Statistical Physics I

Homework 3

Due date: 4/27/2020

Question 1
hP
nε i
from equation Q(z, V, T ) = .The question reduce the N to xed value l.
P∞ 0
ze−βε
Q
N =0 {nε } ε

" l #
−βε nε
Y X

Q(z, V, T ) = ze
ε nε

Y 1 − ze−βε l+1
"
#
=
ε
1 − ze−βε

where we have used

l
X ∞
X ∞
X
xn + xn = xn
n=0 n=l+1 n=0
l
X ∞
X ∞
X
xn = xn − xn
n=0 n=0 n=l+1
X∞ ∞
X
= xn − xl+1 xn
n=0 n=0
l+1
1−x
=
1−x

q-potential is given by

Y 1 − ze−βε l+1
"
#!
PV
q= = ln
kT ε
1 − ze−βε
l
l+1 !
X 1 − ze−βε
= ln
ε
1 − ze−βε
l h 
X
l+1 
i
= ln 1 − ze−βε − ln 1 − ze−βε
ε

0
Png Wen Han R08222077

The mean occupation number for state ε is

 
1 ∂q
hnε i = −
β ∂ε
"
l+1 #
1 (l + 1)β ze−βε βze−βε
=− −
β 1 − (ze−βε )
l+1 1 − ze−βε
1 (l + 1)
= −1 βε −
z e − 1 (z −1 eβε )l+1 − 1

Question 2

The intensity of a spectral linshape is proportional to the velocity distribution of molecule between v and
v + dv . Consider only one direction without losing the generality, we have
2
 
−mvx
I(λ) ∝ f (v)dv ∝ exp 2kB T

Assume the molecule moving at vx , the relative motion of the molecule from the observer can be written as
vx
c = − (f −f
f0
0)
= λ−λ0
λ0 , which we have consider non-relativistic limit

Therefore, using the doppler-shifted frequency, we get the relative intensity

Question 3

Cosider the a molecule being reected from a wall in x direction. The velocity of the molecule being vx and
the recoil velocity being vx0 = −vx . The receeding wall having opposing velocity with magnitude of v0 . The
velocity becomes vx0 − v0 = −(vx − v0 ) → vx0 = −(vx − 2v0 )

The translational energy is

1 1
∆ε = mv 0 2 − mvx2
2 x 2
1
2 1
= m vx − 2v) − mvx2
2 2
 2
1 2v 0 1
= mvx2 1 − − mvx2
2 vx 2
∼ 1 1
= m vx2 − 4v0 vx − mvx2


2 2
∼
= −2mv0 vx
or ∼
= −2mv0 v cos θ

 2  
where under adiabatic consideration 2v
vx  1, 1 − 2v
vx = 1− 4v
vx

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Png Wen Han R08222077

The translational energy of the gas is

Z
E= ∆εnvx f (v)d3 v
Z 2π Z π/2 Z ∞
2
= −2mv0 (v cos θ) nf (v)v 2 sin θdvdφdθ
0 0 0
!Z
Z 2π  Z π/2 ∞
= nv0 dφ cos2 θ sin θdθ −2mv 2 f (v)v 2 dv
0 0 0
Z 1 Z ∞
2
= −nv0 (4π) mv 2 f (v)v 2 dv
u du
0 0
 Z ∞
2 1
= −nv0 mv 2 f (v)4πv 2 dv
3 0 2
 
2
= −nv0 εk
3
 
v0 2
=− Ek
V 3

where εk = , Ek = N εk
R∞ 1 2 2
0 2 mv f (v)4πv dv

The energy change with time on the wall with area of A

δE = AδtE
 
1 2
= −Av0 δt Ek
V 3
 
δx 1 2
= −A δt Ek
δt V 3
 
δV 2
=− Ek
V 3

which δV = Aδx

Now dene a ratio a as ratio of translational energy and total energy U .

1
δE = δU
a
2 δV
=− Ek
3a V

We know P V = 23 Ek ,then

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Png Wen Han R08222077

δP δV δEk
+ =
P V Ek
δP δV 2 δV
+ =−
P Z V 3a
Z V 
δP 2 δV
=− 1+
P 3a V
ln P = −γ ln V + C
1
P =A γ
V
P V γ = const

where γ = 1 + 3a
2
or 3a+2



3a

Question 4
for two-hydrogen diatomic molecule, the rotational energy resemble the form of rigid rotator
p2θ p2φ
Hrot = 2I + 2I sin2 θ

The rotational partition function is given by

Z
1
jrot = dθdφdpθ dpφ e−βHrot
(2π~)2
s s
2πI π 2πI sin2 θ 2π
Z Z
1
= dθ dφ
(2π~)2 β o β o
2πI
= 4π
(2π~)2 β
2I
= 2
~ β

here I = µr02 and µ = m2 /2m = m/2

~2
Θr =
mr02 k

Plugging the data given in question ,the temperature that start contributing to the specic heat is mΘr =
75.71K

In search for the vibrational quanta, we have expand the morse potential to 2nd order around the equilibirum
point r0 .

     
2 2 1 4 2 2
V (r) = V0 −1 + − + (r − r0 ) + − (r − r0 )
a a 2 a2 a2
   
1
= V0 −1 + (r − r0 )2
a2
V0
' 2 (r − r0 )2
a

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Png Wen Han R08222077

the vibrational partition function is given by

Z  2 
1 p V0
jvib = drdp exp − − 2 (r − r0 )2
2π~ 2µ a
r r
1 2µπ π
=
2π~ β β
s
1 2µa2
=
2~β V0
s
kT ma2
=
~ 4V0

q
thus Θv = ~
k
4V0
ma2 = 6267K

Question 5

Eusion of gas applies here but now we are considering the area of eusion be the surface of sphere. This
argument is valid as the question require the radius of the small sphere to be smaller than the free mean
path of the gas molecule. Under quasistatic euqilibirum, the energy owing in and out of the sphere is the
same.

The gas of the system obey maxwell boltzman distribution E = 23 N kT .

Now we wish to nd the mean energy of eused molecule, the direction that we concern is in r̂. The
transformation give u = (u sin θ cos φ, u sin θ sin φ, u cos θ). Note that the condition ur > 0, thus the range is
choosen at 0 < θ < π , 0 < φ < π/2
1 2


f (v)dv = exp 2 βmv v 2 dv

The average energy of the euse molecule is given by

R π/2 R π R ∞ 3

2 (u sin θ cos φ) f (~u)u2 sin θdudθdφ
ur = R0π/2 R0π R0∞
0 0 0
(u sin θ cos φ) f (~u)u2 sin θdudθdφ
R π/2 Rπ R∞
0
cos3 φdφ 0 sin4 θdθ 0 f (~u)u5 du
= R π/2 Rπ R∞
0
cos φdφ 0 sin2 θdθ 0 f (~u)u3 du
2 3π

3
3 8 u
= π
hui

2 3 
1 u
=
2 hui

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Png Wen Han R08222077

R π/2 R π R ∞ 3
(u sin θ sin φ) f (~u)u2 sin θdudθdφ
u2θ = R0π/2 R0π R0∞



0 0 0
(u sin θ sin φ) f (~u)u2 sin θdudθdφ
R π/2 3 Rπ R∞
0
sin φdφ 0 sin4 θdθ 0 f (~u)u5 du
= R π/2 Rπ R∞
0
sin φdφ 0 sin2 θdθ 0 f (~u)u3 du
2 3π

3
3 8 u
= π
hui

2 3 
1 u
=
2 hui

R π/2 R π R ∞ 3

2 1 (u cos θ) f (~u)u2 sin θdudθdφ
uφ = m R0π/2 R0π R0∞
2 (u cos θ) f (~u)u2 sin θdudθdφ
0 0 0
R π/2 Rπ R∞
1 0
φdφ 0 cos3 θ sin θdθ 0 f (~u)u5 du
= m R π/2 R π R∞
2 dφ cos θ sin θdθ f (~u)u3 du
0 0 0
=0

 
1 1
mu2 m u2r + u2θ + u2φ





=
2 2

3
1 u
= m
2 hui
1 I5
= m
2 I3
2
=
β
2kT

the rate of change of two distribution namely 32 kT and 2kT are the same at quasiequilibirum

d 3 d
( N kT ) = (2N kT )
dt 2 dt
3 dT 3 dN dN
Nk + kT = 2kT
2 dt 2 dt dt
1 dN 3 dT
kT = Nk
2 dt 2 dt
dN dT
=
3N T

The variation of T can be obtained from equation 6.13 (pathria)

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Png Wen Han R08222077

dN 1 N
= − A hui
dt 4 V r
1 dT 1 2 3 8kT
3 = − (4πr )
T dt 4 4πr3 πm
Z T r Z
1 8k
T −3/2 dT = − dt
T0 4r πm
r

−1/2 −1/2
 1 8k
(−1/2) T − T0 =− t
4r πm
√ √ r
T0 − T 2k
√ = t
T T0 πmr2
√
r
p 2kT T0
T0 − T = t
πmr2
√
r
p 2kT T0
T = T0 − t
πmr2
!
√
r
2kT0 p
T 1+ 2
t = T0
πmr
r !−2
2kT0
T = T0 1 + t
πmr2

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