Statistical Physics I

Homework 2

Due date: 4/19/2020

Question 1

the energy of one diatomic molecule is describe by

( )
p2 p2θ p2φ
εi = + + − µE cos θi
2m 2I 2I sin2 θi
= εt + εr

p2θ p2φ
n o
p2
where εt = 2m , εr = 2I + 2I sin2 θi
− µE cos θi

The hamiltonian consist of translational part and rotatinal part. The translational part by convention has
3N degree of freedom. The rotational part has only 2N due to equal weights for equal solid angle. The
partition function of the system is

Z N
! Z N
!
1 1 Y 1 Y
QN (β) = e−βεt d3N qt d3N pt e−βεr d2N qr d2N pr
N! h3N i=1
h2N i=1
 N  Z N
1 V 3 1
= 3
(2πmkT ) 2 e−βε dθdφdpθ dpφ
N! h h2
Z
V
Q1 (β) = 3 2 e−βε dθdφdpθ dpφ
λ h
where λ = √ h
(2πmkT )

0
Png Wen Han R08222077

Z
V
Q1 (β) = e−βε dθdφdpθ dpφ
λ3 h2
!
∞
p2θ p2φ
Z Z
V
= 3 2 exp −β −β dpθ dpφ exp (µβE cos θ) dθdφ
λ h 0 2I 2I sin2 θi
Z 2π Z πs s
V 2πI 2πI
= dφ exp (µβE cos θ) sin θdθ
λ3 h2 0 0 β β
Z 2π Z 1s s
V 2πI 2πI
= dφ exp (µβEu) du
λ3 h2 0 −1 β β
V (2π)2 I 1
Z
= exp (µβEu) du
λ3 h2 β −1
V 2I 1
= (exp (µβE) − exp (−µβE))
λ3 ~2 β 2µβE
V 2I
= sinh(µβE)
λ3 µ~2 β 2 E

The denition of electric polarization is Pz = N hµ cos θi. It will be shown that P is solely depend on rota-
tional part.

N ∂ ln Z
Pz =
β ∂E
 
N ∂ V 2I
= ln 3 2 2 + ln sinh(µβE) − ln E
β ∂E λ µ~ β
 
N µβ cosh(µβE) 1
= −
β sinh(µβE) E
 
1
= N µ coth(µβE) −
βµE
= N µL(βµE)

assume a classical system |µE|  kT → βµE  1,then we can assume L(βµE) ∼

= βµE
3

2
µ2 nE
Hence, Pz = N βµ3 E . Then, the polarization per unit volume is P = 3kT ,where n = N/V

The relation between dielectric constant and polarization is given by

√ E
4πε0 P = (ε − ε0 ) √
4πε0
ε
4πP = ( − 1)E
ε0
ε 4πP + E
=
ε0 E
4πnµ2
ε=1+
3kT
note that here ε
ε0 (S.I) = ε(G.C.S)

Page 1 of 5
Png Wen Han R08222077

Question 2

With the energy of the nuclei dene as {E± = , E0 = 0}, where E± are the degenerate states. The partition
function of the system is

X
QN (T ) = gi exp (−βEi )
i

= 2 exp (−β) + 1
= 2 exp (−β) + 1

(a) The probabilities of three spin state is as follow:

gi exp (−βEr )
Pr =
QN (T )

then P0 = 1
2 exp(−β)+1 and P± = 2 exp(−β)+1 .
2 exp(−β)

Here r = ± is denote as degenerate energy states with energy , note that P+ = P− = 2 exp(−β)+1 .
exp(−β)

(b) the mean energy

P
i Ei gi exp (−βEi )
hEi = P
i exp (−βEi )
2 exp (−β)
=
2 exp (−β) + 1

similarly the mean energy can be obtained through partition function.

∂
U =− (ln{2 exp (−β) + 1})
∂β
2 exp (−β)
=
2 exp (−β) + 1

(c) Mean energy for N nuclei

Since nuclei are indistinguisable and non-interacting.

N
X
EN = hEii
i

= N hEi
N  exp (−β)
=
exp (−β) + 12

Page 2 of 5
Png Wen Han R08222077

or
∂ N  exp(−β)
U = − ∂β (N ln{2 exp (−β) + 1}) = exp(−β)+ 12

The Hemlholtz free energy can be obtained through the partition function.

A = −N kT ln{2 exp (−β) + 1}

Then, the entropy for N nuclei

1
S= (U − A)
T
N  exp (−β)
= N k ln{2 exp (−β) + 1} +
T exp (−β) + 12
N 1
= N k ln{2 exp (−β) + 1} +
T 1 + 12 exp (β)

double check:

 
∂A
S=−
∂T N,V
∂
= (N kT ln{2 exp (−β) + 1})
∂T
kT  


2N kT 2 exp − kT
= N k ln{2 exp (−β) + 1} + 


2 exp − kT +1
N 1
= N k ln{2 exp (−β) + 1} +
T 1 + 12 exp (β)

when kT  , β → 0, exp (−β) = exp (β) → 1, 

T =0

S = N k ln 3

when kT  , β → ∞, exp (−β) → 0 ,exp (β) → ∞

S = k ln{1} = 0

this is consistent with third law of thermodynamics.

Page 3 of 5
Png Wen Han R08222077

Question 3

for non-interacting absorbed molecules

QN (N0 , T ) = g(N )aN

N0 !
= aN
N !(N0 − N )
ln QN (N0 , T ) = N0 ln (N0 ) − N ln (N ) − (N0 − N ) ln(N0 − N )
− N0 + N + N0 − N + N ln (a)
= N0 ln (N0 ) − N ln (N ) − (N0 − N ) ln(N0 − N ) + N ln (a)

the chemical potential is

1 ∂
µ=− ln QN
β ∂N
1 ∂
=− (−N ln N − (N0 − N ) ln(N0 − N ) + N ln a)
β ∂N
1
= − (− ln N − 1 + ln(N0 − N ) + 1 + ln a)
β
1
= (ln N − ln(N0 − N ) − ln a)
β
 
1 N
= ln
β (N0 − N )a

Page 4 of 5
Png Wen Han R08222077

Question 4

At a triple point, the chemical potential of three phases are the same

µg = µl = µs ,where g, l, s stands for gas, solid liquid.

It has been shown in lecture notes that

µg (Pσ (T ), T ) = µl (Pσ (T ), T )
       
∂µg ∂µg dPσ ∂µl ∂µl dPσ
+ = +
∂T P ∂P T dT ∂T P ∂P T dT
dPσ dPσ
−sg + vg = −sl + vl
dT dT
sl − sg dPσ
=
vl − vg dT
dPσ ∆slg
=
dT ∆vlg

similarly, µl = µs gives ∆ssl

∆vsl = dPσ
dT and µs = µg = gives ∆sgs
∆vgs = dPσ
dT

It can be clearly seen that ∆slg + ∆ssl + ∆sgs = 0 and ∆vlg + ∆vsl + ∆vgs = 0.Thus, this guarantee each
coexistence line between two phases at triple point points into third phase.

A more general mathematical detail can be summarized as follow:

     
∆vij ∆vjk ∆vki
the slope from each coexistence curve is dPσ ∆y ∆sij
result in vectors of + =−


dT ij = ∆x = ∆vij .
∆sij ∆sjk ∆ski

The third vector must be the negative of sum of the other two in stated case ,guaranteeing the third phase
must not be the same as the previous two. In other words, the two phase points must point to a third phase.

Page 5 of 5