PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

Solution to assignment 9 of Thermodynamics and Statistical Mechanics1

(Due on October 25 2024 at 2pm. Submit your solution to Canvas as a PDF file.)

Problem 1 (10 points). In class, we have discussed the probability to find a state in a system that has
a fixed temperature T , and this probability is given by e−βE /Z, where β = 1/(kT ), E is the energy of
this state and Z is the partition function. In this problem, we discuss this probability distribution in more
detail. In particular, we would like to understand the fluctuations of energy around its average value.
(1) (2 points) Denote the energy of the system by U . Show that the average value of U n is given by

(−1)n ∂ n Z
Un = . (1)
Z ∂β n

(2) (2 points) The fluctuations of the energy around its average value can be characterized by the standard
2
deviation, σU , which is determined by σU = (U − U )2 . Show that
2
σU = U 2 − (U )2 . (2)

Namely, the standard deviation squared is the average of the squares minus the square of the average.
(3) (4 points) Show that the standard deviation of energy can be related to the heat capacity of the system,
C = ∂U∂T , via
p
σU = kT C/k. (3)

(4) (2 points) How do the heat capacity C and energy U scale with the number of particles in all systems
we have examined so far, which is denoted by N ? Namely, if C ∼ N αC and U ∼ N αU , what are αC and
αU ? How does the relative deviation of energy scale with the particle number? Namely, if σU /U ∼ N α ,
what is α?
Solution:
P e−βE n P −βE
(1) The average value of U n can be calculated as U n = Z E . With the partition function Z = e ,
we have
∂nZ X
= (−1) n
E n e−βE (4)
∂β n
Thus, we get the Eq. (1).

(−1)n ∂ n Z
Un = (5)
Z ∂β n
1 You are welcome to get back with questions and clarifications if the wording of problems is ambiguous.

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

(2) In this part,

2
σU = (U − U )2 (6)
X e−βE  X e−βE 2
= E− E (7)
Z Z
X e−βE  2

= E 2 − 2EU + U (8)
Z
= U − (U )2
2 (9)

(3) With the results in part 1 and part 2, we have

1∂2Z
U2 = (10)
Z∂β 2
1 ∂
= (−ZU ) (11)
Z∂β
∂U 1 ∂Z
=− − U (12)
∂β Z ∂β
∂U
=− + (U )2 (13)
∂β
Thus,
2
σU = U 2 − (U )2 (14)
∂U
=− (15)
∂β
∂U
= kT 2 (16)
∂T
p
⇒ σU = kT C/k (17)

(4) In the systems we have examined so far, U ∝ N T . Thus, we have

U ∼ N, αU = 1 (18)

∂U
C= ∼ N, αC = 1 (19)
∂T
and,
1 −1 1 1
σU /U ∼ C 2 U ∼ N−2 , α = − (20)
2

Problem 2 (10 points). In class, we have discussed diatomic molecules made of two different atoms. In this
problem, we will discuss diatomic molecules made of two identical atoms. In particular, we will investigate

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

the behavior of ordinary hydrogen, H2 , at low temperatures. The rotational energy of a hydrogen molecule
is given by E(j) = ϵj(j + 1), where the constant ϵ is 0.0076 eV and j is the orbital angular momentum. For
each j, there are 2j + 1 states. The set of allowed j values is determined by the spin configuration of the two
atomic nuclei. There are four independent spin configurations, classified as a single “singlet” state and three
“triplet” states. The time required for a molecule to convert between the singlet and triplet configurations
is ordinarily quite long, so the properties of the two types of molecules can be studied independently. The
singlet molecules are known as parahydrogen while the triplet molecules are known as orthohydrogen.
(1) (2 points) For parahydrogen, only the rotational states with even values of j are allowed. Use a computer
to calculate the rotational partition function, average energy, and heat capacity of a parahydrogen molecule.
Sketch the heat capacity as a function of kT /ϵ. When you calculate the partition function by a computer,
you will need to truncate j at some appropriate value. You should determine the cutoff of j and numerically
verify that ignoring the contributions from larger j’s does not induce a sizable error in the partition function.
(2) (2 points) For orthohydrogen, only the rotational states with odd values of j are allowed. Repeat part
(1) for orthohydrogen.
(3) (2 points) At high temperatures, where the number of accessible even-j states is essentially the same
as the number of accessible odd-j states, a sample of hydrogen gas will ordinarily consist of a mixture of
1/4 parahydrogen and 3/4 orthohydrogen. A mixture with these proportions is called normal hydrogen.
Suppose that normal hydrogen is cooled to low temperature without allowing the spin configurations of the
molecules to change. Sketch the rotational heat capacity of this mixture as a function of temperature. At
what temperature does the rotational heat capacity fall to half its high-temperature value (i.e., to k/2 per
molecule)?
(4) (2 points) Suppose now that some hydrogen is cooled in the presence of a catalyst that allows the nuclear
spins to frequently change alignment. In this case all values of j are allowed, but the odd-j terms should be
counted three times each because of the nuclear spin degeneracy. Calculate the rotational partition function,
average energy, and heat capacity of this system, and plot the heat capacity as a function of kT /ϵ.
(5) (2 points) A deuterium molecule, D2 , has nine independent nuclear spin configurations, of which six
are “symmetric” and three are “antisymmetric.” The rule for nomenclature is that the variety with more
independent states gets called “ortho-,” while the other gets called “para-.” For orthodeuterium only even-j
rotational states are allowed, while for paradeuterium only odd-j states are allowed. Suppose, then, that a
sample of D2 gas, consisting of a normal equilibrium mixture of 2/3 ortho and 1/3 para, is cooled without
allowing the nuclear spin configurations to change. Calculate and plot the rotational heat capacity of this
system as a function of temperature.
Solution:
(1) For parahydrogen, only the rotational states with even values of j = 2n (n = 0, 1, 2, ...) are allowed. We
have
X∞
Zp = (4n + 1)e−βϵ2n(2n+1) (21)
n=0
1 ∂Zp
Ep = − (22)
Zp ∂β
dEp
Cp = (23)
dT
In this part, we choose the cutoff of j to be jc = 10. The heat capacity is plotted below:

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

(2) For orthohydrogen, only the rotational states with odd values of j = 2n + 1 (n = 0, 1, 2, ...) are allowed.
In this part, we choose the cutoff of j to be jc = 11. The heat capacity is plotted below:
∞
X
Zo = (4n + 3)e−βϵ(2n+1)(2n+2) (24)
n=0

(3) For the normal hydrogen, its rotational heat capacity is

1 3
Cnormal = Cp + Co (25)
4 4

The heat capacity reaches half its asymptotic value at kT /ϵ ≈ 1.67. For ϵ = 0.0076 eV, the corresponding
T ≈ 150 K.

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

(4)The new partition function is

Znew = Zp + 3Zo (26)
In this part, we choose the cutoff of j to be jc = 11. The heat capacity is plotted below:

(5) In this part, for D2 system, its Zp′ = Zo and Zo′ = Zp . Its partition function:

2 ′ 1 ′
ZD2 = Z + Z (27)
3 o 3 p

Problem 3 (10 points). In this course, we have encountered the equipartition theorem in the first week,
seen its manifestation in many examples, and learnt its proof. In this problem, we apply the equipartition
theorem to a simple pendulum, which consists of a mass m that is attached to a massless string with length
L (see figure 1). Suppose the pendulum is in an environment with temperature T . We would like to discuss
the effect of the thermal fluctuations on the position of this pendulum.
(1) (3 points) Suppose the mass m slightly moves away from its equilibrium position, so that the angle
between the string and the vertical direction is θ and the angular velocity is ω (namely, ω = dθ/dt where t is
time). What is the total energy of the pendulum, which includes both the kinetic energy and gravitational
energy? Denote the gravitational acceleration by g, and assume θ is small in order to simplify the result.
(2) (4 points) In thermal equilibrium at temperature T , what is θ, the average value of θ? What q is σθ , the
standard deviation of θ? Similar to problem 1, here the standard deviation of θ is defined as σθ = θ2 − (θ)2 .
Namely, the square of σθ is the average of θ2 minus the square of the average of θ.

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

Figure 1: A simple pendulum consists of a mass m attached to a massless string.

(3) (3 points) Suppose T = 300 K, L = 0.5 m, m = 0.1 kg and g = 10 m/s2 . What is the value of σθ ? Is
the assumption of a small θ valid?
Solution:
(1) For the total energy of the pendulum, we have

E = Eg + Ek (28)
1
= mgL(1 − cos θ) + mω 2 L2 (29)
2
With limθ→0 cos θ = 1 − 12 θ2 + o(θ4 ), we can further simplify the expression of the total energy.
1 1
E= mgLθ2 + mω 2 L2 (30)
2 2
1 2
e− 2 βmgLθ . For the
P
(2) In thermal equilibrium at temperature T , we have the partition function Zθ =
θ, we have
Z t0 − 1 βmgLθ2
e 2
θ= θdθ = 0 (31)
−t0 Zθ

For the θ2 , by using the equipartition theorem, we have

1 1
Eθ = mgLθ2 = kT (32)
2 2

kT
θ2 = (33)
mgL
Thus, the standard deviation of θ is
s
kT
σθ = (34)
mgL

(3) With T = 300 K, L = 0.5 m, m = 0.1 kg and g = 10 m/s2 , we have

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

σθ ≈ 9.1 × 10−11 ≪ 1 (35)

Thus, the assumption of a small θ is valid.