n
= + 1 e
c
0
kT c
0
kT
)
+
(
e
c
0
kT
3
2 3

1
c
0
kT
+
(
e
2
)
+ 1+ x+ x + x + =
1 x
wherex e
1
q
conf
=
1 e
c
0
kT

Soq
conf
takesaverysimpleclosedform.Everythingelsefollows.
Q
conf
=
(
q
conf
)
N
=
|

1 e
1
c
0
kT |
.
|
N
\

A = kTlnQ = NkTlnq = NkTln = NkTln1
conf conf conf
|

1
c
0
kT |
|
(
e
c
0
kT
)
\
1 e
.
=
|
cA
conf
|
=
(
e
c
0
kT
)
A
conf
scaleswithN,
conf
=A
conf
/N
conf
\
cN
|
.
T,V
kTln 1
2
dlnq
conf 2
1
c
0
kT |
c
0
|
= Nc
e
c
0
kT
= Nc
1
)
( )
kT .
| 0
1 e
U
conf
= NkT
dT
= NkT
(
1 e
c
0
kT
e
\
2
(

c
0
kT
)
0
(
e
c
0
kT
1
)

2 c
0
kT
2
dU
conf
e
(
c
0
kT
)
|
c
0
| e
c kT
0
C
V
conf
= = Nc
0 2
= Nk
| 2
dT
(
e
c
0
kT
1
)
\
kT
.
(
e
c
0
kT
1
)
conf
A
conf
U
conf

(
c
0
kT
)
c
c
0
kT
kT (
S = + = Nk ln 1 e
T T

+
e
0
1

(
ParticularlyimportantareU
conf
andC
Vconf
andtheirhighTandlowTlimits.Both
quantitiesscalewithN,sowehavethempermoleculetoo.
LowTlimit:U
conf
=0,C
Vconf
=0.Asweveseenbefore,atlowTallthemolecules
areinthegroundstate,andaslightincreaseinTleavesthemthere,sothe
systemenergydoesnotincrease.
HighTlimit:
limU = c
1
, limC = Nk
T
conf
N
0
(
1+ c
0
kT 1
)
= NkT
T
V
conf
5.60 Spring 2008 Lecture #28 page 3
OncekTexceedstheenergyspacing,thenfurtherincreaseinTincreasesthe
occupationofhigherlevels,buttheamountofenergyincreasewithTdoesnt
changeanyfurther:U
conf
T,C
Vconf
isTindependentinthehighTlimit.
Entropy & probability distributions
LowTlimit:S
conf
=0=klnO
conf
sinceonlythegroundstateisoccupied.
HighTlimit:
limS = Nk

ln 1 1 c kT
))
+
c
0
kT
(
(
= Nk ln
(
c kT + 1
)
(

T
conf

( (
0
1+ c
0
kT 1

0
(
= Nkln kT c = kln kT
0
) (
c
0
)
N
NotehighTlimitsforqandQ:
N
q
conf
1 limQ
conf
limq
conf
=
kT
, limQ
conf
| kT|
lim = = =
|
T 0 T0 T
c
0
T
\
c
0 .

qisameasureofhowmanystatesthemoleculehasthermalaccessto.
ForkT>>c
o
,itsjusttheratiokT/c
o
IfkT=10c
o
thenmoleculeshavethermalaccessto~10states.
BoltzmanndistributionP
i
(c
i
)givesprobabilitiesforeachstate:
P
i
(c
i
)
0 1 2 3 4 5 6 7 8 9101112 1314151617 18 xc
0
Molecularenergyc
i
Mostlikelymolecularenergycis0(fornondegeneratelevels)
Widerangeofmolecularlevelsmaybeoccupied
Averagemolecularenergy<c>>>0
SystemenergyU=N<c>>>0
Individualmolecularenergiesvarywidely,butsystemenergydoesnot
Howcome?
i i
Recall Q=

e
E kT
=

O
E
e
E kT
i
system system
statesi energiesE
i
5.60 Spring 2008 Lecture #28 page 4
Alsorecall
i
P=
i
i
E kT
E kT
e
e

i
E
P =
i
i
i
E kT
E
E kT
e
e


O

=
i
i
E kT
E
e
Q

O
i i
Measurementofmacroscopicsystemenergyalwaysyieldsthesameresult
P(E)1forthatsystemenergy!
SystemdegeneracyO(E
i
)increasessharplyassystemenergyE
i
increases.
e.g.O(0)=1;O(c
0
)=N;O(2c
0
)=N(N1)/2+NN
2
/2;etc.
Thisweightsprobabilityinfavorofhighersystemenergy.
Boltzmannfactordecreasesassystemenergyincreases.
Thisweightsprobabilityinfavoroflowersystemenergy.
Averageisabalancebetweenthesefactors.Probabilityisverysharplypeaked!
Howmuchdoesthesystemenergyfluctuate?
Molecularaverageenergy=<c>,molecularstandarddeviationo <c>
Systemenergy=Nxmolecularaverageenergy=N<c>
Systemstandarddeviation=
Relativesystemenergyvariation=
No N <c>
12
12
24
N N 10
10
N N 10

c
= ~ =
c
Fluctuationsareimmeasurablysmallforamacroscopicsystem!
Systementropy S= k

p lnp forsystematconstantT
i i
i
Butwecanapproximate S= klnOwhereO(E)isthedegeneracyforthemost
probablelevel.ThisisOKbecausetherangeofsystemenergiesisverysmall.
Vibrational partition function & thermodynamics
Thedoublestrandedpolymermodelusedheregivesthesameenergiesas
quantummechanicalvibrationalmodesofmoleculesandmaterials.
Classicalvibration:E=mv
2
+kx
2
=K.E.+P.E.,wheremismass,visvelocity,k
isforceconstant(forthissectiononly,normallyitstheBoltzmannconstant),
andxisdisplacement.
Naturalresonancefrequency v =
1 k
0
2t m
Vibrationalamplitude&energycantakeonanyvalue,continuously.
5.60 Spring 2008 Lecture #28 page 5
QMvibrationalstates:nondegenerate,spacedbyequalamounts.Spacingis
1 k
hPlancksconstant c =
0
hv
0
= h
2t m
Wevealreadydonethisproblem!Wecandefinethezeroofvibrationalenergy
asthelowestvibrationallevel,andwegetidenticalresults.

q
vib
=

e
c
n
kT n
0
kT c
0
kT 2
0
+ e
c kT 3
0
+ e
c kT
~

e
c
= 1+ e +
n n
c kT c
0
kT
)
2
+
(
e
c
0
kT
3
2 3

1
c
0
kT
= +
0
1 e +
(
e
)
+ 1+ x+ x + x + =
1 x
wherex e
1
= q
vib
1 e
c
0
kT

Q
vib
= (q
vib
)
N
=
|

\
1 e
1
c
0
kT
.
|
|
N
A = kTlnQ = NkTlnq = NkTln = NkTln1 e
vib vib vib
|

1
c
0
kT |
|
(
c
0
kT
)
\
1 e
.
|
cA
vib
|
kTln 1 e
c
0
kT

vib
=
|
=
( )
A
vib
scaleswithN,
vib
=A
vib
/N
\ cN .
T,V
c
0
kT
U
vib
= NkT
2
dlnq
vib
= NkT
2
1
c
0
kT
)
(
e
c
0
kT
)
|
c
0
2
|
|
= Nc
0
e
c
0
kT
)
= Nc
0
(
e
c
0
kT
1
1
)
dT
(
\ kT
(
1 e . 1 e
dU
vib
e
c
0
kT
(
c
0
kT
2
)
|
c
0
|
2
e
c
0
kT
C
V
= = Nc
0 2
= Nk
|
vib
dT
(
e
c
0
kT
1
)
\
kT
.
(
e
c
0
kT
1
)
2
S
vib
=
A
T
vib
+
U
T
vib
= Nk

(
e
c
0
kT
)
+
e
c
c
0
kT
kT (
(
ln 1
0
1

Resultsareimportantformolecular&materialvibrations.
Vibrationalenergy&heatcapacityresults&limitingvalues:
5.60 Spring 2008 Lecture #28 page 6
LowTlimit:U
vib
=0(=N(c
0
)withthezeroasusuallydefined),C
Vvib
=0.
HighTlimit:limU = NkT, lim C = Nk
T
vib
T
V
vib
Molecularvibrationalfrequencies~
10003000cm
1
.kTat300K~200cm
1
.
mostmoleculesingroundvibrational
statesatroomT(lowTlimit).
C
Vvib
3R
Crystallatticeacousticvibrational
frequencies~30cm
1
mostcrystals
areinthehighTlimit.ForNatomsin
anatomiccrystal,thereare3N
vibrationalmodes,soatroomT,C
V
=
3Nk=3nR.Thiswasusedtodetermine
kT c
0
molecularweights!
NoonecouldexplainwhyC
V
0atlowTuntilEinsteinsuggestedin1905that
ifenergywasquantized,notcontinuous,thenkTcanbemuchlowerthanthe
firstexcitedstateenergy.(Notpossibleifenergyiscontinuous.)
Molecular translation & rotation, classical equipartition of energy
Resultsarederivedinstatisticalmechanicscourse5.62(andinyourtext).
Onekeyresult:foreachdegreeoffreedom(3translational,2or3rotational),
highTlimitforenergyis<c>=kT&forheatcapacityisCv=k.
<c
trans
>=kTx3=3/2kT
<c
rot
>=kTx2=kT(linear)orkTx3=3/2kT(nonlinear)
<c
vib
>=kTpervibrationalmode
Thisistheclassicalequipartitionofenergy.Whydoesitcomeabout?
Eachdegreeoffreedomhaskineticenergygivenclassicallybymv
2
.(Ie
2
for
rotationwhereI=momentofinertiaande=angularvelocity.)
Vibrationaldegreesoffreedom:kineticenergymv
2
&potentialenergykx
2
.
Allthesesquaredenergytermscanbewrittenintheformay
2
.
5.60 Spring 2008 Lecture #28 page 7
Theaveragemolecularenergyforanyofthesedegreesoffreedomisgivenby

e
c
i
kT
<c>= c =

c
i
e
c
i
kT
i i
ButifthelevelsarespacedclosetogetherrelativetokT,thenwecanconvert
thesumsintointegrals.Ifwetreattheenergyclassicallythenitsjust

ay
2
kT
2
c =
}

ay
2

e
ay
2
kT
dy
=
kT
}

x
2
e
2
x
dx
wherex
2
=ay
2
/kT
e dy
}
e
x
dx
}

Integratenumeratorbyparts
2 2 2 2
x
2
e
x
dx= x xe
x
dx [x u,xe
x
dv,v= 1/2 e
x
] ABC
}

}

( )
( )
1
= xe
x
2

+
1
}

e
x
2
dx=
1
}

e
x
2
dx

2 2 2
<c>=kT
kTenergyperkineticandpotentialenergydegreeoffreedominhighTlimit