Ben Sauerwine

Statistical Mechanics Homework 6

26) (Pathria 3.30) The energy levels of a quantum-mechanical, one dimensional,

anharmonic oscillator may be approximated as
2
⎛ 1⎞ ⎛ 1⎞
ε n = ⎜ n + ⎟hω − x⎜ n + ⎟ hω where n ∈ {0,1,2,...}.
⎝ 2⎠ ⎝ 2⎠
The parameter x, usually much smaller than 1, represents the degree of
anharmonicity. Show that, to the first order in x and the fourth order in
hω
u≡ , the specific heat of a system of N such oscillators is given by
kT
⎡⎛ 1 1 4 ⎞ ⎛1 1 ⎞⎤
C = Nk ⎢⎜1 − u 2 + u + ...⎟ + 4 x⎜ + u 3 ⎟⎥
⎣⎝ 12 240 ⎠ ⎝ u 80 ⎠⎦
Note that the correction term increases with temperature!

⎛ ⎛ 1 ⎞ ⎛ 1 ⎞2 ⎞
∞ ∞ − βh ω ⎜ ⎜ n + ⎟ − x ⎜ n + ⎟ ⎟ ∞ ⎛ 1 ⎞⎛ ⎛ 1 ⎞⎞
⎜⎝ 2 ⎠ ⎝ 2 ⎠ ⎟ − βhω ⎜ n + ⎟ ⎜⎜ 1− x ⎜ n + ⎟ ⎟⎟
Z = ∑e − βε n
= ∑e ⎝ ⎠
= ∑e ⎝ 2 ⎠⎝ ⎝ 2 ⎠⎠

n =0 n =0 n =0
⎛ ⎛ 1 ⎞⎞
⎛ ⎛ 1 ⎞ ⎛ 1 ⎞2 ⎞ ⎜⎜ 1− x ⎜ n + ⎟ ⎟⎟
∞ − β hω ⎜ ⎜ n + ⎟ − x ⎜ n + ⎟ ⎟
⎜⎝ 2 ⎠ ⎝ 2 ⎠ ⎟ ∞ ⎛ ⎛ 1⎞
− βhω ⎜ n + ⎟ ⎞ ⎝ ⎝ 2 ⎠⎠
= ∑e ⎝ ⎠
= ∑⎜e ⎝ 2⎠ ⎟
⎜ ⎟
n =0 n =0
⎝ ⎠
∞ ⎛ 1⎞
− βhω ⎜ n + ⎟
βhω = u z0 = ∑ e ⎝ 2⎠

n =0
Now I expand in x for
∂2
≈ z 0 + ux 2 (z 0 )
∂u
⎛ ∂2 ⎞ ⎛ ∂2 ⎞ ∂2
ln⎜⎜ z 0 + ux 2 ( z 0 )⎟⎟ = ln z 0 + ln⎜⎜1 + ux 2 ( z 0 )⎟⎟ ≈ ln( z 0 ) + ux 2 ( z 0 )
1 1
⎝ ∂u ⎠ ⎝ z 0 ∂u ⎠ z 0 ∂u
1 hω ⎡ 1 ∂2 ⎤
A = − ln Z = − ⎢ 0
ln z + ux 2 0⎥
z
β u ⎣ z 0 ∂u ⎦
hω ∂ ∂u ∂ ⎛ hω ⎞ ∂ ∂ − ku 2 ∂
T=
1
kβ
=
ku
= = ⎜− 2 ⎟
∂T ∂T ∂u ⎝ kT ⎠ ∂u
= − khωβ 2
∂u
=
hω ∂u
( )
∂ 2 A hω − ku 2 ∂ − ku 2 ∂ ⎛⎜ hω ⎡ 1 ∂2 ⎤⎞
C = −T = − ⎢ 0
ln z + ux z ⎟
2 0 ⎥⎟
∂T 2 ku hω ∂u hω ∂u ⎜⎝ u ⎣ z 0 ∂u ⎦⎠
Done simply in Mathematica, the result is:
which agrees with the result from the book.
27) (a) A small system consists of a single harmonic oscillator of angular
frequency ω in equilibrium with a reservoir at temperature T. What is the
probability of the oscillator being in a state of odd quantum number,
n ∈ {1,3,...} ? What does this probability reduce to at T = 0, T = ∞ ? Why do
you expect these results?
⎛ 1⎞
∞ ∞ − β hω ⎜ n + ⎟ 1 ⎛ hωβ ⎞
Z total = ∑ e − βε n
= ∑e ⎝ 2⎠
= csc h⎜ ⎟
n =0 n =0 2 ⎝ 2 ⎠
⎛ 1⎞ hωβ
∞ − βhω ⎜ ( 2 n +1)+ ⎟
Z odd = ∑ e ⎝ 2⎠ 1
= e 2
(coth (hωβ ) − 1)
n =0 2
Z odd 1
Podd = =
Z total 1 + e hωβ
As T → 0, β → ∞, Podd → 0 . This is to be expected since the oscillator will tend to
the lowest, even state as temperature goes very low.
1
As T → ∞, β → 1, Podd → . This is to be expected since the oscillator will be in an
2
essentially random state, and half of the states are odd.
(b) A small system consists of two harmonic oscillators, each of frequency ω , in
equilibrium with a reservoir of temperature T. If the oscillators are in different
quantum states, they do not interact, but if they are in a state having the same
quantum number n, they interact and have a combined energy (including the
zero point energy) of hω + 2nhω + Δε . Find the probability that the two
oscillators have identical quantum numbers.
 ⎛ 1⎞
ε n = ⎜ n + ⎟hω ε combined ,n = hω + 2nhω + Δε
⎝ 2⎠
∞ ∞ ∞ ∞
Z total = ∑ ∑ e − ∑e + ∑e
− βε n − βε m − βε n − βε n − βε combined , n
e e
n =0 m =0 n =0 n =0
βhω
csc h(βhω )
2e 1 − βΔε
= + e
(e βhω
)(
+ 1 e β hω − 1 ) 2
2
∞
Z same = ∑ e
− βε combined , n

n =0

=
1 − βΔε − βhω
e e (1 + coth (βhω ))
2
Z 1
Psame = same = β ( Δε −hω ) βhω
Z total 2e e
1+ β hω
e −1
Above, I have let Mathematica do all of the work for me. As a function of
temperature, the plot of this probability will look like this:

0.1

0.08

0.06

0.04

0.02

1 2 3 4 5 6
Fascinatingly, it appears that at some energy the probability is a maximum (probably
as the two oscillators enter their first state or so together), then tapers off as the
oscillators may suddenly take an extraordinary range of values.

28) (a) Use the grand canonical ensemble with a variable set β ,V , λ to show

that (N − N
2
) ⎛∂ N
= ⎜⎜
⎞
⎟
⎟ .
⎝ ∂ ln λ ⎠ β ,V
Here I follow the procedure from Sekerka, notes online. http://sekerka.phys.cmu.edu
 (N − N ) 2
= N 2 − 2N N + N
2
= N2 − N
2

Recall that
⎛ ∂ ⎞ 1⎛ ∂ ⎞
λ = e βμ ln λ = βμ ⎜ ⎟ = ⎜⎜ ⎟⎟
⎝ ∂ ln λ ⎠ β ,V β ⎝ ∂μ ⎠ β ,V
Certainly,
− βε r , s
e e βμN s
Z = ∑e
− βε r , s
e βμN s Prs =
r ,s Z
∂2z 1 1 ⎛ ∂2Z ⎞
= ∑ N Prs = β 2 ∑ N s e − βε rs e βμN s = 2 ⎜⎜ 2 ⎟⎟
2 2 2 2
N N
∂μ β Z ⎝ ∂μ ⎠V , β
s 2
r ,s rs

And of course
1 ⎛ ∂ ln Z ⎞ 1 1 ⎛ ∂Z ⎞
N = ⎜⎜ ⎟⎟ = ⎜ ⎟
β ⎝ ∂μ ⎠V , β β Z ⎜⎝ ∂μ ⎟⎠V , β
Now
1 ⎛∂ N ⎞ ⎛∂ N ⎞
2
1 1 ∂2Z 1 1 ⎛ ∂Z ⎞ 1 ⎛ ∂ 2 ln Z ⎞
N − N = 2 − ⎜ ⎟ = ⎜ ⎟ = ⎜ ⎟ =⎜ ⎟
2 2
2 ⎜ ⎟ 2 ⎜ 2 ⎟
β Z ∂μ 2
β Z ⎝ ∂μ ⎠
2
β ⎝ ∂μ ⎠ β ,V β ⎝ ∂μ ⎠ β ,V ⎜⎝ ∂ ln λ ⎟⎠ β ,V
⎜ ⎟

28) (b) For an ideal gas with energy levels independent of spin s, show that
3
⎛ mk T ⎞ 2
λVnQ ( 2 s +1)
ln Z ≡ q = e NQ ≡ ⎜ B 2 ⎟ .
⎝ 2πh ⎠
Here I follow the procedure from Sekerka, notes online. http://sekerka.phys.cmu.edu
v
f kv ,ms = v
1
≈e eβμ ( )
− βε k

e ( ( ) ) +σ
β ε k −μ
In a classical ideal gas, . Now

certainly N = e βμ ∑ e − βε . Let z = ∑ e βε . −

ε ε
Using K = F − μN K = −k B ln Z
F = −k B T ln Z , (henceforth, Z means Grand
Canonical, and Z means canonical partition function). Now ln Z = ln Z − μβ N ,
and using the results for Fermi and Bose gases combined:
ln Z Fermi = ln ∏ (1 + e β ( μ −ε ) ) ln Z Bose = ln ∏
1
ε (1 −e )
β ( μ −ε )
ε

ln Z Total = ± ∑ ln 1 ±e β ( μ −ε ) ( )
ε
which in the classical limit described earlier gives
ln Z = ∑ e β ( μ −ε ) = λz = N . However, from problem 25b last week, I determined
ε

that N = (2s + 1)VnQ e βμ , so ln Z = (2s + 1)VnQ e βμ . Notice that I certainly do not get
the exponential part of the result. Was this a typo?
28) (c) Evaluate (N − N )
2
, λ , μ for an ideal gas.
⎛∂ N ⎞ 1 ∂
N2 − N
2
= ⎜⎜ ⎟ =
⎟ (2s + 1)VnQ e βμ = (2s + 1)VnQ e βμ
⎝ ∂ ln λ ⎠ β ,V β ∂μ
PV
and of course λ = e βμ . From Pathria, I see that for an ideal gase q = ln Z = .
kT
Then I have ln Z = (2s + 1)VnQ e βμ = βPV . Based on this,
1 ⎡ nQ (1 + 2s ) ⎤
μ =− ln ⎢ ⎥
β ⎣ Pβ ⎦
where PV = nKT
so that now I have
Pβ
λ=
nQ (1 + 2 s )
N2 − N = VPβ
2

28) (d) Suppose that you are able to count, as a function of time, the number of
particles in an ideal gas that are in some subvolume v = 1mm 3 of a large
container of gas at thermal equilibrium at a temperature of 298 K and a
pressure of 1 atm. What is the average number of particles in this volume?
What is the root mean square relative fluctuation of this number? Numerical
answers are required.

Using the results from parts a and c, I see that

N2 − N
2
N
= (2s + 1)VnQ e βμ
= = Pβ for the case of an ideal gas. Now I have
V V
1 1 mm 3 atm 1 1 mm 3 atm
N = N2 − N = PβV = =
2

298 k B K 298 1.38 ⋅ 10 − 23 J

mm 3 atm
= 2.43 ⋅ 10 20

J
N2 − N
2
1
= = 6.415 ⋅ 10 −11
N N
29) (a) For the grand canonical ensemble, show that the entropy can be written
S
in the form = −∑ Pr , s ln Pr , s , where Pr , s is the probability of a state having
kB r ,s

exactly N s particles and an energy ε rs = ε r (N s ) .

 ⎛ ∂K ⎞ e − βε rs e βμN s
S = −⎜ ⎟ Prs =
⎝ ∂T ⎠V , μ Z
Z = ∑ e − βε rs e βμN s = e − βK
r,s

⎛ ∂Z ⎞ kZK ⎛ ∂ ⎡ β 2 ⎛ ∂Z ⎞ ⎤ ⎞ ⎛ ∂K ⎞
⎜ ⎟ = 2 −⎜ ⎢ ⎜ ⎟ ⎥ ⎟⎟ = − ⎜ ⎟ =S
⎝ ∂T ⎠V , μ β ⎜ ∂T ⎢⎣ ⎝
Z ∂T ⎠V , μ ⎥⎦ ⎠V , μ ⎝ ∂T ⎠V , μ
⎝
⎛ ∂K ⎞ kT ∂Z
K = − kT ln Z −⎜ ⎟ = k ln Z +
⎝ ∂T ⎠V , μ Z ∂T
β [ε r , s − N s μ ]e
[
− β ε r ,s − N s μ ]
S T ∂Z
= + ln Z = ∑ − ln Z
k Z ∂T r,s Z
[ ] [ ]
= −∑ Pr , s ln e + 1ln Z = −∑ Pr , s ln e + ∑ Pr , s ln Z
− β ε r ,s − N s μ − β ε r ,s − N s μ

r,s r,s r,s

⎛ − β [ε r , s − N s μ ] ⎞
= −⎜ ∑ Pr , s ln e
⎜ − ∑ Pr , s ln Z ⎟⎟ = −∑ Pr , s ln Pr , s
⎝ r,s r,s ⎠ r,s
29) (b) Now consider the grand canonical ensemble for the case of non-
interacting orbitals having a set of energies ε and probabilities pε (n ) that an
orbital ε has an occupation number of exactly n. Show that in this case the
= −∑∑ pε (n ) ln pε (n ) .
S
entropy can be expressed in the form
kB ε n

From the problem statement, the probability

e − βε rs e βμN s
Prs = = pε (n ) . Since the problem states that these are non-
Z
interacting orbitals, the grand canonical ensemble is appropriate and so I may use the
result from part a,

S
= −∑ Pr , s ln Pr , s
kB r,s
30) In class, we explored a model of adsorption of a gas on a surface having
N s absorption sites. The problem pertains to a modified version of that
model in which two adsorbed molecules on the same site can interact. Take
the energy of an empty site to be zero and that of a singly occupied site to be
ε 1 . Assume that molecules that adsorb on a doubly occupied site interact via
a vibrational mode having frequency ε 2 + n' hω n' = 0,1,2,... as for a
harmonic oscillator. Assume that the adsorption sites are very dilute (non
interacting) and distinguishable by virtue of their position.
a) Calculate the grand canonical partition function z for a single adsorption
site. Then write down the grand canonical partition function q = ln Z for all
sites.
∞
e hωβ
z = 1 + λe − βε 1
+λ 2
∑e
n =0
− β (ε 2 + nhω )
= 1 + λe − βε 1
+λ e 2 − βε 2

e hωβ − 1
βμ ⎡ − βε 1 2 − βε 2 e hωβ ⎤
λ=e Z=z Ns
q = ln Z = N s ln ⎢1 + λe +λ e ⎥
⎣ e hωβ − 1⎦
b) Calculate the mean occupation number and the mean energy of each site.
2 − βε 2 e hωβ
λ e
λe − βε1 e hωβ − 1
occupation = +2
z z
λe − βε1 ∞
e − β (ε 2 + nhω )
energy = ε 1 + λ2 ∑ (ε 2 + nhω )
z n=0 z

= ε1
λe − βε 1

+
λ2 e − β (ε 2 + hω )
(− ε 2 + ε 2 e βhω + hω )
z z −1 (e βhω
) 2

Plotting these versus temperature, I get for occupation with respect to beta for sample
choices of the other variables:
2

1.8

1.6

1.4

1.2

0.5 1 1.5 2 2.5 3

For energy, I get (for the same variable choices):
 200

150

100

50

0.2 0.4 0.6 0.8 1

c) What is the probability that a site will be doubly occupied and in a

vibrational state having a vibrational quantum number n’=3?
λ2 e − β (ε 2 +3hω )
P(occupation = 2, n' = 3) =
z
0.07

0.06
0.05
0.04

0.03
0.02

0.01

0.2 0.4 0.6 0.8 1

For the same choices of variables as above, this plot shows the probability.