Jonathan McFadden

Spring 2010

PHYS 7400
Kubo Solutions

Chapter 1 - Solutions
Problem 1-1): Explain Daltons law for an ideal gas mixture on the basis of elementary kinetic
theory of gas molecules.
, where n is the
Solution 1-1): From Bernoullis Formula, the pressure of an ideal gas can be given as p = 23 n
average number ofPmolecules per unit volume and is the average kinetic energy per molecule. Now, Daltons Law
states that PT = i pi . Applying Bernoullis Formula to Daltons Law gives
PT =

pi =

i=1

X2
i=1

ni i

(1.1.1)

where ni is the average number of molecules of the ith kind per unit volume and i is the average kinetic energy
per molecule of the ith kind. Noting these definitions for ni and i , we can express them as
Ni
V
Ti
i =
Ni

ni =

where Ni is the total number of molecules of the ith kind in the system, V is the volume of the system, and Ti is
the total kinetic energy of all of the molecules of the ith kind. Applying these expressions for ni and i to the
expression in (1.1.1) gives

PT =

X2
i=1

ni i =

2X
3 i=1

Ni
V

Ti
Ni


=

2 X
2 X Ti
=
Ti
3 i=1 V
3V i=1

(1.1.2)

Now, the total kinetic energy of all of the molecules of the ith kind, Ti , can be expressed as

Ti =

X p2ij
2mi
j=1

where pij is the momentum of the jth molecule of the ith kind of molecules and mi is the mass of the ith kind of
molecule. Applying this expression for Ti to the expression in (1.1.2) gives

PT =

2 X
2 X X p2ij
Ti =
3V i=1
3V i=1 j=1 2mi

(1.1.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-2): Imagine a fictitious surface element in an ideal gas. Supposing that momentum
transfer takes place through the surface element due to penetration by gas molecules, find the
formula for calculating the pressure which both sides of the surface element exert upon each other
(Lorentzs Method). Assume that the gas molecules obey a Maxwellian velocity distribution.
Solution 1-2): Using Daltons Law, the pressure exerted across the surface can be given as PT = p1 + p2 , where p1
is the pressure on one side, Side 1, of the membrane and p2 is the pressure on the other side, Side 2, of the surface.
From Bernoullis Principle, the pressure of an ideal gas can be given as p = 32 n
, where n is the number density1 of
the gas in question and is the average kinetic energy per molecule. Adapting Bernoullis Principle for this
situation and applying that adaptation to Daltons Law, as it pertains to this system, gives

PT = p1 + p2 =

2
(n1 1 + n2 2 )
3

(1.2.1)

where n1 and 1 , and n2 and 2 are the number densities and average kinetic energies of the gases on sides Side 1
and Side 2, respectively. Choosing the surface to lie in the yz-plane, the only velocities in the x direction matter,
therefore, 1 and 2 can both be rewritten as 1 = 21 m1 vx 21 and 2 = 21 m2 vx 22 , respectively. This allows the
expression in (1.2.1) to be rewritten as

PT =

 



2
1
1
n1
m1 vx 21 + n2
m2 vx 22
3
2
2

Furthermore, this choice of surface orientation implies that there is only one degree of freedom of consequence in
this system, therefore the re-expression of (1.2.1) above can be simplified to
PT = n1 m1 vx 21 + n2 m2 vx 22

(1.2.2)

Additionally, the gas is the same on both sides of the surface, thus m1 = m2 = m. Now, the distribution of
velocities is Maxwellian on both sides so the distribution function for the velocities, f (vx , vy , vz ), can be given as

f (vx , vy , vz ) =

m
2kB T

 32
e

2
2km T (vx
+vy2 +vz2 )
B

Combining the equivalence of masses with the equivalence of the velocity distributions allows it to be said that
vx 21 = vx 22 = vx 2 . Using this fact, and the Maxwellian distribution of the velocities, the expression for vx 2 can be
rewritten as

ZZZ

vx =

d vf
R3

(vx , vy , vz ) vx2


=

m
2kB T

 32 Z

vx2 dvx

dvy

dvz e

2
2km T (vx
+vy2 +vz2 )
B

(1.2.3)

First, it should be noted that the interation in (1.2.3) is over all the possible particle velocities, not over the
velocity parameter itself. Had the integration been over the velocity parameter itself, the integral over the
distribution of possible velocities would be meaningless and would lead to a dimensionally inconsistent result when
applied to (1.2.2) or any of its successive forms. Second, it should be noted that, technically, this should be a
discrete sum, as consideration of the number of particles or any dependent quantity (like the set of all possible
particle velocities) is necessarily discrete. This would imply that the expression in (1.2.3)
The integral in (1.2.3) is over all velocities in the x-direction because both positive and negative velocities will
effect the pressure experienced across the surface. The integrals over vy and vz are overall velocities for the same
1 The phrase, number density, is equivalent to the statement, average number of molecules per unit volume. (See Problem 1 from
Chapter 1)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

reason; however, their inclusion does not change the result when the integral is evaluated because they have no
weighting factor in the integral. It will be shown that the results be unchanged for vx 2 given as

vx 2 =

dvx f (vx ) vx2 =

 21 Z

m
2kB T

dvx vx2 e

2
2km T vx

(1.2.4)

where the exponent of the 2kmB T goes from 3 to 1 in order to reflect the fact that the integral here has only one
degree of freedom (compared to the three degrees of freedom in other expression for vx 2 ). To continue,
m1 = m2 = m and vx 21 = vx 22 = vx 2 are applied to the expression in (1.2.2) to yield
PT = n1 m1 vx 21 + n2 m2 vx 22
= n1 mvx 2 + n2 mvx 2
= mvx 2 (n1 + n2 )
Noting that n1 + n2 = n, where n is the total number density in the system, allows this above re-expression of
(1.2.2) above to be rewritten as
PT = mvx 2 (n1 + n2 ) = mnvx 2
Finally, the expressions for vx 2 from (1.2.3) and (1.2.4) are applied to this expression to give


PT = mnvx = mn

m
2kB T

 32 Z

vx2

dvx

dvy

dvz e

2
+vy2 +vz2 )
2km T (vx
B

(1.2.5)

and

PT = mnvx = mn

dvx f (vx )

vx2


=

m
2kB T

 12 Z

dvx vx2 e

2
2km T vx
B

(1.2.6)

Using Mathematica to evaluate the integrals in (1.2.5) and (1.2.6) gives the final result as

PT = nkB T

(1.2.7)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-3): A rarefied gas is contained in a vessel of volume V at pressure p. Supposing that the
distribution of molecules of the gas is Maxwellian, calculate the rate at which the gas flows out of
the vessel into a vacuum through a small hole (of area A). Taking the wall of the hole as the y-z
plane, find the velocity distribution in the x-direction of the gas molecules moving out of the hole.
Solution 1-3): The number of particles leaving the vessel at any point, N , in time depends on the area of the hole
in the vessel, A, the positional distribution of the particles (over unit volume), n (~x) at that point in time, and the
position of each of the particles, ~x, at that point in time. Thus, we sum over all of the possible positions of the
particles to obtain the expression for N as
N=

n (~x) A ~x

(1.3.1)

where the sum here is over all positions, (x, y, z), contained within the vessel. Now, the interest is in the rate at
which particles are leaving the vessel, so an expression for dN/dt is required. This is accomplished by converting
the positional distribution, n (~x), in (1.3.1) to a velocity distribution, n (~v ), and the position, ~x, to a velocity, ~v , to
give
X
dN
=
n (~v ) A ~v
dt

(1.3.2)

where the sum is over all possible positive velocities, (vx , vy , vz ); the reason for omitting the negative velocities will
be discussed later. To go from (1.3.1) to (1.3.2), the expression inside the sum in (1.3.1) is differentiated with
respect to t to give


d
d n (~x)
d~x
[n (~x) A ~x] = A ~x
+ n (~x)
dt
dt
dt
Noting that n (~x) represents the positional distribution and is therefore time-independent, it is clear that
d
Thus, the expression for dt
[n (~x) A ~x] becomes

dn(~
x)
dt

= 0.

d
d~x
[n (~x) A ~x] = An (~x)
= A n (~x) ~v
dt
dt
x)
dn(~
v)
Since dn(~
dt = 0 and
dt = 0 (for the same reason stated above) and since the positional distribution at anytime
can be made dependent on the velocities of the particles, it can be said that n (~x) = n (~v ). Thus


i X d
dN
d hX
=
n (~x) A ~x =
[n (~x) A ~x]
dt
dt
dt


X
X
d n (~x)
d~x
=A
~x
+ n (~x)
=A
n (~x) ~v
dt
dt
=A

n (~v ) ~v

(1.3.3)

The importance of n (~x) = n (~v ) can now be seen, as soon as the time derivative moved inside the sum, the index of
summation changes from all possible positions in the container to all possible positive velocities. Thus, the sum in
(1.3.3) is over all possible velocities, as in (1.3.2). To proceed from here, it is assumed that the number of particles
is large enough that the discrete sum in (1.3.3) can be converted into a continuous integral to give
X
dN
dN
=
n (~v ) A ~v
=
dt
dt
4

Z
d~v n (~v ) A ~v

(1.3.4)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Taking the plane to lie in the y-z plane and the velocity distribution to be Maxwellian, the integral in (1.3.4)
becomes

dN
=
dt

Z
d~v n (~v ) A ~v =

m
2kB T

 23 Z

vx dvx

dvy

dvz e

2
+vy2 +vz2 )
2km T (vx
B

(1.3.5)

or equivalently, by omitting the integrals for vy and vz as discussed in Problem 1-2,

dN
=
dt

Z
d~v n (~v ) A ~v =

m
2kB T

 12 Z

dvx vx e

2
2km T vx
B

(1.3.6)

Here, the integrals for the velocity are from 0 because the presence of the vacuum outside the vessel ensures
that the velocities of all of the particles passing through the hole will be positive. That is to say that the flux of
particles through the hole will be directed entirely outward, as no particles will be entering the vessel from the
vacuum. Finally, the integrals in (1.3.5) and (1.3.6) are evaluated using Mathematica to yield
dN
= An
dt

kB T
2m

(1.3.7)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-4): There is a furnace containing a gas at a high temperature. Through a small window
of the furnace, one observes, using a spectrometer, a spectral line of the gas molecules. The width
of one observed spectral line is broadened (this is called Dopler broadening). Show that the relation
between the spectral line intenstity, I, and the wavelength, , is given by the following formula:
"

mc2 ( 0 )
I () exp
220 kB T

Here, T is the temperature of the furnace, c is the speed of light, m is the mass of a molecule, and 0
is the wavelength of the spectral line when the molecule is at rest
Solution 1-4): The doppler redshift parameter for light can be expressed as

d=

0
0

Multiplying both sides of this expression by c yields

cd = c

0
0

Since d is a ratio such that d [0, 1), the expression c d is defined to be c d = v, where v is some positive velocity
which is a fraction of c. Specifically, this velocity v is the velocity with which the particles in the furnace are
moving. Therefore, the velocity v can be given as

v = cd = c

0
0

(1.4.1)

Now, the intensity of the light is proportional to the number of light emitting particles, n, and the amount of light
each particle emits, which is in turn proportional to the velocity of each particle. For a system of many particles
like this one, the dependence of the intensity of the light on the velocity of each particle becomes a dependence on
the distribution of the velocities of all of the particles in the distribution, f (v). Again, the assumptions is made
that the number of particles is sufficient to allow for treatment as a continuous distribution. Thus
I (v) n f (v)

(1.4.2)

where v is the velocity in the direction of the observer. Due to the hight temperature environment, the particles are
assumed to have a Maxwellian distribution, thus the expression in (1.4.2) becomes

I (v)

mn2
2kT

1/2

e 2kT v

(1.4.3)

Applying the expression and the expression in (1.4.1) to this expression gives

I ()

mn2
2kT

1/2
e

To obtain the final answer, it is noted that

m
2kT
c 0
0

(1.4.4)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

m
2kT
c 0
0

=e

mc2 (0 )2
2kT 2
0

and that, as far as functional proportionality goes, multiplicative constants are inconsequential, the expression in
(1.4.4) becomes

I ()

mn2
2kT

1/2
e

m
2kT
c 0
0

mc2 (0 )2
2kT 2
0

(1.4.5)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-5): A mass point with mass m moves within the range 0 x l and is reflected by walls
at x = 0 and x = l.
(i) Illustrate the trajectory of this mass point in the phase space (x, p)
(ii) Find the volume of the phase space, 0 (E), with energy smaller than E
(iii) Show that 0 (E) is kept constant when the wall at x = l is moved slowly (adiabatic invariance).
(iv) Going over to quantum mechanics, find the number, 0 (E), of quantum states with energy
below E and compare it to 0 (E).
Solution 1-5): The trajectory of the mass point in the phase space (x, p) can be illustrated as

Figure 1.5-1 : Phase space (x, p)

The system has one degree of freedom; therefore, 0 (E) is just an area in the 2-dimensional phase space
representing the motion of the mass. Therefore, 0 (E) (or the area enclosed in Figure 1.5-1 ) can be expressed as
0 (E) = l (p (p)) = l (2p) = 2lp

(1.5.1)

The motion of the mass implies that its Hamiltonian is equivalent to the Hamiltonian of a free particle, therefore

H=
Solving this for p gives p =

p2
=E
2m

2mE. Applying this solution to the expression in (1.5.1) gives

0 (E) = 2lp = 2l 2mE

(1.5.2)

To show that 0 (E) = 0 when the wall at x = l is moved slowly, it is noted that the decrease in the momentum of
the mass, p, during the collision with the moving wall can be expressed using the fraction of change in length of
the masss allowed coordinate space to the original length of the masss allowed coordinate space. This can be
expressed at

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

p = p

l
l

(1.5.3)

Noting that the expression from (1.5.2) implies 0 (E) = (2lp) = 2pl + 2lp, the expression in (1.5.3) is applied
to yield

0 (E) = (2lp) = 2pl + 2lp



l
= 2pl + 2l p
l
= 2pl 2pl = 0
In the quantum case, this is just the infinite square well. Thus the energy for this initial system (before the wall
starts to move) can be given as

En =

n 2 2 ~2
2ml2

Solving this for n gives

r
n=

2En ml2
a 2En m
=
2 ~2
~

(1.5.4)

The expression in Eqn (1.20a) in Kubo gives

0 (E) =

1=

0<En E

1 = n0

0<nn0

where n0 is the quantum

number representing the energy state, E. Applying the solution for n, as it pertains to
the energy level E (E = l 2mE/~), to (1.5.4) to this expression gives
"
#
l 2mE
0 (E) = n0 =
~
where the brackets, [ ], in (1.5.5) denote that the expression in fact represents the integer just below the
numerical value represented inside the brackets.

(1.5.5)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-6): Find the number of quantum states for a particle contained in a cubic box with edge
length l, and compare it with the volume in classical phase space. Obtain also the the density of the
states.
Solution 1-6): This can be interpreted as a three dimensional infinite square well; therefore, the energy levels of
the system can be expressed as

Enx ,ny ,nz =

~2 2 2
nx + n2y + n2z
2
2ml

(1.6.1)

From Eqn (1.20a) in Kubo, 0 (E) can be expressed as

X

0 (E) =

0<Enx ,ny ,nz E

Applying the expression in (1.6.1) to this expression yields

X

0 (E) =

2 2

0< ~
(n2x +n2y +n2z )E
2ml2

(1.6.2)

2E
0<n2x +n2y +n2z 2ml
~2 2

If the integer three space (Z3 ) with coordinates (nx , ny , nz ) is used to represent the possible quantum states of the
system, then the expression in (1.6.2) implies that the number of quantum states
qwith energy less than or equal to
2

E
E is the number of coordinates (nx , ny , nz ) contained within a sphere of radius 2ml
~2 2 . Since the energy is
dependent on the squares of the coordinates there is a two fold degeneracy for each coordinate. This implies that
the system has an eight fold degeneracy since 23 = 8; therefore, only one eighth of the q
volume of the sphere must

be considered. Using the expression for the radius of the sphere developed earlier, r =
for the volume of one eighth of a sphere gives


 

1 4 3
r
=
0 (E) =
8 3
6

2ml2 E
~2 2

!3

=
6

2ml2 E
~2 2 ,

in the expression

!3 


l 2mE
l3
3/2
=
(2mE)
~
6 2 ~3

(1.6.3)

as the number of possible, unique quantum states. Again, the brackets, [ ], in the expressions denote that the
expressions in fact represent the integer just below the numerical value represented inside the brackets. Now, it is
noted that l3 is simply the volume of the cube in which the particle is contained gives l3 = V . This allows the
expression in (1.6.3) to be rewritten as

0 (E) =

 

l3
V
3/2
3/2
(2mE)
=
(2mE)
6 2 ~3
6 2 ~3

(1.6.4)

which is the expression for the number of possible quantum states sought. To find the volume in classical phase
space, it is first noted that the classical phase space for this system is a six dimensional real space, R6 , with
coordinates (qx , qy , qz , px , py , pz ). Therefore, to find the volume contained within this phase space, the integral
ZZ
0 (E) =

ZZZ
d~
p d~q =

ZZZ
dpx dpy dpz

10

dqx dqy dqz

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

must be evaluated. To evaluate this integral definitely, proper bounds must be applied. Since the particle must be
located within the box, qx , qy , and qz can all be integrated from 0 l. This allows the integral for 0 (E) to be
rewritten as
ZZZ

0 (E) =

dpx dpy dpz

dqx
dqy
dqz
0
0
ZZZ
Z 0Z Z
= l3
dpx dpy dpz = V
dpx dpy dpz

(1.6.5)

by again noting that l3 = V . To find bounds for the integration of px , py , and pz , it is noted that the Hamiltonian
for the motion of the particle inside the cube can be written as

H=

p2y
p2
p2
p~2
= x +
+ z = E0
2m
2m 2m 2m

where E0 is some energy that satisfies the inequality 0 E0 E. This expression for the particles Hamiltonian
implies that
p2x + p2y + p2z = p~ p~ = 2mE0
Applying the inequality 0 E0 E to this expression implies
0 p2x + p2y + p2z 2mE
This implies that the volume of interest in momentum space (which q
is a three dimensional subspace of the six

dimensional phase space for the system) is a volume of radius pr0 = p2x + p2y + p2z = 2mE. Therefore, the
integral in (1.6.5) is converted into the spherical coordinate representation of momentum, (pr , p , p ), to give
ZZZ
0 (E) = V

ZZZ
dpx dpy dpz = V

p2r sin p dpr dp dp

(1.6.6)

This conversion to the spherical

momentum coordinates allows the bounds of integration for pr , p , and p to be

respectively given as 0 2mE, 0 and 0 2. Applying these integration bounds to the integral in (1.6.6)
gives

ZZZ
0 (E) = V

p2r

2mE

p2r

sin p dpr dp dp = V

Z
dpr

Z
sin p dp

dp
0

Evaluating this result with Mathematica gives

Z
0 (E) = V
0

2mE

p2r

Z
dpr

Z
sin p dp

dp =
0

4
3/2
V (2mE)
3

(1.6.7)

To compare the number of states in the quantum case to the number of states in the classical case, it is noted that,
for large E, 0 (E) 0 (E) /h3 , where h3 is used instead of h because the system has three degrees of freedom
instead of just one. Applying the expressions from (1.6.7) and (1.6.4) to 0 (E) 0 (E) /h3 gives

11

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

0 (E)
0 (E)
h3 



V
1
4
3/2
3/2
(2mE)
3 3 3
V (2mE)
6 2 ~3
2 ~
3


V
V
3/2
3/2
(2mE)

(2mE)
6 2 ~3
6 2 ~3
which implies, as expected, that the number of states for the quantum and classical systems is equivalent in the
large E limit. Finally, to obtain the density of states for the quantum case, the expression for 0 (E) in (1.6.4) is
differentiated with respect to E, using Mathematica , to give
r


d0 (E)
V
m2 E
d
V
3/2
(E) =
(2mE)
= 2 3
=
2
3
dE
dE 6 ~
~
2
as the expression for the density of states, (E).

12

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-7): What does a surface of constant energy look like in the phase space of an oscillator of
frequency ? Find the volume (E) in the phase space with energy below E. Then find the number
of quantum states, 0 (E) with energy below E for this oscillator, and show that when E is large we
have

0 (E)

0 (E)
h

Solution 1-7): First, an expression for the Hamiltonian of the oscillators motion in phase space is required.
Assuming a one dimensional oscillator, the Hamiltonian can be written as

H=

p2
1
+ m 2 q 2
2m 2

Noting that H = E and that = 2, this expression for the Hamiltonian of the system can be rewritten as
2

1=

m (2) 2
p2
+
q
2mE
2E

(1.7.1)

Noting that the equation for an ellipse in the pq-plane can be given, in general, as
p2
q2
+
=1
a2
b2
Comparing this with the expression in (1.7.1) gives a and b as

a=

2mE

and
1
b=
2

2E
m

These expressions for a and b allow the surface of constant energy in the oscillators phase space to be represented as

Figure 1.7-1 : Phase space (p, q) for an oscillator of frequency

13

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

The area of an ellipse, A, can be given as A = ab. Applying the expressions for a and b given above to this
expression for the area gives

1
2

A = a b = 2mE

2E
m

!
=

4E
E
=
2

which is also the expression for 0 (E) is the phase space with an energy less than E. Thus

0 (E) = A =

(1.7.2)

In the quantum case, the energy of the oscillator can be given as



1
En = ~ n +
2

~
= 2
2

1
n+
2

1
= h n +
2

Solving this for n0 , in terms of E, using Mathematica gives

E
1

h
2

n0 =

(1.7.3)

where n0 is the quantum number which corresponds to the energy E. Applying this expression for n0 to the
expression from Eqn (1.20a) in Kubo gives

0 (E) =

1=

0<En E

X
0<nn0

1
E

1 = [n0 ] =
h
2

For large E, this for 0 (E) expression becomes


0 (E) =
Finally, to show 0 (E)
(1.7.4) to give

0 (E)
h ,

E
h


(1.7.4)

the expression in (1.7.2) is divided by h and compared with the expression in

0 (E)
1
=
h
h

as expected.

14

E
= 0 (E)
h

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-8):
(i) When a system of N oscillators (N  1) with total energy E is in thermal equilibrium, find the
probability that a given oscillator among them is in a quantum state n.
(ii) When an ideal gas of N monoatomic molecules with total energy E is in thermal equilibrium,
show that the probability of a given particle having an energy = p2 /2m is proportional to
e/kB T
Solution 1-8): The expression, at the quantum level, for the energy levels of any given oscillator (the ith
oscillator) can be given as


1
Eni = ~ ni +
2
Defining the total number of possible quantum states the system can take as M implies that
n1 + n2 + + nN = M

(1.8.1)

The total energy of the system of oscillators can be expressed as the sum of the energies of each of the N oscillators

ET =

N
X


Eni = En1 + En2 + EnN = ~

n1 +

i=1

1
2





1
1
+ n2 +
+ + nN +
2
2

Since there are N energy terms in the above expression, there are N of the 1/2 terms in that expression as well;
therefore, the expression for the total energy of the system can be rewritten as

ET = ~

1
n1 +
2







1
1
1
+ n2 +
+ + nN +
= ~ n1 + n2 + + nN + N
2
2
2

Now, applying the expression for the total number of possible quantum states from (1.8.1) to this expression for the
total energy gives


1
ET = ~ n1 + n2 + + nN + N
2

1
= ~ M + N
2

There are M possible states that the system can take and there are N 1 ways to order the N oscillators;
therefore, there are (M + N 1)! total number of ways the system can be arranged. To find the number of
permutations, or the thermodynamic weight, of the system of N oscillators, the (M + N 1)! total number of ways
the system can be arranged is divided by the M ! number of ways the possible states that the system can be
arranged and the (N 1)! number of ways the N oscillators can be arranged to give

WM =

(M + N 1)!
M ! (N 1)!

(1.8.2)

The probability that a given oscillator in the system is in a quantum state n can be found by dividing the number
of permutations, or the thermodynamic weight WM n , for the rest of the system while one of the oscillators is in
the quantum state n by the total number of permutations, or the thermodynamic weight, of the system. The
energy, , of the oscillator in the state n is given by

15

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions



1
= ~ n +
2
This allows the energy of the rest of the system, E 0 , to be expressed as




1
~ n +
2
~
(N 1)
= ~ (M n) +
2

1
E = ET = ~ M + N
2
0

(1.8.3)

Using the same arguments that were used in constructing WM , the expression for E 0 in (1.8.3) can be used to
express WM n as

WM =

(M n + N 1 1)!
(M n + N 2)!
=
(M n)! (N 1 1)!
(M n)! (N 2)!

(1.8.4)

The probability of one of the oscillators being in the quantum state n can therefore be given by

P r (n) =

WM n
WM

Applying the expressions from (1.8.2) and (1.8.4) to this gives



WM n
(M + N n 2)!
M ! (N 1)!
P r (n) =
=
WM
(M n)! (N 2)! (M + N 1)!
M (M 1) (M 2) (M n + 1)
=
(N 1)
(M + N 1) (M + N 2) (M + N n 1)

(1.8.5)

Assuming that the system is sufficiently large, it can be said that M  n. Using this with the fact that N  1
allows the expression in (1.8.5) to be recast, approximately, as

P r (n)

Mn

N
n+1 N = M + N
(M + N )

M
M +N

n
(1.8.6)

To find the probability that a given particle, in an ideal gas of N monoatomic particles with total energy E, has
the energy = p2 /2m an expression for the number of states for the entire system, 0 (E, N ), and an expression for
the number of states of the rest of the system (the remaining N 1 particles), when one of the particles has energy
, 0 (E , N 1), must be found. Since this is an ideal gas, the Hamiltonian of the entire system, and thus its
energy can be expressed as

E=

N
X

j=1

p2xj
2m

p2yj
2m

p2zj

2m

3N
X
p2i
2m
i=1

(1.8.7)

To find the expression for 0 (E, N ), the expression from Eqn (1.17b) in Kubo can be used. Thus, the integral
0 (E)
1
0 (E, N ) = 3N
= 3N
h N!
h N!

Z
d =

1
h3N N !
16

Z
d~q1 d~qN

d~
p1 d~
pN
P

(1.8.8)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

must be evaluated. In (1.8.8), d~qi = dqxi dqyi dqzi and d~

pi = dpxi dpyi dpzi , while V R3 and P R3 represent the
three-spaces of the allowed positions and momenta, respectively. To find integration bounds for the q integrals it is
assumed that the gas is contained in a container of volume V , therefore
Z

ZZZ

dqxi dqyi dqzi = V

d~qi =
V

d~q1 d~qN = V N

Applying this result to the integral in (1.8.8) gives

0 (E, N ) =

1
h3N N !

Z
d~q1 d~qN

VN
= 3N
h N!

d~
p1 d~
pN
P

d~
p1 d~
pN

(1.8.9)

To find integration bounds for the p integrals, the expression in (1.8.7) is considered.
It implies that all of the

possible states of the system lie within a 3N -dimensional hypersphere of radius 2mE, since
3N
3N
X
X
p2i

p2i = p21 + p22 + + p23N = 2mE

E=
2m
i=1
i=1

Thus, the p integral in (1.8.9) evaluates to the volume 3N -dimensional hypersphere of radius
volume, V, of an arbitrary, s-dimensional hypersphere can be given as

V = Cs r s =

2mE. Now the

s/2

rs
2s + 1

The hypersphere here has a radius of r = 2mE and 3N dimensions, thus this general expression for the volume of
a hypersphere allows the p integrals in (1.8.9) to be evaluated to give
Z

d~
p1 d~
pN =

3N
2

3N
2

+1

2mE

3N

3N
2

3N
2

+1

(2mE)

3N
2

Therefore, the expression for 0 (E, N ) in (1.8.9) becomes

VN
0 (E, N ) = 3N
h N!

d~
p1 d~
pN
P

VN
= 3N
h N!

3N

(2mE) 2


3N
2 +1

!
(1.8.10)

Using similar arguments and the fact that = p2 /2m, the expression for 0 (E , N 1) can be given as
V N 1
0 (E , N 1) = 3(N 1)
h
(N 1)!

3 N 21

(2m (E ))


3N2+1

!
(1.8.11)

Now the probability that a given particle has the energy = p2 /2m is defined by

P r () =

W (E , N 1)
W (E, N )

(1.8.12)

Where W (E, N ) and W (E , N 1) are the thermodynamic weights of the system as a whole and the remainder
of the system when one of the particles has energy = p2 /2m, respectively. Noting that, in general,
W (E, N ) = 00 (E, N ) E, the expressions in (1.8.10) and (1.8.11) then imply
17

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

d0 (E, N )
d
W (E, N ) =
E =
dE
dE

"

d
=
dE

"

3N

!#

VN
h3N N !

(2mE) 2


3N
2 +1

VN
3N
h N!

(2m) 2 E 2


3N
2 +1

3N

E
3N

!#
E

!
!
3N
3N
(2m) 2 E 2 1 3N


E
2
3N
2 +1
!
!
3N
3N
(2m) 2 E 2
3N E


2
E
3N
2 +1

VN
h3N N !
VN
h3N N !

(1.8.13)

and
d0 (E , N 1)
E

dE

3(N 1)
N 1
2
d
V
))
(2m(E

 E
=
3(N 1)
dE h3(N 1) (N 1)!

+
1
2

3(N 1)
3(N 1)
2
2
d
V N 1
(2m)
(E

E


=
dE h3(N 1) (N 1)!
3(N21) + 1

3(N 3)
3(N 1)
N 1
2
2
(E

)
3(N

1)
V
(2m)



= 3(N 1)
3(N 1)
2
h
(N 1)!

+1
2

3(N 1)
3(N 1)
N 1
2
2
V
(E )
(2m) 
3(N 1) E

= 3(N 1)
3(N 1)
2
E
h
(N 1)!

+1

W (E , N 1) =

(1.8.14)

Now, the expressions form (1.8.13) and (1.8.14) are applied to the expression for the probability in (1.8.12) to yield

W (E , N 1)
P r () =
=
W (E, N )

V N 1
h3(N 1) (N 1)!

h3 N
=
V 2m




(2m)

3(N 1)
3(N 1)
2
2
(E)
3(N 1)

+1
2

VN
h3N N !

3N 1
3N

3N

)

3N

(2m) 2 E 2
( 3N
2 +1)

3N
2 +1
3(N 1)
+
2

3N
2

3(N 1)
2

E
E

E
E

(E )


3(N 1)
2

3N
2

1

 3N
h3 N
E 2
E

= (3N 1)
5N
E
3V 2m
(E ) 2
!
E
3N
h3 N
E

= (3N 1)
e 2 log( E )
5N
3V 2m (E ) 2

E
E

For a monoatomic ideal gas, E = 3N kB T /2, so the expression for P r () above becomes
h3 N

P r () = (3N 1)
3V 2m

18

E
(E )

5N
2

e kB T

log( E
E )

(1.8.15)

Jonathan McFadden
Spring 2010

Now, log

E
E

PHYS 7400
Kubo Solutions

can be expanded in terms of /E as


log

E
E


=

E
2E 2
2E 3
E
E

For large E and N , only the first term of this expansion matters, thus the log
(1.8.15) is replaced with /E to obtain
h3 N

P r () = (3N 1)
3V 2m
h3 N

= (3N 1)
3V 2m

(E )

as expected.

19

5N
2

(E )

k T
B

5N
2

in the exponent for e in

e kB T (

E
)

From the expression in (1.8.16), it is clear that

P r () e

k T
B

(1.8.16)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-9): A vessel of volume V contains N gas molecules. Let n be the number of molecules in a
part of the vessel of volume v. Considering that the probability of finding a certain molecule in v is
equal to v/V in the thermal equilibrium state of this system.
(i) Find the probability distribution f (n) of the number n.
2

) .
(ii) Calculate n
and (n n
(iii) Making use of Stirlings formula, show that when N and n are both large, f (n) is
approximately Gaussian.
(iv) Show that in the limit of v/V 0 and V , with N/V held constant, f (n) approaches the
Poisson distribution f (n) = en (
n) /n!
Solution 1-9): This is clearly a Binomial Probability Distribution, since the probability of finding a certain
molecule in v, pr, is given as p = v/V , while the probability of finding the certain molecule in the rest of the volume
can be expressed as q = 1 p = 1 v/V . Applying this to the Binomial Probability Distribution gives f (n) as
(k + n)! n k
N!
p q =
pn q N n
n!k!
n! (N n)!
N!
N n
pn (1 p)
=
n! (N n)!
 v n  V v N n
N!
=
n! (N n)! V
V
N!
N n
= N
v n (V v)
V n! (N n)!

f (n) =

(1.9.1)

(1.9.2)

where f (n) is the probability of finding n molecules in the volume v and k = N n molecules in the rest of the
volume, V v. To find expression for n
, it is simplest to proceed with the form of the binomial distribution given
in (1.9.1) and the apply the values for p and q once an expression for n
has been found in terms of them. For this
system p = v/V and q = 1 v/V . Therefore, to find n
, the expression

n
=

N
X

n f (n) =

n=1

N 
X

n=1

N!
pn q N n
n! (N n)!

must be evaluated. Noting that

(p + q)

N 
X
n=1

N!
pn q N n
n! (N n)!

both sides of this are differentiated with respect to p to give

"N 
#
i
h
X
N!
N
n N n
(p + q)
=
p q
p
p n=1 n! (N n)!

N 
X
N!
N 1
n1 N n
N (p + q)
=
np
q
n! (N n)!
n=1
Multiplying both sides of this expression by p gives

20

(1.9.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

N 1

p N (p + q)

N 1

pN (p + q)

N 
X

N!
=p
n pn1 q N n
n!
(N

n)!
n=1

N
X
N!
=
n pn q N n
n! (N n)!
n=1

!

(1.9.4)

The right side of the expression in (1.9.4) is that same as the right side of the expression in (1.9.3), thus

n
=

N
X

n f (n) =

n=1

N 
X

n=1

N!
pn q N n
n! (N n)!

N 1

= pN (p + q)

Noting that, by the definition of the Binomial Probability Distribution, p + q = 1, the expression for n
becomes
N 1

n
= pN (p + q)

= Np

Finally, the fact that p = v/V is applied to express n

as

n
= Np = N
2

v
V

(1.9.5)

To calculate (n n
) , it is noted that (n n
) can be alternatively expressed as
2

(n n
) = n2 n
2

(1.9.6)

The expression for n

2 can be found by squaring the result obtained in (1.9.5), so all that remains to do is find an
expression for n2 . As when calculating n
, the form of the binomial distribution given in (1.9.1) will be used with
the values p = v/V and q = 1 v/V substituted in the final step. Thus, the expression

n2

N
X

n f (n) =

n=1

N 
X
n=1

N!
pn q N n
n
n! (N n)!
2


(1.9.7)

must be evaluated. Now, the expression in (1.9.4) differentiated with respect to p to obtain
"N 
#
i
X
h

N
!
N 1
pN (p + q)
=
n pn q N n
p
p n=1 n! (N n)!

N 
X
N!
N 1
N 2
N (p + q)
+ pN (N 1) (p + q)
=
n2 pn1 q N n ,
n! (N n)!
n=1
which is then simplified by noting, by the definition of the Binomial Probability Distribution, that p + q = 1. Thus

N + pN (N 1) =

N 
X
n=1

N!
n2 pn1 q N n
n! (N n)!

Multiplying both sides of this expression by p yields

21

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

N 
X

N!
p (N + pN (N 1)) = p
n2 pn1 q N n
n!
(N

n)!
n=1

N
X
N!
pN + p2 N 2 p2 N =
n2 pn q N n
n! (N n)!
n=1

!

which can be applied to the expression for n2 in (1.9.7) since is clear that this result and the result in (1.9.7) have
equivalent right hand sides. Thus, the expression in (1.9.7) becomes

n2

N 
X
n=1

N!
pn q N n
n
n! (N n)!
2

= pN + p2 N 2 p2 N

Applying p = v/V to this expression allows n2 to be expressed as

n2 = pN + p2 N 2 p2 N = N

v
v2
v2
+ N2 2 N 2
V
V
V
2

) in (1.9.6) to obtain
which, along with the result from (1.9.5), can be applied to the expression for (n n

(n n
) = n2 n
2 =


 
v
v2
v2
v 
v
v 2
N + N2 2 N 2 N
=N
1
V
V
V
V
V
V

(1.9.8)

Stirlings formula is given, in general, as ln p! p ln p p, for p R 3 p 0. This is applied to the expression for
f (n) in (1.9.2) by first taking the natural log of both sides to obtain

N!
N n
n
v
(V

v)
V N n! (N n)!
h
i


N n
= ln [N !] + ln [v n ] + ln (V v)
ln V N ln [n!] ln [(N n)!]


ln [f (n)] = ln

= ln [N !] ln [n!] ln [(N n)!] + (N n) ln [V v] N ln [V ] + n ln [v]

(1.9.9)

Applying Sterlings formula to the ln [N !], ln [n!], and ln [(N n)!] terms in (1.9.9) gives
ln [N !] N ln N N
ln [n!] n ln n n
ln [(N n)!] (N n) ln [N n] + n N
Thus, the expression in (1.9.9) becomes
ln [f (n)] (N ln N N ) (n ln n n) ((N n) ln [N n] + n N )
Using Mathematica to simplify this expression gives

f (n) = n ln

hvi
n


+ (n N ) ln

22


 
nN
N
+ N ln
vV
V

(1.9.10)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Since N is large, Mathematica is used to expand this expression about n = N v/V gives

ln [f (n)]

V2
2N v (v V )


2
Nv
n
V

(1.9.11)

Noting that the expression for a Gaussian distribution, g (n) is proportional to

g (n) e

(n)
2 2

(1.9.12)

For this system, and are given as

=n
=N

v
V

and
2

) = n2 n
2 = N
= (n n

v 
v
1
V
V

so the expression in (1.9.12) becomes

(N vnV )2

g (n) e 2N v(vV )

Since this is to be compared to the expression for ln [f (n)], the natural log of g (n) must be taken. Thus
2

ln [g (n)]

(N v nV )
2N v (v V )

(1.9.13)

Using Mathematica , the expression in (1.9.13) is compared with the expression in (1.9.12) to yield
2

(N v nV )

2N v (v V )

V2
2N v (v V )


2
Nv
n
=0
V

which implies that, for large N , the distribution given by f (n) becomes Gaussian.
To show that f (n) becomes a Poisson distribution as v/V 0 and V , while N/V remains constant, the
expression for f (n) in (1.9.1) is examined, noting that p = v/V and q = 1 p = 1 v/V . Thus

f (n) =

 v n 
N!
N!
v N n
pn q N n =
1
n! (N n)!
n! (N n)! V
V

Applying n
= N v/V v = n
V /N to this expression for f (n) using Mathematica yields
N n

f (n) =

N N (N n
)
n
n N !
n! (N n)!

Before proceeding, this new expression for f (n) is rewritten in the more useful and suggestive form
N n

f (n) = (N n
)

23

N N N !
(N n)!

n
n
n!


(1.9.14)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Clearly, the expression in (1.9.14) is close to what would be expected for a Poisson Distribution, in that the n
n and
1/n! terms are already present, since a Poisson Distribution, h (n) can be given as

h (n) = en

n
n
n!


(1.9.15)

Therefore, all that remains to do is show that the terms not in parentheses in (1.9.14) are, at least, proportional to
en . That is to say, it remains to be shown that
N n

N N (N n
)
(N n)!

en
N n

To accomplish this, (N n
)

(N n
)

N n

N!

is expanded, using the Binomial Theorem, to yield

N
n 
X

N N ni ()

i=1
N n

Now, this to binomial expansion for (N n

)

(N n)!
i! (N n i)!


= (N n)!

N
n
X
i=1

N N ni ()
i! (N n i)!

is multiplied by the expression

N N N !
(N n)!

to obtain the result

N n

(N n
)

N N N !
N N N !
=

(N n)!
(N n)!

N
n
X

N N ni ()
(N n)!
i! (N n i)!
i=1
(
)
N
n
i
X
N N ni ()
N
= N N!
i! (N n i)!
i=1
(
)

N
n
i
X
N N N ! N N ni ()
=
(N n i)!
i!
i=1
(
)

N
n 
i
X
N ! N ni
()
=
(N n i)!
i!
i=1

)!

Now, the approximation

N ! N ni
1
(N n i)!
can be made for large N ; however, since N/V is constant as V , it is guaranteed that N will be sufficiently
large. Thus, the expression in (1.9.16) becomes

(N n
)

N n

(
) N n

N n1



N
n 
i
X
X i
X i
N N N !
N ! N ni
()
=

(N n)!
(N n i)!
i!
i!
i!
i=1
i=1
i=0

Noting that the Taylor series expansion for e can be given as

24

(1.9.16)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

e =

K
X
X
i
i

i!
i!
j=0
j=0

for a sufficiently large K R+ , the expression in (1.9.16) clearly implies

N n

(N n
)

N N N !
= e
(N n)!

Applying this expression to the expression for f (n) in (1.9.14) yields

f (n) = (N n
)

N n

N N N !
(N n)!

n
n
n!


=e

n
n
n!


(1.9.17)

Thus, for v/V 0 and V , while N/V remains constant, f (n) does indeed become a Poisson distribution.

25

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-10): As illustrated in Figure P1.10, a string with a lead ball of mass m is slowly pulled
upward through a small hole. Consider the work done on the system during this process and find
the change in the energy and frequency of this pendulum during this adiabatic process, assuming
the amplitude of the pendulum to be small.

Figure P1.10
Solution 1-10): First, expressions for the energy of the system and the tension in the pendulum string are
required. To create the desired expression for the energy of the system and the tension in the pendulum string, the
variables , l, Tp , and T~ are defined, respectively, to be the angle the pendulum makes with the y-axis, the length
of the pendulum, the tension in the pendulum string, and the force pulling the pendulum up. These quantities are
illustrated below in Figure 1.10-1

Figure 1.10-1
Using the variables illustrated above, the energy of the system can be expressed as

26

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

E = Ep mgl
1
= ml2 2 mgl + mg (l l cos )
2
1
= ml2 2 mgl + mgl (1 cos )
2

(1.10.1)

where Ep = E + mgl is the energy associated with the motion of the pendulum and as such, dependent on .
Furthermore, the tension in the pendulum string can be given using the expression
T = ml2 + mg cos

(1.10.2)

To simplify the expression for the energy of the system in (1.10.1), the trig identity cos ( ) cos ( + ) =
= 2 sin sin is employed by setting = = /2 to obtain

1 cos = cos 0 cos = cos

   
 
 
   

+ cos

= 2 sin
sin
2
2
2
2
2
2

Thus, the expression for E in (1.10.1) becomes

E=


 
 

1
1 2 2
ml mgl + mg (1 cos ) = ml2 2 mgl + mgl 2 sin
sin
2
2
2
2

Since is said to be small, the small angle approximation for sine can be used. Thus, the expression for E can be
given, approximately, as
 

 
1 2 2

E = ml mgl + mgl 2 sin

sin
2
2
2
"   #
2
1 2 2

= ml mgl + mgl 2
2
2
=

1 2 2
1
ml mgl + mgl2
2
2

(1.10.3)

Similarly, to simplify the expression for the tension in the pendulum string in (1.10.2), the same trig identity used
above is used to obtain

cos = 1 + 2 sin

 
 

sin
2
2

Thus, the expression for T in (1.10.2) becomes


 
 

T = ml + mg 1 2 sin
sin
2
2
Again, the fact that is considered to be small is used. Thus, the small angle, approximation for sine, allows the
expression for T to be rewritten, approximately, as

27

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

 

 

T = ml + mg 1 2 sin
sin
2
2
"
 2 #

= ml2 + mg 1 2
2
1
= ml2 + mg mg2
2

(1.10.4)

Now, the expressions for the energy of the system and the tension in the pendulum string are time averaged over
the period of one oscillation. Since the pendulum is executing simple harmonic motion, the average kinetic and
potential energies resulting for the motion of the pendulum are equal, thus
KE = P E
1 2 2
1
ml = mgl2
2
2
l2 = g2
Applying this to the time average of the expression for T gives
1
T = ml2 + mg mg2
2
1
2

= ml + mg mg2
2
1
2
= mg + mg mg2
2
1
2
= mg + mg
2
Since the amount of work done on the system when the string is pulled up by l is given as T l, the average
amount of work done on the system, and thus the change in the energy of the system, can be expressed as
1
E = T l = mg l mg2 l
2

(1.10.5)

by using the result for T above. Thus, using the expression for E = T l in (1.10.5) and the fact that
Ep = E + mgl, the change in the energy of the pendulum is simply
1
1
E p = E + mg l = mg l mg2 l + mg l = mg2 l
2
2

(1.10.6)

Now, combining the expression for E given in (1.10.3) with Ep = E + mgl allows Ep to be expressed as
Ep = E + mgl =

1 2 2
1
1
1
ml mgl + mgl2 + mgl = ml2 2 + mgl2
2
2
2
2

This E p can be given as

1 2 2
ml +
2
1
= ml2 2 +
2

Ep =

1
mgl2
2
1
mgl2 = mgl2
2

28

(1.10.7)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Comparing the expressions in (1.10.6) and (1.10.7) gives

1 mg2 l
l
E p
l
=
E p = E p
= 2
2
2l
2l
Ep
mgl

(1.10.8)

Since the energy of a harmonic oscillator is proportional to is frequency, , the expression in (1.10.8) implies that
the change is the frequency of oscillation can be expressed as

l
|l|
=

2l
2l

since l 0, as l is decreasing.

29

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-11): Prove, on the base of the principle of entropy increase, that when a coordinate x
varies extremely slowly through a quasi-static adiabatic process (1.35), the entropy, S (x), does not
change.
Solution 1-11): It is to be shown that dS
dt = 0, where S (x (t)) is a function of x (t), which is a function of t;
dS
therefore, using the chain rule, dt can be rewritten as
dS
dx dS
=
dt
dt dx
Now x, varies adiabatically, so

dx
dt

0. Applying this, to the expression in (1.11.1) implies that

dS
dx dS
dS
=
=0
=0
dt
dt dx
dx

QED.

30

(1.11.1)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-12): As in figure P12.1, a system under consideration is contained in a box made of
insulating walls and a moveable piston.

Figure P1.12
A weight w is placed on the piston. Regarding the total system, including the weight, as an isolated
system derive, from the micro-canonical ensemble, the relation

p=

E
V


S

Apply this formula to an ideal gas of monoatomic molecules and prove the equation of state p =

3E
2V .

Solution 1-12): To begin, the volume enclosed, V , is defined as V = xA where A is the area of the piston and x is
the potion of the piston above the bottom of the cylinder. Clearly, the pressure exerted by the piston is then given
w
w
by p = A
, so a differential expression for A
is required. Since the system will come to equilibrium when the number
of available states is the greatest, when entropy is the greatest, an expression for the entropy of the system is
required. From eqn (1.18) in Kubo, entropy can be given as
S (x) = kB ln [ (E, V )] = kB ln [ (x)]

(1.12.1)

since both E, the total energy of the gas, and V , the volume of the container and thus the gas, both depend on x.
Thus, the point at which the entropy is greatest can be found using
dS
=0
dx
Applying the expression for (1.12.1) to this and using the chain rule gives
dS
= kB
dx

E ln [ (E, V )] V kB ln [ (E, V )]
+
x
E
x
V


=0

(1.12.2)

An expression for V in terms of x already exists, so all that remains is to find an expression for E in terms of x;
however, the total energy of the system ET is the sum of energy of the gas and the potential energy of the weight.
Thus,
ET = E + wx E = ET wx
Applying this expression for E and V = Ax to the expression in (1.12.2) yields

31

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions




ln [ (E, V )]
ln [ (E, V )]
+A
E
V
E


 V
S
S
= w
+A
E V
V E

0 = w

which implies that

w
=
A

S
V

 
E

S
E

 1
(1.12.3)
V

since
E
(ET wx)
=
= w
x
x
(Ax)
V
=
=A
x
x
Using this expression, the chain rule, and p = w/A, the expression for the pressure in the container becomes
w
p=
=
A

S
V

 
E

S
E

 1


=

E
V


(1.12.4)
S

Finally, the entropy of an ideal gas can be given by

"
S = N kB

V
3 2E
m3/2 e3/2
ln
+ ln
+ ln
N
2 3N
~3

Applying the expression for S to the expression for p in (1.12.3), using Mathematica , and noting that p = w/A,
yields
w
p=
=
A

S
V

 
E

S
E

 1
V

kB N
=
V

3kB N
2E

1
=

2E
3V

Noting that for a monatomic ideal gas, E = 32 N kB T verifies this expression for the pressure, since

p=

2E
2
=
3V
3V

3
N kB T
2

32


=

kB T N
V

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-13): There is a one-dimensional chain consisting of n (n 1) elements, as seen in figure

P1.13. Let the length of each element be a and the distance between the end points x, as shown.

Figure P1.13
Find the entropy of this chain as function of x and obtain the relation between the temperature, T ,
of the chain and the force (tension) which is necessary to maintain the distance x, assuming the
joints to turn freely.
Solution 1-13): First, it is noted that the total distance, x, can be expressed in terms of the total number of
segments going to the right, n+ ; the total number of segments going to the left, n ; and the length of each
individual segment, a. Clearly, this can be accomplished using the relation
x = (n+ n ) a
Similarly, the total number of segments, n, can be expressed in terms of n+ and n by
n = n+ + n
Solving these expressions for n+ and n in terms of x, a and n gives n+ and n as
1
n+
2

1
n =
n
2
n+ =

x
a
x
a

(1.13.1)
(1.13.2)

Since the entropy of the chain is sought, the expression for eqn (1.18) in Kubo is useful as it expresses entropy in
terms of the number of system states,

S = kb ln [W (x)]
This is useful, since the number of states for this system is easily obtained using

W (x) =

n!
n+ !n !

Applying this to the expression for the entropy of the system in (1.13.3) yields

S = kb ln [W (x)] = kb ln


n!
= kB (ln n! ln n+ ! ln n !)
n+ !n !
33

(1.13.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Now, n, n+ and n are all considered to be large, thus Stirlings Approximation can be used to simplify the
expression for the entropy, yielding
S = kB [n ln n n (n+ ln n+ n+ ) (n ln n n )]
Noting that n = n+ + n , it is clear that this expression for the entropy further simplifies to
S = kB (n ln n n+ ln n+ n ln n )
Now, using the expressions for n+ and n in (1.13.1) and (1.13.2) are applied, using Mathematica , to yield

S = kB

an ln 4 + 2an ln [an] (x an) ln [an x] (x + an) ln [an + x]

2a


(1.13.4)

Now, the tension in the system, T~ , can be expressed using the Helmholtz Free Energy

T~ =

F
x


=
T

(U T S)
x


T

However, due to the fact that the joints of the system are free to rotate, the internal energy of the system, U , in
independent of x. Thus, the expression for T~ simplifies to

T~ =

F
x


=
T

(U T S)
x


=
T

(T S)
x


= T
T

S
x


T

Applying the expression for entropy given in (1.13.4) to this expression for T~ , and using Mathematica to simplify,
yields
 


S
kB T
2an
T~ = T
=
ln
1
x T
2a
an + x
kB T
kB T
2 x + 4 2 x3 +
a n
3a n

34

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-14): There is a system consisting of N oscillators of frequency . Discussing the system
classically,
(i) Find the number of states.
(ii) Using the results for the number of states, derive the relation between the energy and
temperature of the system
Solution 1-14): The Hamiltonian of this system of oscillators can be expressed as

H=


N  2
X
k
pi
+ qi2
2m 2
i=1

by assuming that all of the oscillators

phave identical mass and frequency of oscillation. If the angular frequency of
the oscillations is defined to be = k/m = 2, then this expression for the Hamiltonian can be simplified to

N  2
N
X

pi
k 2
1 X 2
H=
+ qi =
pi + 2 qi2
2m 2
2 i=1
i=1

(1.14.1)

Then, the number of possible system states, 0 (E) can be found by evaluating the volume integral


N Z Z
N Z Z

Y
Y
0 (E)
1
1
2
ff
dqi dpi = N
0 (E) =
= N
dq
dp
i
i
P
N
p
N
k 2

i
~
~ i=1
~ i=1
HE
E
i=1
2m + 2 qi
where E

PN n p2i
i=1

2m

(1.14.2)

o
+ k2 qi2 0, serves as the bounds of integration, since H = E. To simplify the Hamiltonian,

and thus obtain an simpler integral than the one in (1.14.2), H will be expressed in terms of the normal coordinate
~ R2N . Thus, the pi s and qi s in (1.14.1) are replaced according to

p i = i 2

N +i 2
qi =

Applying these expressions for the pi s and qi s to the expression for H in (1.14.1) yields the simplified Hamlitonian

N
N 
X
2

1 X 2
1
H=
pi + 2 qi2 =
i 2 + 2
2 i=1
2 i=1
N

!2
N +i 2

2N

X 2
X 2
1 X 2
2
2
2i + 2N
i + N
i
+i =
+i =
2 i=1
i=1
i=1

(1.14.3)

The desire is to apply this simplification of the Hamiltonian to normal coordinates, given in (1.14.3), to the integral
for 0 (E), given in (1.14.2); however, to accomplish this, the differential relations

dpi = di 2
dqi =

dN +i 2

35

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

are required. Applying these differential relations and the expression for the Hamiltonian in normal coordinates to
the integral for 0 (E) in (1.14.2) yields

N Z Z
1 Y
0 (E)
=
dq
dp
i
i
~N
~N i=1
HE
(Z Z
)
N
dN +i 2
1 Y
di 2
= N
~ i=1

HE
(
)
 N Y
Z
Z
N
2
=
di dN +i
P2N 2
~
i=1 i E
i=1
(Z Z
)
 N Y
2N
2
di
=
P2N 2
~
i=1 i E
i=1

0 (E) =

(1.14.4)

Thus, the integral here is over a 2N -dimensional sphere of radius E, as opposed to over an ellipsoid as in (1.14.2).
Using the expression for the volume of a sphere in an arbitrary number of dimensions, the integral in (1.14.4)
evaluates to

0 (E) =

2
~

(Z Z
N Y
2N

)
di
P2N

i=1

i=1

2
~

N

 2N
2N/2
E
[2N/2 + 1]

2
~

N

N
EN
[N + 1]

i2 E

Noting that [N + 1] = N ! allows this expression for 0 (E) to be simplified to its final form, yielding

0 (E) =

2
~

N

N
1
EN =
[N + 1]
N!

2E
~

N
(1.14.5)

or, by noting that = 2

0 (E)

1
N!

E
~

N
(1.14.5 a)

To find the relation between the energy and the temperature of the system, the expression
S
1
=
E
T

(1.14.6)

from eqn (1.28) in Kubo is noted. Thus, an expression for the entropy of the system is required; however, noting
eqn (1.18) in Kubo and the expression for 0 (E) given in (1.14.5), the entropy of the system can be given as
S = kB ln [0 (E, N )] = kB ln [0 (E)]
"

N #
1 2E
= kB ln
N ! ~




2E
= kB N ln
ln N !
~
36

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Applying this expression for S to the expression in (1.14.6) yields

 



1
S

2E
=
=
kB N ln
ln N !
T
E
E
~
 



2E
2 1
2kB N

ln
= kB N
=
= kB N
E
~
~ E
~E

(1.14.7)

Finally, this expression is solved for E in terms of T and = 2 is applied to the result in (1.14.7) to yield the
final results

E=

2kB N
kB N
T =
T
~
~

37

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-15): For an oscillator with mass m and angular frequency ,

(i) Calculate the partition function classically.
(ii) Calculate the partition function quantally (quantum mechanically).
(iii) Find the internal energy, entropy, and the heat capacity of a system consisting of N such
oscillators in terms of temperature.
Solution 1-15): The Hamiltonian of a single oscillator can be given as

H=

p2
k
+ q2
2m 2

(1.15.1)

p
where the angular frequency, , is defined = k/m. Using the expression given in eqn (1.71 a) in Kubo and the
expression for the Hamiltonian of a single oscillator given in (1.15.2) allows the classical partition function for the
single oscillator to be given as

Z0C =

1
~

1
~

eH/kB T dp dq =

1
~

p
2mk

BT

kq
2k

BT

dp dq =

p
2mk

BT

kq
+ 2k

BT

dp dq

Carrying out this integration using Mathematica and noting that =

Z0C =

p
k/m gives

2kB T
~

m
2kB T
=
k
~

(1.15.2)

For the quantum case, the energy of a single oscillator can be given as


1
En = ~ n +
2


(1.15.3)

Using the expression given in (1.71b) in Kubo and the expression for the nth energy state of the oscillator given in
(1.15.3), the quantum partition function for the single oscillator to be expressed as

Z0q =

eEn =

n=0

k~T (n+ 12 )
B

n=0

Using Mathematica to evaluate this sum gives

Z0Q =

k~T (n+ 12 )
B

n=0



1
~
= csch
2
2kB T

(1.15.4)

To find the internal energy of a system of N oscillators (of the kind described above), the expression from eqn (1.80
a) in Kubo is used

U =

ln ZQ

(1.15.5)

Since the N oscillators are identical the partition function of the system, ZQ can be given using the partition
function of one of the oscillators. Thus, using the expression in (1.15.4) and = 1/kB T , ZQ can be given as
38

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

N
ZQ = ZQ
=
0


N 

N
1
~
~
1
=
csch
csch
2
2kB T
2
2

(1.15.6)

This expression for ZQ allows the expression for U in (1.15.5) to become

U =
ln ZQ =
ln

"


N #
~
1
csch
2
2

which, using Mathematica , evaluates to




N ~
~
U =
ln ZQ =
coth

2
2

(1.15.7)

Now, the heat capacity of a system can be expressed using the relation

C=

U
T


(1.15.8)
N,

Before applying the expression for U given in (1.15.7) to this relation for C, the substitution = 1/kB T is made to
obtain




N ~
~
~
N ~
U=
coth
coth
=
2
2
2
2kB T

(1.15.7 a)

Applying this expression for U to the relation in (1.15.8), using Mathematica , yields

C=

U
T


=
N,





N 2 ~2
N ~
~
~
2
=
coth
csch
2
2kB T N,
4kB T 2
2kB T

(1.15.9)

Finally, to find the entropy, it is noted that

S=

U F
T

(1.15.10)

where F is the Helmholtz Free Energy. Using the expression in eqn (1.81) in Kubo, the Helmholtz Free Energy can
be expressed in terms of the partition function, ZQ , as
F = kB T ln ZQ
Applying the expression for ZQ from (1.15.6) allows F to be given as
"
F = kB T ln ZQ = kB T ln


N #
1
~
csch
2
2

Using this expression for F and the expression for U , given in (1.15.7 a), in the expression for S in (1.15.10) allows
S to be given as

39

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

U F
1
S=
=
T
T

"



N #!
N ~
~
1
~
coth
+ kB T ln
csch
2
2kB T
2
2

Using Mathematica to simplify this result, gives

S=






N ~
~
~
coth
kB ln 2N sinhN
2T
2kB T
2kB T

40

(1.15.11)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-16): Show that, the temperature is uniform, the pressure of a gas in a uniform
gravitational field decreases with height according to p (z) = p (0) emgz/kB T , where m is the mass of
a molecule.
Solution 1-16): The pressure at a given point z1 above z = 0 depends on the number of particles above that
point, n (z) and the weight, mg, of each of the particles above the height z0 . Thus,
p (z) = mg n (z)

(1.16.1)

Since the Hamiltonian for the ith particle of this gas can be given as

Hi =

p~2
+ mgz
2m

the number of particles above the point z0 can be given as

ZZZ

d3 p~

n (z) = N

d p~

dz P (z)

z0
Ly

dx

0
Lx

Ly

dy

=N

Z
dx

ZZZ

Lx

dy

dz

e (p

/2m+mgz )

(1.16.2)

z0

where Z is the partition function of the system. This partition function can be given as
ZZZ

d3 p~

Z=

Lx

ZZZ

Ly

Z
dx

dy

dz P (z)

Z Lx
Z Ly Z
2
d3 p~
dx
dy
dz e (p /2m+mgz)

0
0
0
s
s
3
3
A 8m
Lx Lz 8m
=
=
g
5
g
5

using Mathematica to evaluate the integrals. Applying this expression for Z to the expression for n (z) in (1.16.2)
gives
Ng
n (z) =
A

Ng
=
A

5
8m 3
5
8m 3

ZZZ

d3 p~

gmz1

Lx

A
g

Ly

dx
0

8m 3
5

dy

dz e (p

/2m+mgz )

z0

!
= N egmz1

Applying this to the expression in (1.16.1) gives p (z) as

p (z) = mg n (z) = mg N egmz1

(1.16.3)

To complete the proof, an expression for p (z) at z = 0, p (0), is required. Setting z = 0 in (1.16.3) gives p (0) as
p (0) = mgN , thus the expression for p (z) in (1.16.3) becomes
p (z) = mg N egmz1 = p (0) egmz1

41

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-17): Consider an ideal gas consisting of N particles obeying classical statistics. Suppose
that the energy of one particle, , is proportional to the magnitude of momentum, p, such that = cp
where c R. Find the thermodynamic functions of this gas without considering the internal
structure of the particles.
Solution 1-17): The desire is to calculate, in terms of V , N , and T , the Helmholtz Free Energy, F ; the pressure,
p; the internal energy, U ; the entropy, S; the enthalpy, H; the Gibbs Free Energy, G; the heat capacity at constant
volume, CV ; and the heat capacity at constant pressure, Cp ; therefore, an expression for the systems partition
function is required. Using the expression in eqn (1.71 a) in Kubo, with HN = = pc, allows the partition function
of the system, Z, to be given as
 ZZZ
N
ZZZ
1
1
EN /kB T
dqx dqy dqz
Z=
dpx dpy dpz e
N ! ~3
RRR
Noting that the q integrals evaluate to
dqx dqy dqz = V and that EN = = cp allows the expression for Z to

be rewritten as

Z=

 ZZZ
N
1 V
pc/kB T
dp
dp
dp
e
x
y
z
N ! ~3

Converting the remaining integral, in p, in the expression for Z to spherical coordinates, in p, yeilds

Z=

 Z 2 Z Z
N
1 V
pc/kB T 2
e
p
sin
p
dp
dp
dp

N ! ~3 0
0
0

Evaluating this integral using Mathematica gives the final expression for Z as
"

V
Z=
N!

kB T
c~

3 # N
(1.17.1)

Using this expression for Z in F = kB T ln Z gives


3 !N
V
k
T
B

F = kB T ln Z = kB T ln
N!
c~
"

3 #




kB T
V kB T
= kB T N ln [V ] + 3 ln
ln N !
= kB T N ln
N!
c~
c~
Since N is considered to be large, Stirlings formula applies; therefore, the expression for F becomes




kB T
ln N !
c~




kB T
= kB T N ln [V ] + 3 ln
N ln N N
c~

F = kB T N

ln [V ] + 3 ln

Now, it is noted that p and U can be expressed, using F , as

42

(1.17.2)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions


p=
U = T

F
V


T,N

F
T


V,N

Applying the expression for F in (1.17.3) to these expressions, using Mathematica , gives p and U as
kB N T
V
U = 3kB N T
p=

(1.17.3)
(1.17.4)

Now, the enthaply of the system, H, can be given as H = U + pV and the entropy of the system, S, can be given as
S = (U F )/T . Therefore, using the expressions for p and U from (1.17.3) and (1.17.3) and Mathematica , H can
be expressed as

H = U + pV = 4kB N T

(1.17.5)

and using the expressions for F and U from (1.17.2) and (1.17.4), S can be expressed as
U F
= kB N
S=
T

kB T
3 N N ln N + ln [V ] + 2 ln
c~


(1.17.6)

Finally, the heat capacity at constant volume, Cv , can be expressed as Cv = U

T ; the heat capacity at constant
H
pressure, Cp , can be expressed as Cp = T ; and the Gibbs Free Energy, G, can be expressed as G = F + pV , thus
Cv , Cp and G can be given as

[3kB T N ] = 3kB N
T

Cp =
[4kB T N ] = 4kB N
T



kB T
G = kB T N 1 + N + N ln N ln [V ] 3 ln
c~

Cv =

using Mathematica .

43

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-18): We are given an ideal gas consisting of N monoatomic molecules and a system
consisting of N oscillators. Supposing that they have a canonical distribution at temperature T , find
the most probable value, E , of the total energy E of the respective systems and confirm that it
in the canonical distribution.
agrees with the mean value E
Solution 1-18): First, partition function for the ideal gas system is required. This partition function is given as

ZG =


Z
N Z
1 Y
Hi
d~
q
d~
p
e
i
i
N !~3N i=1 V3

where V3 represents the three dimensional volume where the gas
is contained. Using this (information about V3 )
and the Hamiltonian of an ideal gas, H = p~2 /2m = p2x + p2y + p2z /2m, the expression for ZG can be simplified to

ZG =


Z
N 
~
p2
1 Y
2mi
V
d~
q
d~
p
e
i
i
N !~3N i=1

Using Mathematica to evaluate the integral over p~ allows the expression for ZG to finally be given as
VN
ZG =
N !~3N

2m

3N/2

VN
V N 23N
3N/2
=
(2mk
T
)
=
B
N !~3N
N !~3N

Em
3T

3N/2
(1.18.1)

since = 1/kB T and E = 3N kB T /2. Using the partition function ZG , as given in (1.18.1), the probability of the
ideal gas having an energy level, E, is

P rG (E) =

1
N !~3N

eE
ZG


=

eE/kB T
23N V N

3T
mE

3N/2

Finding the most probable value for E is equivalent to finding the maximum of this expression for the probability
of various energy values. Thus, the first derivative, with respect to E, of this expression is required. Using
Mathematica , this derivative can be given as
(2E + 3kB N T ) eE/kB T
dP rG (E)
=
dE
23N +1 V N EkB T

3T
mE

3N/2
(1.18.2)

Setting the expression in (1.18.2) equal to zero and solving for E, using Mathematica , give E as


 3
 3

E =  kB T N  = kB N T
2
2

which is identical to the value from the ideal gas law. Now, for the system of oscillators, the energy of the system
depends on the number of states the system can take. As discussed inPProblem 1-8, the total number of states the
N
system of oscillators can take, M , implies the requirement that M = i ni = n1 + n2 + n3 + + nN . Thus,
removing the dependence of this system on M and replacing it with a dependence on T will yield an expression for
the most probable energy at a particular temperature. To accomplish this, an expression for the thermodynamic
weight of the entire system is required. First, the maximum possible energy of this system, can be expressed as


1
E = ~ M + N
2
44

(1.18.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Thus, as in Problem 1-8, the thermodynamic weight of the system can be given as

W =

(M + N 1)!
M ! (N 1)!

Considering M and N to be sufficiently large (and sufficiently greater than 1), Stirlings Approximation is applied
to yield
ln [W ] (M + N ) ln [M + N ] (M + N ) (M ln [M ] M ) (N ln [N ] N )
(M + N ) ln [M + N ] M ln M N ln N
Now, the entropy of the system, S, can be given in terms of the thermodynamic weight of the system as
S = kB ln [W ]. Combining this expression for the entropy with the above expression for yields
S = kB ln [W ] = kB ((M + N ) ln [M + N ] M ln M N ln N )
Noting that 1/T = S/E and the expression for the entropy above, and applying the chain rule implies
S
M S
M
1
=
=
=
T
E
E M
E




kB
[((M + N ) ln [M + N ] M ln M N ln N )]
M

(1.18.4)

To proceed with the expression in (1.18.4) an expression for M in terms of E is required. Noting the expression in
(1.18.3), we clearly have

M=

E
N

~
2

(1.18.5)

using Mathematica to solve for M . Now, Mathematica is used to evaluate the partial derivative of S with respect
to M and M with respect to E and the results are applied to the expression in (1.18.4) in order to obtain
S
M S
1
1
=
=
=
T
E
E M
~

M +N
kB ln
M



Now, the aim is to obtain an expression for the energy of the system which depends on the temperature of the
system and is independent of M . Thus, the expression for M in terms of E in (1.18.5) is applied to the above
expression, with the help of Mathematica , to obtain






E + 12 N ~
1
kB
4E
kB
2E + N ~
kB
=
ln
=
ln
=
ln
T
~
2E N ~
~
2E N ~
~
E 12 N ~
Finally, the expression no longer depends on M , so the final step of solving for E in terms of T is undertaken, using
Mathematica , to give


1
~
E = N ~ coth
2
2kB T
as the most probable value of E, which compares well with the expression for the average value of E for this system
given in expression (1.15.7 a) in Problem 1-15.

45

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-19): Show that the grand canonical distribution function of a classical ideal gas of
monatomic molecules is given by
= ef
What is the significance of and f ?
Solution 1-19): In the classical case, can be found using

X
X

NA =0 NB =0

Ni =NA ,NB ,...

1
Ni !~3Ni

HNA ,NB ,...

PNA ,NB ,...

j=0

Ni i

Since this is an ideal gas, with one type of particle, this expression for simplifies to

N =0

)
(
)
 Z
N

N Z
X


1 Y
1
1
Hi
H
N
e
e
d =
e
d
e
N !~3N i=0
N ! ~3
N =0

For a monatomic ideal gas, H can be expressed as H =

therefore, the expression for becomes

N =0

p
~
2m .

Further, using eqn (1.74 c) in Kubo, e = ;

)
(
 Z
 Z
N
N )

X
p
~2
p
~2
1
1
1
2m
2m
N
e
e
d
=
d
N ! ~3
N ! ~3

(1.19.1)

N =0

Evaluating the integral in (1.19.1) gives

Z
e

ZZZ

p
~
2m

d =

ZZZ

= L3

p
~2

dpx dpy dpz e 2m

dqx dqy dqz

0

ZZZ

dpx dpy dpz e (px +py +pz )/2m = V

m
2

3/2

Applying this to the expression in (1.19.1) gives

"
" 

3/2 #N X
3/2 #N

N
X
1 V m

V m
=
=
N ! ~3

N ! ~3 2

2
N =0

(1.19.2)

N =0

If f is now defined as
1
f= 3
~

p
~2

e 2m d =
=

N ! ZN = Zi

V
~3

m
2

Then, the expression for , in (1.19.2) becomes

N
X
X
N N
(f )
f =
N!
N!

N =0

N =0

46

(1.19.3 a)

3/2
(1.19.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

which is just the series expansion for = ef . Thus,

N
X
X
N N
(f )
f =
= ef
N!
N!

N =0

(1.19.4)

N =0

where = e is the absolute activity and f , given in (1.19.3) or (1.19.3 a), is the partition function of the ith
particle.

47

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-20): Consider a monatomic ideal gas of N molecules in a volume V . Show, with the help
of the T - distribution, that the number of n of molecules contained in a small element of volume v
is given by the Poisson distribution
Pn = en

n
n
n!

Solution 1-20): Using the expression in Eqn (1.75) in Kubo, the distribution of particle numbers (n/v) can be
given as

Pn (NA , NB , . . . ) =

N N ZN
e(NA A +NB B + ) ZN
= A B

Since this is an ideal gas, there is only one type of particle. Thus, the expression for Pn (NA , NB , . . . ) simplifies to
Pn (N ) = N

ZN

(1.20.1)

Using the the expression in (1.19.3.a) in Problem 19, ZN = f N /N ! and the expression in (1.19.4), = ef , the
expression in (1.20.1) becomes

Pn (N ) = N

ZN
fN
= N

N!

ef

= N

( f ) f
f N f
e
=
e
N!
N!

(1.20.2)

= f . Again using the expressions from Eqn (1.75) and Eqn (1.74 c) in Kubo
Finally, is must be shown that N

allows N to be written as
(

!)
N
N
N
i
X i1
X
1X i

i Zi =
i Zi =
Zi
N=
i=0
i=0
i=0

(
!)
"
#


N
N
i Zi
X
X i
=
=
Zi
i=0

i=0
Noting that =

PN

i=0

to be given as
i Zi , allows the expression for N
"N
#

ln
X i

Zi =
=
N=
i=0

to give
Finally, the expression from (1.19.4) in Problem 19, = ef is applied to this expression for N
= ln = f = f
N

to the expression for Pn (N ) in (1.20.2) gives

Applying this expression for N

Pn (N ) =

N
N
( f ) f
N

e
=
e N
N!
N!

48

(1.20.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-21): Show that the T -p distribution the quantity

G (T, p, N ) = kB T ln Y
is equal to the Gibbs free energy, where Y is the partition function.
Solution 1-21): Noting that Y can be given as

ZN (V ) epV dV

Y =
0

This expression for Y is applied to G (T, p, N ) = kB T ln Y to obtain

Z
G (T, p, N ) = kB T ln

ZN (V ) epV dV


(1.21.1)

The ZN (V ) term in the integral is now rewritten as ZN (V ) = eln[ZN (V )] ; however, ln [Z (V )] = F (, V, N ).

Thus, Z (N ) can be rewritten as ZN (V ) = eF (,V,N ) , which allows the expression in (1.21.1) to be rewritten as
Z

G (T, p, N ) = kB T ln

eF (,V,N ) epV dV


(1.21.2)

Now, it is noted that

eG(,p) =

eF (,V,N ) epV dV

since the V terms are be integrated to zero due to the negative exponent and the infinite integration limits, so the
expression in (1.21.2) becomes
h
i
G (T, p, N ) = kB T ln eG(,p) = kB T (G (, p)) = G (, p) = G (T, p, N )

49

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-22): Classify the following particles according to Fermi or Bose statistics :

particle

He

H2 molecule
Positron

Li

ion

Li

ion

Solution 1-22): Whether a particle will obey Fermi or Bose statistics depends on the number of Fermi particles
present. An even number of Fermi particles implies Bose statistics, while an odd number of Fermi particles implies
Fermi statistics. Noting that protons, neutrons, electrons and positrons are all Fermi particles gives

particle - 2 protons, 2 neutrons - Bose

He - 2 Protons, 1 neutrons, 2 electrons - Fermi

H2 molecule - 2 Protons, 2 electrons - Bose

Positron - e+ - Fermi

Li

ion - 3 Protons, 3 Neutrons, 2 electrons - Bose

Li

ion - 3 Protons, 4 Neutrons, 2 electrons - Fermi

50

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-23): Show that, when the density of a gas consisting of particles with mass m is
sufficiently low and its temperature is sufficiently high so that the condition,
mean de Broglie wavelength  mean distance between particles
is satisfied, one can use Boltzman statistics as a good approximation irrespective of whether the
particles obey Fermi of Bose statistics.
Solution 1-23): First, an expression for the de Broglie wavelength is required. Since , the de Broglie wavelength,
R
2
can be expressed as = ~/p and the p can be given as p 0 ep /2m , can be expressed as
~
= =~
p

Z

p2 /2m

1
dp

r
=

2~2
m

(1.23.1)

using Mathematica to evaluate the integral for p. For high temperature, e( )/kB T  1, thus the expression in
both Eqn (1.90) in Kubo and in Eqn (1.91) in Kubo reduce to
n
= e( )/kB T
which can be applied, along with e( )/kB T  1, to the classical equivalent of the expression from Eqn (1.93) in
Kubo to obtain


N

(Z Z

e( )/kB T

V
d = e 3
~

e~p

/2m


d~
p = V

m
2~2

3/2 )

This reduces to

3/2

m
N

V
2~2

(1.23.2)

which is equivalent to the condition given in Eqn (1.95) in Kubo for high temperature, low density systems.
Additionally, the expression for in (1.23.1) can be rewritten as
r
=

2~2
1
3 =
m

m
2~2

3/2

Applying the above expression, derived from the expression for , to the expression in (1.23.2) gives
 1/3

N
1
V
V
 3 3  
V

N
N

(1.23.3)

Now, the average distance between each particle can be found by dividing the volume occupied by the entire
system by the average number of particles in the system and taking the cube root (to convert it from average
volume per particle to average distance per particle). Thus, the expression in (1.23.3) implies that the de Broglie
wavelength is much less than the average distance between particles as desired.
Alternatively, the problem can be solved by starting with the condition mean de Broglie wavelength  mean
distance between particles in the form of (1.23.3). Then the expression for the de Broglie wavelength from (1.23.1)
could have been applied to give
51

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions




1/3

 1/3
2~2
V

m
N
 2 3/2
2~
V

m
N

3/2

N
m

V
2~2

(1.23.3)

(1.23.2)

which is to the condition given in Eqn (1.95) in Kubo for high temperature, low density systems and to the result
from (1.23.2).

52

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-24): Let ps be the probability that a system is in a state s with energy Es . Show that if
entropy is defined by
S = kB

ps ln ps

the values ps which make S a maximum under the condition that the mean energy of the system is
follows the canonical distribution.
E,
Solution 1-24): Since ps is the probability that the system is in a given state with energy Es , by the definition of
probabilities
X

ps = 1

(1.24.1)

from the definition of the first moment

must hold. Furthermore, since the average energy of the system is E,
(average),
X

= constant
Es ps = E

(1.24.2)

must hold as well. Since the desire is to maximize S,

!
S = kB

ps ln ps

= kB

X  (ps ln ps ) 

ps

ps = kB

{ln ps + 1} ps = 0

(1.24.3)

must hold, while subject to the constraints given in (1.24.1) and (1.24.2). Thus, using the method of Lagrange
Multipliers, expressions for the multipliers 1 and 2 , such that
!
0 = S + 1

Es p s

+ 2

= S + 1

X
s

= S + 1

ps

ps
Es
ps


ps + 2

X  ps 
s

ps

ps

{Es + 1} ps

holds, are sought. This can be rewritten by applying the expression for S from (1.24.3) to give
0 = kB

{ln ps + 1} ps + 1

0=

{Es } ps + 2

{1} ps

{kB ln ps kB + 1 Es + 2 } ps

For the expression in (1.24.4) to hold in general, kB ln ps kB + 1 Es + 2 = 0 must also hold in general. Solving
this for ps gives


2
1 Es
+
1
ps = exp
kB
kB
53


(1.24.4)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Now, 1 and 2 must be such that (1.24.1) and (1.24.2) still hold when ps is replaced by the expression in (1.24.4).
Thus, from (1.24.1)

1=

X

ps =


exp


1 Es
2
+
1
kB
kB

(1.24.1 a)

and from (1.24.2)

=
E

Es p s =

X


Es exp


1 Es
2
+
1
kB
kB

(1.24.2 a)

Since Es is, in general, unbounded 1 /kB must be less than zero for (1.24.1 a) and (1.24.2 a) to both converge.
Thus, 1 can be defined as 1 = kB , where R+ . This allows (1.24.1 a) to be rewritten as

1=

X
s



X
2
1
= e2 /kB 1
eEs = e2 /kB 1 Z ()
exp Es +
kB
s

(1.24.1 b)

by using the definition of the canonical partition function. This implies that Z () can be given as
Z () = e12 /kB
By using the definition 1 = kB , R+ and this expression for the partition function, Z, the expression in
(1.24.2 a) to be rewritten as

=
E

X
s



X


2
1 X
Es eEs
1
= e2 /kB 1
Es exp Es +
Es eEs =
kB
Z
()
s
s

(1.24.2 b)

By comparing (1.24.1) with (1.24.1 b) and (1.24.2) with (1.24.2 b) and using the expression for the partition
function, Z () = e12 /kB , it is clear that
ps = eEs e2 /kB 1 = eEs

1
Z ()

(1.24.5)

since,
X

ps = e2 /kB 1

eEs = e2 /kB 1 Z () =

1
Z () = 1
Z ()

and

X
s

Es ps = e2 /kB 1

X
s

Es eEs =

P
Es
1 X
s Es e

Es eEs = P
=E
E
s
Z () s
se

1
, the system does indeed follow the canonical distribution.
Since ps can be given as in (1.24.5), ps = eEs Z()

54

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-25): Derive, from an elementary molecular kinetic theory, Poissons equation,
pV = constant, for a quasi-static process of an ideal gas.
~
Solution 1-25): First an expression for the change in the energy of the system, E, is required. Since E = F~ d,
E can be expressed as
E = F~ d~ + F~ d~
Now, F~ = (Fx , Fy , Fz ) so F~ = (Fx , Fy , Fz ). Similarly, d~ = (x, y, z) so d~ = (x, y, z). These expressions allow
the expression for E to be rewritten as
E = F~ d~ + F~ d~
= (Fx , Fy , Fz ) (x, y, z) +
+ (Fx , Fy , Fz ) (x, y, z)
= xFx + yFy + zFz +
+ Fx x + Fy y + Fz z
The forces Fx , Fy , and Fz can be expressed as Fx = Ax p, Fy = Ay p, and Fz = Az p, respectively; therefore,
Fx , Fy , and Fz can be expressed as Fx = Ax p + Ax p, Fy = Ay p + Ay p, and Fz = Az p + Az p,
respectively. This allows the expression for E to be further refined to give

E = xFx + yFy + zFz +

+ Fx x + Fy y + Fz z
= xAx p + xAx p + yAy p+
+ yAy p + zAz p + zAz p+
+ Ax px + Ay py + Az pz
The areas, Ax , Ay , and Az can be expressed as Ax = yz, Ay = xz, and Az = xy, respectively; therefore, Ax , Ay ,
and Az can be expressed as Ax = yx + xy, Ay = zx + xz, and Az = zx + xz, respectively. These
expressions allow the expression for E to be rewritten as

E = xAx p + xAx p + yAy p+

+ yAy p + zAz p + zAz p+
+ Ax px + Ay py + Az pz
= xpyz + xpzy + ypzx+
+ ypxz + zpyx + zpxy+
+ xyxp + yxzp + zxyp+
+ yzpx + xzpy + xyp
= 3p (yzx + xzy + xyz) + 3xyzp

55

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

If it is noted that the volume occupied by the system, V , can be expressed as V = xyz, then V can be expressed
as V = yzx + xzy + xyz. Thus, the expression for E can be simplified to give E = 3pV + 3V p. This, in
turn, can be further simplified using pV = 32 E to give
E = 3pV + 3V p
E
V
p

=
+
3pV
V
p
V
p
E
=
+

2E
V
p
Without loss of generality, the system is considered to be contained within a box. For the one dimensional case the
box is considered to be expanding in only one direction; again, without loss of generality (for the case of one
dimensional expansion of the system), the expansion of the volume is said to be in the x-direction. That is to say,
that one of the walls perpendicular to the x-direction is moving such that the volume contained within the system
changes with respect to the change in x, V x. This is illustrated below in Figure 1.25-1.

Figure 1.25-1 : Adiabatic expansion of the volume occupied by the system

Therefore,, the change in the energy of the system, E, can also be given by the change in the kinetic energy of the
particles colliding with the moving wall during some period of time t. Thus, E can be given as

E = n t

(1.25.1)

where A is the area of the moving wall, n is the number of particles impacting the wall during the time interval t,
and is the change in the average kinetic energy per particle for the particles impacting the wall. Now, can be
written as = p2x /2m so can be given as

=

px
m

56

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Defining the speed with which the wall is moving as vx implies that the change in the momentum of a particle
striking the wall is 2mvx . This allows to be given as

0
1
p2
4vx px m + 4m2 vx2
*
2
2

(px 2mvx ) x =
2vx px + 
2mv
=
2vx px
x
2m
2m
2m

The vx2 term in above is neglected due to the adiabatic nature of the expansion. That is to say, for the expansion of
the system to be adiabatic, vx must be small; therefore vx2 must be infinitesimal and can therefore be neglected.
Applying this expression for to the expression for above allows to be expressed as

=

px
m


=

px (2vx px )
m


=

2vx p2x
m

Applying this expression for to the expression for E and using the definition of average value allows the
expression for E to be expressed as

E = n

2vx p2x
m

Ly

Lz

ZZZ

2vx p2x
m

dy
dz
f (~
p) d3 p~
0
0
ZZZ 2
ZZZ 2
px
px
= n A vx t
f (~
p) d3 p~ = n V
f (~
p) d2 p~
m
m
0
0

t = n t

(1.25.2)

where f (~
p) is the distribution of the particles. The distribution f (~
p) depends only on p~ for the same reason that
the spatial integration in (1.25.3) is only over y and z, but not x; the region of space of interest is the moving wall.
In going to n V from n A vx t in the expressions in (1.25.3) it is noted that vx t = x, which implies
n A vx t = n A x = n V . Now, noting that

ZZZ
2
0

p2x
p2
f (~
p) d2 p~ = 4 x = 4
m
2m

allows the expression for E given in (1.25.3) to be rewritten as

ZZZ
E = 2 n V
0

Using p = 32 n = 2 n = 3p and pV = 32 E = p =

p2x
f (~
p) d2 p~ = 4 n V
m

2 1
3V

E, this expression for E becomes

E = 4 n V = 2 2 n V = 2 V p =

4 V
E
3 V

(1.25.3)

Combining this expression for Ewith the expression for E in (1.25.1) gives
V
p
E
1
+
=
=
V
p
2E
2E

4 V

E
3 V


=

2 V
V
p
2 V

+
=
3 V
V
p
3 V

This expression implies

V
p
2 V
5 V
p
5
+
=

+
= 0
( ln V ) + ln p = ln A
V
p
3 V
3 V
p
3

57

(1.25.4)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

since ln V = V /V , ln p = p/p, and ln A = 0, where A R is an arbitrary constant. This simplifies to

5
ln V + ln p = ln A
i
h3

ln V 5/3 + ln p = ln A
h
i
ln V 5/3 p = ln A
V 5/3 p = A

(1.25.5)

by canceling the logarithms. Thus, for this specific case, V 5/3 p = A. To show this for the general case, taking into
account internal degrees of freedom, E a E, where a 3a > 1, in (1.25.3) implies E = 23 V
V Ea. Applying this
p
E
= V
+
implies
to 2E
V
p

V
p
E
a V
a  V
p
V
p
+
=
=
1 +
+
=
+
=0
V
p
2E
3 V
3 V
p
V
p
where R 3 n > 1. Using the same arguments used for expressions (1.25.4) and (1.25.5), this implies that
pV = Constant, as desired.

58

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-26): Discuss the number of states, 0 (E), of a system of N oscillators and show that this
system is normal in the sense discussed in Section 1.6.
Solution 1-26): From the expression in (1.18.3), the maximum energy of the system can be given as


E = ~ M + 21 N ; however, the number of states in the system is independent of the terms corresponding to the
zero pointa of the oscillation, 12 N ~. ignoring the zero point terms in the oscillations gives the maximum energy of
the system, E, as E = ~M , which implies that M = E/~. Since the number of states for a system, 0 (E),
PE
can be written as 0 (E) = M =0 WM , the expression for M , M = E/~, implies that 0 (E) can be given as

0 (E) =

M
X

E/~

WM =

M =0

Applying the expression for WM given in (1.8.2),

WM

M =0

(M +N 1)!
M !(N 1)! ,

to this expression for 0 (E) gives

E/~

0 (E) =

X (M + N 1)!
(E/~ + N )!
=
M ! (N 1)!
(E/~)!N !

M =0

Taking the natural log of this expression for 0 (E) and using Stirlings Approximation gives


 

 
E
E
E
E
ln 0 (E) =
+ N ln
+N
ln
N ln N
~
~
~
~

 



E
E
E
E
=N
+ 1 ln
+1 N
ln
~N
~N
~N
~N

 



E
E
E
E
=N
+ 1 ln
+1
ln
~N
~N
~N
~N



E
, the expression in (1.26.1) implies
Using the expression in Eqn (1.24 a) in Kubo, 0 (E) v exp N N

v

(1.26.1)

 



E
E
E
E
+ 1 ln
+1
ln
~N
~N
~N
~N

For the system to be normal as described in Section 1.6, > 0, 0 > 0, and 00 < 0 must be satisfied. Using
Mathematica , limE {} is given as

lim {} =

lim

 



E
E
E
E
+ 1 ln
+1
ln
= +
~N
~N
~N
~N

Since + > 0, the condition > 0 holds. Again, using Mathematica , 0 can be given as




N ~
E + N ~
= ln 1 +
= ln
E
E
0

Thus, using Mathematica again, limE0+ {0 } can be given as

 

E + N ~
lim+ {0 } = lim+ ln
= +
E
E0
E0

59

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Since + > 0, the condition 0 > 0 holds. Again, using Mathematica , 00 can be given as
00 =

N 2 2 ~2
E 2 + EN ~

(1.26.2)

Thus, using Mathematica again, limE0+ {00 } can be given as

lim {0 } = lim

E0+

E0+

N 2 2 ~2
2
E + EN ~


=

Since < 0, the condition 00 < 0 holds. Thus, the conditions in (1.25) are satisfied. This can also be seen
graphically

Figure 1.26-1 : Plot of

Figure 1.26-2 : Plot of 0

60

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Figure 1.26-3 : Plot of 00

Figure 1.26-4 : Plot of , 0 , and 00

61

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-27): Let N atoms be arranged regularly so as for form a perfect crystal. If one places n
atoms among them ( 1  n  N ) from the lattice sites to interstices of the lattice, this becomes an
imperfect crystal with n defects of the Frenkel type. The number N 0 is interstitial sites into which
an atom can enter is of the same order of magnitude as N . Let w be the energy necessary to remove
an atom from a lattice site to an interstitial site. Show that in the equilibrium state, at temperature
T R+ 3 w  kB T , the following relation is valid:
n2
= ew/kB T
(N n) (N 0 n)

or

n;

N N 0 ew/2kB T

Solution 1-27): Since the amount of energy required to move a single atom from a lattice site to an interstitial
site is w, the amount of energy to move n atoms from lattice sites to interstitial sites is E (n) = nw. Thus, the
energy of the imperfect crystal is E (n) = nw greater than the perfect crystal. Now, the thermodynamic weight of
the system can be expressed in terms of the thermodynamic weights of the lattice sites, WN (n), and interstitial
sites, WN 0 (n), to be given as
W (n) = WN (n) WN 0 (n)
The thermodynamic weight of the lattice sites is simply the number of ways that n atoms can be removed from
their lattice sites, so
 
N
N!
WN (n) =
=
n! (N n)!
n
Similarly, the thermodynamic weight of the lattice sites is simply the number of ways that n atoms can be moved
to interstitial sites, so

WN 0 (n) =

N0
n


=

N 0!
n! (N 0 n)!

Applying these expressions for WN (n) and WN 0 (n) to the expression for the thermodynamic weight of the system
given above yields

W (n) = WN (n) WN 0 (n) =

  0 


N
N
N!
N 0!
=
n
n
n! (N n)! n! (N 0 n)!

Thus, the partition function of the system can be given as

Z (n) = W (n) e E(n) =

  0 


N
N
N!
N 0!
e n w =
e n w
n
n! (N n)! n! (N 0 n)!
n

(1.27.1)

The free energy of the system is given as F = kB T ln [ (n)] and at thermodynamic equilibrium F/n = 0, thus,
using Stirlings Approximation, we have

62

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

 



F
ln [Z (n)]

N!
N 0!
n w
= kB T
= 0 = kB T
ln
e
n
n
n
n! (N n)! n! (N 0 n)!

=
[N ln N N n ln n + n (N n) ln [N n]
n
n + N + N 0 ln N 0 N 0 n ln n + n
(N 0 n) ln [N 0 n] + N 0 n nw]
=

[N ln N n ln n (N n) ln [N n] + N 0 ln N 0
n
n ln n (N 0 n) ln [N 0 n] nw]

(n ln n) {(N n) ln [N n]}

n
n
{(N 0 n) ln [N 0 n]} (nw)

n
n
= w 2 ln [n] + ln [N n] + ln [N 0 n]
= 2

This implies

 
w = 2 ln [n] ln [N n] ln [N 0 n] = ln n2 ln [N n] ln [N 0 n] = ln

n2
(N n) (N 0 n)

which can be rewritten as

ew =

n2
(N n) (N 0 n)

(1.27.2)

For N  n and N 0  n, the expression in (1.27.2) becomes

ew =

n2
n ; ew/2 N N 0
0
NN

63

(1.27.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-28): If n atoms in a perfect crystal formed by N atoms ( 1  n  N ) are displaced from
lattice sites inside the crystal to lattice sites on the surface, it becomes imperfect, having defects of
the Schottky type. Let w be the energy necessary to displace an atom from inside to the surface.
Show that in the equilibrium state, at temperature T satisfying w  kB T , one has
n
= ew
N +n

or

n ; N ew

Solution 1-28): Using the same arguments as in Problem 1-27, the partition function of the system can be given as

Z (n) =




N + n E(n)
N + n E(n)
(N + n)! E(n)
e
=
e
=
e
N
n
N ! n!

Again, the energy required to move n atoms from lattice sites inside the crystal to lattice sites on the surface of the
crystal is E (n) = nw. As in Problem 1-27, the free energy of the system is F = kB T ln [Z (n)] and at
thermodynamic equilibrium F/n = 0, thus, using Stirlings Approximation, we have

 
ln [Z (n)]

(N + n)! E(n)
F
= kB T
= 0 = kB T
e
ln
n
n
n
N ! n!

= kB T
[(N + n) ln [N + n] N n
n
N ln N + N n ln n + n nw]

= kB T
[(N + n) ln [N + n] N ln N n ln n nw]
n
= w ln n + ln [n + N ]
This implies
w = ln n ln [n + N ]


n
w = ln
N +n
n
ew =
N +n
Since n  N , the expression in (1.28.1) becomes
ew =

n
n ; N ew
N

64

(1.28.1)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-29): Consider an adsorbent surface having N sites each of which can absorb one gas
molecule. Suppose that it is in a contact with an ideal gas with the chemical potential
(determined by the pressure p and the temperature T ). Assuming that an adsorbed molecule has
energy 0 compared to one in a free state, determine in this case the covering ratio, (the ratio of
adsorbed molecules to adsorbing sites). Using the grand canonical ensemble, find, in particular, the
relation between and p in the case of monatomic molecules, utilizing the result for in example 8.
Solution 1-29): The covering ratio, , can be expressed as the average number of molecules which are adsorbed,
n
, over the total number of molecules in the system
n

(1.29.1)
N
Using the same arguments as in Problems 1-27 and 1-28, the thermodynamic weight of the system can be given as
=

 
N
N!
W (n) =
=
n! (N n)!
n
Using this expression for the thermodynamic weight of the system and the expression for the energy change when n
atoms are adsorbed, the canonical partition function, Z, of the system can be expressed as
Zn =

N!
e0 n
n! (N n)!

which in turn allows the expression for the grand canonical (T, distribution) partition function, , to be given as

N
X

Zn e

n=0

N 
X
n=0



N!
0 n
n
e
e
n! (N n)!

This expression for can be simplified using Mathematica to give


N
= 1 + e(0 +)
Noting that and n are conjugate variables and that is the moment generating function, n
can be given as
1 ln
=N
n
=


1

1 + e(0 +)

Applying the above expression for n

to the expression for in (1.29.1) gives

 

n

1
1
1
1
=
N 1
=1
=
N
N
1 + e(0 +)
1 + e(0 +)
1 + e(0 +)

(1.29.2)

Now, a relation between the chemical potential, , and the pressure of the system, p, is required. Specifically, and
expressions for e in terms of p is desired. Since the gas here is ideal, the canonical partition function of the
system can also be given as
1
Z=
N !~3N

"Z

N N
LN
x Ly Lz
=
N !~3N

Lx

Ly

dqx
0

dpx

(p2x +p2y +p2z )/2m

d p~ e

dpy

dqz
0

#N

ZZZ

dqy
0

Z

Lz

dpz e

(p2x +p2y +p2z )/2m

65

N

VN
=
N !~3N

2m

3N/2

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

which allows the Helmholtz Free Energy of the system to be given as

"

"

3N/2 #
3N/2 #

2m
VN
V N 2m
1
F = kB T ln [Z] = kB T ln
= ln
N !~3N

N!
~2








1
1
3N
2m
3N
2m
ln N !
N ln N + N
=
N ln V +
ln
N ln V +
ln

2
~2

2
~2
Now, since = (F/N )T,V , the above expression for the Helmholtz Free Energy of the system implies that




1
3N
2m

N
ln
N
+
N
N ln V +
ln

2
~2
T,V



3
2m
ln N ln V ln
2
~2
"
3/2 #!
 
N
2m
ln
ln
V
~2
" 
3/2 #
N ~2
ln
V 2m

= (F/N )T,V =
=

The equation of state for an ideal gas implies that V = N kB T /p which allows the above equation for to be
rewritten as
"
" 
 2 3/2 #
3/2 #
~
~2
1
p
1
= ln p
= ln

kB T 2m

2m
which implies

e = p

~2
2m

3/2
(1.29.3)

The expression for given in (1.29.2) can be rewritten as

1
1 + e(0 +)

e
e + e0

which allows the expression for e from (1.29.3) to be applied to give

 2 3/2
~
p 2m
=
=
 2 3/2
~
p 2m
+ e0
p+

66

p


2m
~2

3/2

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-30): Find the fluctuation M M

discussed in Example 10.

2

of the total magnetic moment M of the spin system

Solution 1-30): Since any spin 1/2 particles has either energy E = H or energy E = H, the partition
function of a single particle can be given as
Z1 = eH + eH
which allows the partition function for the entire system to be given as
ZN = Z1N = eH + eH

N

= 2N coshN [H]

(1.30.1)

Using the expression for ZN in (1.30.1) in F = kB T log [ZN ] allows the Helmholtz Free Energy of the system to
be given as
h
i
F = kB T log 2N coshN [H] = kB N T log [2 cosh [H]]

(1.30.2)

Noting that H and are conjugate variables and that the Helmholtz Free Energy of the system is also the


2 to be expressed as
cumulant generating function for the system allows M M

M M

2

1 2F
= N 2 sech2 [H]
H 2

67

(1.30.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-31): Consider a system consisting of N particles. Let us divide all the quantum states of
an individual particle into groups, each of which contains states with nearly equal energy. Let the
energy of the j-th group be j and the number of states contained within it to be cj . A state of the
whole system can then be specified by the set of the number of particles Nj in each group.
(i) Show that the thermodynamic weight of the sate specified by the set {Nj } is given by

W {Nj } =

Y (Nj + cj 1)!
, B. E.
Nj ! (cj 1)!
j

W {Nj } =

Y
j

cj !
, F. D.
Nj ! (cj Nj )!

according to the statistics of the particle system

(ii) Supposing that the whole system is in contact with a heat bath at temperature T , find the
most probable set among {Nj } and derived from this result the Bose-Einstein or Fermi-Dirac
Distribution as the probability of each state of an individual particle being occupied.
(iii) Assuming that the energy of the whole system, E, is constant (use a microcanonical ensemble),
derived the same result as in Part (ii).
Solution 1-31): For Fermi-Dirac statistics, we simply have cj choose Nj , since only one particle can occur in each
state. Thus, the thermodynamic weight of a single group of particles, Wj , can be given as

Wj =

cj
Nj


=

cj !
Nj ! (cj Nj )!

(1.31.1)

since the thermodynamic weight of the wholeQsystem is just the product of the thermodynamic weights of the
groups that compose the system, W {Nj } = j Wj . Combining this with the last result, gives
W {Nj } =

Y
j

cj !
Nj ! (cj Nj )!

For Bose-Einstein statistics, any number of particles can occur in each state. Thus, we have (Nj + cj 1)! possible
state combinations and Nj particles that can take states. Thus Wj for Bose-Einstein statistics is

Wj =
Again, W {Nj } =


Nj + cj 1
(Nj + cj 1)!
=
Nj
Nj ! (cj 1)!

Wj , so W {Nj } can be given as

W {Nj } =

Y (Nj + cj 1)!
Nj ! (cj 1)!
j

To obtain
n
=
n
=

1
e( )/kB t

+1

1
e( )/kB t
68

, F. D.
, B. E.

(1.31.2)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Note that the partition functions for the Fermi-Dirac and Bose-Einstein systems can be given, respectively, as

F D =

j Nj +Nj

Wj =

Nj =0

BE =

X
Nj =0


X

j Nj +Nj

j Nj +Nj

Nj =0

j Nj +Nj

Wj =


X
Nj =0

cj !
Nj ! (cj Nj )!

cj !
Nj ! (cj Nj )!

j /cj , we note that N

can be found
Noting that n
is just the average number of particles per occupation number, N
j , thus for the Fermi-Dirac and Bose-Einstein systems, respectively, Nj
by solving 0 = ln [] /Nj for Nj to give N
can be given as

j 
ln []
cj N
0=
= ( j ) + ln
j
Nj
N
1
Nj = cj ( )
e j
+1
Nj
1
n
j =
= ( )
j
cj
e
+1


ln []
Nj
0=
= ( j ) + ln
j
Nj
cj N
1
Nj = cj ( )
j
e
1
Nj
1
n
j =
= ( )
j
cj
e
1

(1.31.3)

(1.31.4)

which are the desired expressions for the state densities in Fermi-Dirac, (1.31.3), and Bose-Einstein, (1.31.4),
statistics.

69

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 1-32): Show that for an ideal gas, the relation

p=

2 Ein
3 V

holds irrespective of its statistics, where Ein is the total kinetic energy.
Solution 1-32):

70

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Chapter 2 - Solutions
Problem 2-1): Show that the energy fluctuation in a canonical distribution is given by

EE

2

= kB T 2 Cv

where T is the absolute temperature and Cv is the heat capacity at constant volume. Prove the
following relation in a similar manner:

EE

3

2
kB


T

Cv
T

+ 2T Cv
V

Show that, in particular, for an ideal gas consisting of N monatomic molecules (disregard the
internal structure) these equations can be reduced to

EE
2
E

2

EE
3
E

2
=
,
3N

3
=

8
9N 2

Solution 2-1): The cumulant generating function for the system can be given as ln [Z]; therefore an expression for
the partition function of the system is required. From the expression in Eqn (2.1) in Kubo, the partition function of
the system can be given, in general, as
Z

eE (E) dE

= 1
E
Z

eE E (E) dE

2 = 1
E
Z

eE E 2 (E) dE

3 = 1
E
Z

eE E 3 (E) dE

Z=
E
2 , and E
3 can be expressed as
By definition, E,

so the derivatives

Z 2 Z
, 2 ,

Z
e

2Z
2
=
2
2

Z

3Z
2
=
3
2

Z

and

3Z
3

imlpy


(E) dE =

00


2 Z = Z 00 Z = E
2
E 2 eE (E) dE = E
Z

000


3 Z = Z 000 Z = E
3
E 3 eE (E) dE = E
Z

(E) dE =


(E) dE =

0


Z = Z 0 Z = E

EeE (E) dE = E
Z

71

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

where Z, Z 0 , and Z 000 are defined as Z 0 =

and the values for

Z Z
, 2 ,

and

Z
3 ,

the

3
2Z
000
= Z3 . Using the definitions
2 , and Z
3
ln Z 2 ln Z
derivatives
, 2 , and ln3Z can be given as

Z
,

Z 00 =

Z
ln Z

1
Z

Z
ln

eE (E) dE


=

E
2 , and E
3
of E,


 E
e
(E) dE
Z

eE (E) dE




1 Z
Z0

EeE (E) dE =
=
= E
Z
Z



 
 0 2
2
2 ln Z
ln Z
Z 00
Z0
Z Z 00 (Z 0 )
Z
=
=
=
=

Z
Z2
Z
Z


2




Z0
Z 00
2 = E2 E
2 = E E
2

= E 2 E
=
Z
Z
"
 0 2 #


3 ln Z
Z
2 ln Z
Z 00
=

=
3
2

Z
Z
!


2
Z0
Z Z 000 Z 00 Z 0
Z Z 00 (Z 0 )
2
=
Z2
Z
Z2
 0
 0 2 !
Z 00 Z 0
Z
Z
Z 000
Z 00

=
2
Z
Z
Z
Z
Z


+ 2E
E2 E
2
= E 3 + E 2 E


E 2 2E
E 2 + 2E
3
= E3 E




E 2 + 2E
3 = E E
3
= E 3 3E

(2.1.1)

(2.1.2)

(2.1.3)

From (2.1.1) and (2.1.2) and the definition of specific heat, Cv , it is clear that

EE

2



 




ln Z
E
T E
1

=
=
=
= Cv

T
kB




1
= Cv kB T 2 = Cv kB T 2
= Cv
kB 2

(2.1.4)

Similarly, from (2.1.2), (2.1.3) and (2.1.4) and the definition of Cv , it is also clear that

EE

3









3 ln Z

2 ln Z
2 = Cv kB T 2
=

E
3
2








T

C
Cv
v
2
=
Cv kB T 2 = kB T 2 2Cv kB T + T 2 kB
= kB
2Cv T 3 + T 4
T
T
T
=

= 3 N kB T and Cv = 3 N kB , therefore, (2.1.4) and (2.1.5) imply

For an ideal gas, E
2
2

72

(2.1.5)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

EE
2
E

2

EE
3
E

3

3
2 2
N kB
T
2
2
=
=
9 2 2 2
3N
N kB T
4
=

3 3
3N kB
T
8
=
27 3 3 3
9N 2
N kB T
8

73

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-2): A weight of mass m is fixed to the middle point of a string of length L as shown in the
figure and rotates about an axis joining the ends of a string. The system is in contact with its
environment at a temperature T . Calculate the tension X acting between the ends of the string in
terms of its dependence upon the distance x between the ends.
~ and the centripetal force acting on the rotating mass, F~c ,
Solution 2-2): The tension at the attachment points, X,
be be expressed in terms of the force in the cable between an attachment point and the rotating mass, F~ , as
~
~ = F cos
X
2
(2.2.1)
F~c = F~ sin
as shown in Figure 2.2-1 below

Figure 2.2-1 : Force diagram

The expressions in (2.2.1) can be combined by eliminating F~ to give


~
2X
F~c
F~c
F~c x 2
x F~c
~
=
X =
cot =
=
cos
sin
2
2 2r
4r

From Figure 2.2-1 it is clear that r = 21 l2 x2 . Thus, the expression in (2.2.1 a) becomes
~
~
~ = x Fc = x Fc
X
2
4r
2 l x2

(2.2.1 a)

(2.2.1 b)

~ in (2.2.1 b) to be rewritten as
Noting that F~c = m 2 r and = p /mr2 allows the expression for X






~
x m 2 r
x mp2 r
x mp2
xp2
~ = x Fc

X
=
=
=
=
2
mr (l2 x2 )
2 l2 x2
2 l 2 x2
2m2 r4 l2 x2
m 2 r 3 l 2 x2
~ the the Partition Function of the system is required. Thus, integral
To obtain an expression for X,
Z

Z=

ep /2mr dp

is evaluated using Mathematica to obtain

74

(2.2.1 c)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Z=

3/2

ep /2mr dp = r (2)

(2.2.2)

~ can be found by evaluating the integral

Therefore, the expression for X
~ = 1
X
Z

~ p2 /2mr2 dp = 1
Xe
Z

xp2
mr2 (l2 x2 )

ep /2mr dp

~ becomes
must be evaluated. Using Mathematica and the expression for Z in (2.2.2), the expression for X
~ = 1
X
Z

xp2
2
mr (l2 x2 )

ep /2mr dp =

which is the desired answer.

75

x
l 2 x2

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-3): An ideal gas consisting of N particles of mass m (classical statistics being obeyed) is
enclosed in an infinitely tall cylindrical container placed in a uniform gravitational field, and is in
thermal equilibrium. Calculate the classical partition function, Helmholtz Free Energy, mean energy
and heat capacity of the system.
Solution 2-3): Since the system obeys classical statistics, the Hamiltonian of the a single particle of gas can be
given as

HN =

p2x + p2y + p2z

+ mgz
2m

which allows the partition function of a single particle of gas to be expressed as

ZN

1
= 3
~

r0

dpy

dpx

dz

r dr
0

dpz e

2
2
p2
x +py +pz
2m

+mgz

Using Mathematica , this integral for ZN can be evaluated as

ZN

A
=
g ~3

m 3 23
5

Which allows the partition function of the system to be given as

1
ZN
Z= N =
N!
N!

A
g ~3

m 3 23
5

!N

Using this expression for Z, the Helmholtz Free Energy of the system can be given as
s
!N
m 3 23
A

g ~3
5
s
#
A
m 3 23
= kB T N ln
+ kB T N ln N
g ~3
5
s
"
#
" p
#
5 T5
A m 3 23 kB
m 3 23
A
= kB T N ln
= kB T N ln
g ~3 N
5
g ~3 N

1
F = kB T ln [Z] = kB T ln
N!
"

(2.3.1)

by using Stirlings Approximation and noting that = 1/kB T . Using Mathematica and the expression for F in
(2.3.1), allows U and Cv to be given as

U = T 2

F
T


=

5
kB N T
2

and

Cv =

U
5
= kB N
T
2

76

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-4): A cylinder of radius R and length L rotates about its axis with a constant angular
velocity . Evaluate the density distribution of an ideal gas enclosed in the cylinder. Ignore the
effect of gravitation. Carry out classical calculations assuming that thermal equilibrium is
established at T .
Solution 2-4): Orienting the cylinders axis in the z-direction allows the angular momentum of a particle in the
cylinder to be given as

 x

~
Lj = ~rj p~j =  xj
 pxj

y
yj
pyj






 = z xj pyj yj pxj Lj = xj pyj yj pxj



z
0
0

Since the Hamiltonian that describes motion in a rotating coordinate system, H , can be given as H = H L,
where H is the Hamiltonian in the coordinate system at rest and Lj is the angular momentum, the Hamiltonian of
a single particle in the cylinder can be given as

Hj = Hj Lj =

p2xj + p2yj + p2zj

2m

+ (xj , yj , zj ) xj pyj yj pxj

(2.4.1)

where (xj , yj , zj ) is the potential due to the walls of the vessel, which can be given as

(xj , yj , zj ) =

0
r [0, R] , z [0, L]
+ r
6 [0, R] , z 6 [0, L]

Using the expression for the Hamiltonian of a single particle in (2.4.1), the Hamiltonian of the system of N
particles can be given as

H=

N
X

Hj

j=1

N
X

p2xj + p2yj + p2zj

2m

j=1

)
xj pyj yj pxj

as long as the domain of consideration is restricted to inside the container. This expression allows the partition
function of the system to be given, using Mathematica , as

Rx2

1
dz
dx
dy
dpx
~3 0
Rx2
R

5/2 


2 2
L m 2
= 2 3
em R /2 1
~

ZN =

dpy

dpz e

2
2
p2
xj +pyj +pzj
2m

!
(xj pyj yj pxj )

(2.4.2)

Using the expression for the partition function of a single particle given in (2.4.2) allows the partition function of
the system to be given as

Z L
Z R
Z Rx2j
Z
Z
Z
N

Y
1
Z=
dz
dx
dy
dp
dp
dp
e
j
j
j
x
y
z
j
j
j

~3 0
R
Rx2j

j=1
1
=
N!

5/2 


L m 2
m 2 R2 /2
e

1
2 ~3

2
2
p2
xj +pyj +pzj
2m

(xj pyj yj pxj )

!N
(2.4.3)

Now, the density of gas molecules can be given as

77

Jonathan McFadden
Spring 2010

=m

PHYS 7400
Kubo Solutions

N
X

{ (x xi ) (y yi ) (z zi )} = m

i=1

N 
X
1
i=1

ri


(r ri ) (z zi ) ( i )

This allows the average density of particles in the system to be given as

!

2
2
p2
xj +pyj +pzj
Z
Z
Z L
Z R
Z Rx2j
Z
N

x
p
y
p
Y
(
)
j
y
j
x
2m
j
j
1
dpzj e
dpyj
dzj
dxj
dyj
dpxj
=

~3 Z 0

Rx2j
j=1
))
N 
X
1
(r ri ) (z zi ) ( i )
m
ri
i=1
!

3N/2
5/2 

 N 1
1
2m
L m 2
m 2 r 2 /2
m 2 R2 /2
=
N me

e
1
Z N ! ~2
2 ~3

!
3N/2
5/2 



L m 2
2m
m 2 r 2 /2
m 2 R2 /2
N me

e
1
=
~2
2 ~3

for r [0, R] , z [0, L].

78

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-5): In special relativity, the momentum components and the energy of a mass point m
are given by

pi = p

mvi

(i = x, y, z)

1 (v/c)2

and
mc2
= p
1 (v/c)2
q
respectively, where c is the speed of light; v = vx2 + vy2 + vz2 is the velocity; and vx , vy , and vz are the
velocity components of the mass point. Show that the Maxwell-Boltzmann distribution yields

mvi2
p
1 (v/c)2

1
=
Z

p
1 (v/c)2

Solution 2-5): By definition, the average value of

1
2

mvi2

1
2

1
2

1
kB T
2

mvi2

is given as

1(v/c)2

1
2

mvi2
p

1 (v/c)2

e/kB T dvx dvy dvz

(2.5.1)

however, this integral cannot be evaluated in its present form. If the energy, , is rewritten as

= p

mc2
1 (v/c)2

r
1

v2
mc2
=
c2

(2.5.2)

or
q
= c m2 c2 + p2x + p2y + p2z

(2.5.3)

Using the relativistic momentum relation

pi = p

mvi
1 (v/c)2

vi =

and the expressions in (2.5.2) and (2.5.3), the expression

1
2

mvi2
p
1 (v/c)2

p2
= x
2m

p2
v2
1 2 = x
c
2m

1
2

mc2

pi p
1 v 2 /c2
m


mvi2
1(v/c)2


=

can be rewritten as

p2x c2
p2x c
= q
2
2 m2 c2 + p2x + p2y + p2z

Applying this to the expression and the expression in (2.5.3) in (2.5.1) yields

79

Jonathan McFadden
Spring 2010

1
2

PHYS 7400
Kubo Solutions

mvi2
p

1 (v/c)2

q
ec m2 c2 +p2x +p2y +p2z /kB T dpx dpy dpz

2 m2 c2 + p2x + p2y + p2z
Z
Z
Z
/kB T

1
px
= pi
=
e
dpx dpy dpz
px
Z
px


Z Z Z
e/kB T
1
px kB T
=
dpx dpy dpz
2Z
px

Z Z h
Z
ip =

1
c m2 c2 +p2x +p2y +p2z /kB T x
kB T
px e
+
e
dpx dpy dpz
= kB T
2Z
px =

Z Z Z
1
ekB T dpx dpy dpz
(2.5.4)
= kB T
2Z
1
=
Z

p2x c

Noting that Z can be given as

Z

ekB T dpx dpy dpz

Z=

allows the expression in (2.5.4) to be rewritten as

1
2

mvi2
p
1 (v/c)2

!
= = kB T

1
2Z

as desired.

80

ekB T dpx dpy dpz =

1
kB T
2

(2.5.5)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-6): Generalized coordinates specifying the state of a system having 3N degrees of
freedom are denoted by q1 , q2 , . . . , q3N . The force corresponding to a coordinated qj is Xj . (When the
Hamiltonian of the system is expressed by H, Xj = H/qj .) Show that
3N
X

qj Xj = 3N kB T

j=1

where T is the absolute temperature. This is the virial theorem.

In particular, when a gas made up of N molecules having an intermolecular interaction potential
U (q1 , q2 , . . . , q3N ) is enclosed in a vessel of volume V , the virial theorem takes the following form:
3N

1 X U
pV = N kB T
qj
3 j=1 qj
where p is the pressure exerted by the gas molecules on the wall of the vessel. Here, q1 , q2 , . . . , q3N
are Cartesian coordinates specifying the coordinates of these N molecules.
H
,
Solution 2-6): By extension of the expression form Eqn (1) from Example 1 in Chapter 2 the expression, qi q
j
can be expressed as

qi

H
= kB T ij
qj

(2.6.1)

H
, allows the expression in (2.6.1) to be rewritten as
Noting that Xj = q
j

qi

H
= qi Xj = kB T ij
qj

This expression, in turn, implies that

3N
X

qi

j=1

3N
3N
3N
X
X
X
H
=
qj Xj =
qi Xj =
kB T ij = 3N kB T
qj
j=1
j=1
j=1

(2.6.2)

as desired. Since Xj is the total force acting of the particles, it can be expressed as

Xj =

U
+ Fj
qj

Applying this expression for Xj to the expression in (2.6.2) yields

3N kB T =

3N
X


 X
3N
3N
3N
3N
N
X
X
U
U X
U X
qj Xj =
qj
+ Fj =
qj

qj Fj =
qj

~rj F~j
qj
qj j=1
qj j=1
j=1
j=1
j=1
j=1

Examining the expression

PN

rj
j=1 ~

F~j , it is clear that

81

(2.6.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

N
X

~rj F~j =

ZZ

~r F~ d~a

j=1

where the integral is over to the area exerted on the wall of the vessel. Since, F~ is the force on the wall of the
vessel, it can be rewritten as F~ = p n
where p is the pressure on the vessel wall and n
is the vector normal the the
PN
wall of the vessel. Thus, using the divergence theorem, the expression for j=1 ~rj F~j becomes
Z Z
ZZ
ZZZ
N
X

~rj F~j =
~r F~ d~a =
~r (p n
) d~a = p
~r dV = 3pV
j=1

This allows the expression in (2.6.3) to be rewritten as

3N kB T =

3N
X
j=1

qj

3N

X U
U X
~rj F~j =
qj

3pV
qj j=1
qj
j=1

which can be rewritten as

3N

pV = N kB T
as desired.

82

1 X U
qj
3 j=1 qj

(2.6.4)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-13): Let N monomeric units be arranged along a straight line to form a chain molecule.
Each monomeric units is assumed to be capable of being in state or state . In state , the length
of the unit is a and the energy of the unit is E . In state , the length of the unit is b and the
energy of the unit is E . Derive the relation between the length L of the chain molecule and the
tension applied between both ends of the molecule. Use the canonical ensemble at constant tension.
Solution 2-13): To find L in terms X and , it is noted that L and X are conjugate variables and that ln Y is the
cumulant generating function of the system. Thus,

L=

ln Y
X

(2.13.1)

so an expression for Y (X, ) is required. Denoting the number of units in state as N and the number of units in
state as N allows the energy and length of the system to be given as
E (N , N ) = E N + E N E (N ) = N (E E ) + N E
L (N , N ) = aN + bN L (N ) = N (a b) + N b
by nothing that N = N + N . Thus, Y (X, ) is

Y (X, ) =

N n
N n
o
o
X
X
ZN eXL(N ) =
WN e[E(N )XL(N )]
N =0
N
X

N =0

N!
e[N (E E )+N E XN (ab)XN b]
N !N !
N =0

N
= eN (XbE ) 1 + e(E E +XaXb)
=

(2.13.2)

using Mathematica to evaluate the sum. Applying the expression for Y (X, ) in (2.13.2) to the expression for L to
(2.13.1), using Mathematica , gives

L=

 

N 

ln Y
=
ln eN (XbE ) 1 + e(E E +XaXb)
X
X


ba
= 2N 1 +
1 + e(E E +XaXb)

83

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-14): Show that the partition function Z (N, V, T ) of the canonical ensemble satisfies the
following relation

N

ln Z
N


+V
V,T

ln Z
V


= ln Z
N,T

It is assumed for simplicity that the system is a one-component system made up of N particles and
that only the volume V is involved as an external variable, as T denotes the absolute temperature.
Solution 2-14): The partition function for x of these systems can be written as
x

[Z (N, V, T )]
or, equivalently, as

Z (xN, xV, T )
Thus,
x

[Z (N, V, T )] = Z (xN, xV, T )

holds. Taking the natural log of both sides of the expression in (2.14.1) gives

x ln [Z (N, V, T )] = ln [Z (xN, xV, T )]

(2.14.1)
Differentiating this result with respect to x gives

[ln [Z (xN, xV, T )]]

x


V x
N x
=
+
ln [Z (xN, xV, T )]
x V x
x N x



ln [Z (xN, xV, T )]
= V
+N
V x
N x

ln [Z (N, V, T )] =

For only one system, x = 1, so this result becomes




ln [Z (N, V, T )] = V
+N
ln [Z (N, V, T )]
V
N

84

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-16): Evaluate the contribution of a one-dimensional anharmonic oscillator having a

potential V (q) = cq 2 gq 3 f q 4 to the heat capacity. Discuss the dependence of the mean
p value of
position, q, of the oscillator on the temperature T . Here f, g, c R+ . Usually, g  c1/2 1/ and
f  c2 .
Problem 2-16): First, an expression for the partition function of the system is required. Since the potential added
to the system can be given as
V (q) = cq 2 gq 3 f q 4
Thus, the partition function of the system can be given as

e (cq

Z=

gq 3 f q 4 )

dq =

e (cq

+gq 3 +f q 4 )

dq

This integral has no closed form solution; however, by definition, c  f and c  g so, by rewriting the expression
for the partition function as
Z

e (cq

Z=

+gq 3 +f q 4 )

ecq egq

dq =

+f q 4

dq

the integral can be made solvable by expanding the egq

gives
egq

+f q 4

term in a series. Expanding egq

+f q 4

in a series

1
= 1 + gq 3 + f q 4 + g 2 q 6 2
2

+f q 4

so that the expression for the partition function becomes

Z

ecq

Z=



1
1 + gq 3 + f q 4 + g 2 q 6 2 dq
2

This integral is solvable, using Mathematica , and yields

r
Z=

c3 3



15g 2
3f
1+ 2 +
4c
16c3

(2.16.1)

Now, the heat capacity of the system can be given as C = U/T so an expression for the energy of the system, U ,
is required; however, an expression for U can be found using U = kB T 2 ln Z/T . Thus, the expression for Z in
(2.16.1) is transformed by making the substitution 1/kB T to give the equivalent expression for Z

Z=

ckB T

!


16c3 + 3 4cf + 5g 2 kB T
16c4

Applying this expression for Z to U = kB T 2 ln Z/T , using Mathematica , gives

U = kB T

!


16c3 + 9 4cf + 5g 2 kB T
32c3 + 6 (4cf + 5g 2 ) kB T

85

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Now, this expression for U is applied, using Mathematica , to the expression for C, C = U/T , to give

C=

3kB
256c6 kB

2
2
(16c3 + 3 (4cf + 5g 2 ) kB T )

The first term in (2.16.2) is what would be expected from a linear harmonic oscillator; therefore, the second term in
(2.16.2) arises due to the anharmonicity of the oscillator. Finally, to find the dependence of q on T , can be found
by evaluating the integral

q=

1
Z

qe (cq

gq 3 f q 4 )

dq

(2.16.2)

Using the same approximation scheme that was used when calculating Z, the expression in (2.16.3) becomes
Z
Z
1 (cq2 gq3 f q4 )
1 cq2 gq3 +f q4
qe
qe
e
dq
dq =
Z
Z


Z
1 2 6 2
1 cq2
3
4
qe
1 + gq + f q + g q dq
=
Z
2
12cg
=
12cf + 15g 2 + 16c3

q=

86

(2.16.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-17): As shown in the figure, a chain molecule consists of N units, each having a length a.
The units are joined so as to permit free rotation about the joints. Derive the relation between the
tension X acting between both ends of the three dimensional chain molecule and the distance L
between the ends. (Assume that the vibrational and other forms of energy are independent of the
shape of the molecule).
Solution 2-17): To derive the relation between the tension between the ends of the molecule, X, and the distance
between the ends of the molecule, L, it is noted that L and X are conjugate variables, and that ln Y , where Y is the
partition function of the system, is the cumulant generating function for the system. Thus, L can be expressed as

L=

1 (ln Y )
X

(2.17.1)

To continue, an expression for the partition function, Y , is required. Denoting, as shown in Figure 2.17-1, the
z-axis as the line connecting the ends of the molecule and noting that the tension, overall, acts only in the
z-direction allows the energy of an individual unit to be given as E = Xa cos i .

Figure 2.17-1 : Components of the ith unit of the molecule,

showing the representation of the angles i and i .
Thus, the partition function for a single unit is
Z

li

yi =

eXzi dzi =

eXa cos i sin i di di

where li is the length of the unit projected onto the z axis and zi is the z-coordinate for the ith unit. Evaluating
this integral with Mathematica gives yi as
2

yi
0

eXa cos i sin i di di =

4 sinh [aX]
aX

The paritition function of the entire system, Y , is therefore

Y =

N
Y
i=1

zi =

N
Y
4 sinh [aX]
i=1

aX

87


=

4 sinh [aX]
aX

N
(2.17.2)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Apply the expression for Y from (2.17.2) to the expression for L in (2.17.1), using Mathematica gives
"

N #!
4 sinh [aX]
ln
aX
 

4 sinh [aX]
N
N
ln
=
+ aN coth [aX]
=
X
aX
X

1 (ln Y )
1
L=
=
X
X

88

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-19): Wave motions, having the dispersion formula (relation of the frequency and the
wave number q) = Aq n , exist in a solid. They yield a specific heat because they are excited as
thermal motion at high temperature. Show that the specific heat is proportional to T 3/n at low
temperature.
Solution 2-19): First, an expression for the specific heat capacity of the system, CV ; however, by definition, CV
can be expressed as

CV =

U
T


(2.19.1)
V,N

Thus, an expression for the internal energy of the system, U , is required; however, from the expression in Eqn
(1.82) in Kubo, U can be expressed as
 

 

F
2
U=
U = T
(1/T ) T
T T
V,N

(2.19.2)

so an expression for the Helmholtz Free Energy, F , is required to continued. Noting the expression in Eqn (1.81) in
Kubo, F can be expressed by
F = kB T ln Z

(2.19.3)

therefore, an expression for the partition function, zj , is required. Using the expression in Eqn (1.71 b) in Kubo,
the partition function for one element of this system (harmonic oscillator) with the angular frequency j can be
written as

zj =


X

j
n+ 1
e ( 2 ) kB T

n=0



j ~
1
csch
2
2kB T

where the sum is evaluated using Mathematica . Thus, the expression for the partition function of the entire
system, Z, can be given as

Z=

Y
j

zj =

Y 1
j


csch

j ~
2kB T



Applying this expression for Z to the expression for the Helmholtz Free Energy given in (2.19.3) yields



Y 1

~
j

csch
F = kB T ln Z = kB T ln
2
2k
T
B
j


X  1
j ~
= kB T
ln
csch
2
2kB T
j
( "
1 )#

X
j ~
= kB T
ln 2 sinh
2kB T
j




X
j ~
= kB T
ln 2 sinh
2kB T
j
89

(2.19.4)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Clearly, the energy of the system depends on j so the expression for the partition function of a system with a
continuous energy spectrum from Eqn (1.71 c) in Kubo can be adapted for this system to give

Z
Z=

E()

eE() g () d

(E ()) dE () Z =

Therefore, defining D as the Debye Frequency and assuming that the angular frequencies available to the system
are in the interval [0, D ] 3 [0, D ] R+ allows the expression for the Helmholtz Free Energy given in (2.19.4) can
be rewritten as

F = kB T

X
j






Z D 
~
j ~
F = kB T
ln 2 sinh
g () d
ln 2 sinh
2kB T
2kB T
0

(2.19.5)

To proceed from here, expressions for the spectral function, g (), and the Debye Frequency, D , are required. The
spectral function represents the number of vibrational modes in an arbitrary volume element, thus g (q) is given as


ZZZ
g (q) =

q<

L
dqx
2



L
dqy
2



L
dqz
2


(2.19.6)

2 +q 2 +q 2 <q+dq
qx
y
z

q+dq

=
q

V 2
L3
dq sin dq q 2 dq =
q dq
3
8
2 2

Making the change of variable from q using the dispersion relation = Aq n q =

expression for g (q) to be rewritten as g (), using Mathematica , giving

g (q) =

p
n
/A allows the

 1

1
V 2  d 
V  2/n  d [Aq n ] 
V  2/n
V 2
1
q
dq
=
q
=
=




2
2
2
2
2
dq
2 A
dq
2 2 A
Anq n1

g () =

3n
  3n
V  2/n
V
1
V n
n
=
=
n1
2 2 A
2An 2 A
2n 2 A3/n
An (/A) n

(2.19.7)

To obtain an expression for the Debye Frequency, D , it is noted that D must satisfy
Z

g () d = 3n
0

Applying the expression for g () given in (2.19.7) to this and solving for D , using Mathematica , gives
Z
3n =

g () d =
0

3n

3/n

V D
V n
d =
D =
2
3/n
6A 2
2n A

18 2 An
V

n/3
(2.19.8)

Applying the expression for the Debye Frequency in (2.19.8) and the expression for the Spectral Function given in
(2.19.7) to the expression for the Helmholtz Free Energy given in (2.19.5) yields
D




~
g () d
ln 2 sinh
2kB T
0



Z 18V2 An n/3 
3n
~
V n
= kB T
ln 2 sinh
d
2kB T
2n 2 A3/n
0
Z

F = kB T

90

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Applying this expression for the Helmholtz Free Energy to the expression for U in (2.19.2) gives



Z 18V2 An n/3 
3n
n
1

~
V

kB T
U = T 2
ln 2 sinh
d
T T
2kB T
2n 2 A3/n
0
V,N



Z 18V2 An n/3 
3n

V n
~
kB
d
= T 2
ln 2 sinh
T
2kB T
2n 2 A3/n
0

V,N

18 2 An
V

n/3

=
0

~
V ~  3/n
coth
4n 2 A
2kB T


d

Now, this expression for U is applied to the expression for CV in (2.19.1) to yield

CV =
0

2 n/3



Z 18V An
U
V ~  3/n
~

g () d =
coth
d
T
T
4n 2 A
2kB T
0

18 2 An
V

n/3

18 2 An
V

n/3

18 2 An
V

n/3

Z
=
0

Z
=
0

Z
=
0

From the

kB T
A~

3/n

3/n

 

csch
d
2

3/n

 
V ~
kB T
kB T
2
csch
d
8n 2 T
A~
2
~

3/n
 
V kB kB T
2
csch
d
8n 2
A~
2
V ~
8n 2 T

kB T
A~

term in the expression in (2.19.9), it is clear that CV T 3/n .

91

(2.19.9)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-20): The figure shows the dependence of the heat capacity CV of a solid, at constant
volume, on the temperature. C at high temperature is the classical value (Dulong-Petits Law).
Show that the shaded area above the heat capacity curve in the figure corresponds to the zero-point
energy.
Solution 2-20): Using the same argument as in Problem 2-19, the heat capacity of a solid, at constant volume,
can be expressed as
Z

CV =
0

U
g () d
T

(2.20.1)

Using the expression for the energy of a system of oscillators,





N ~
~
N ~
~
U (, ) =
coth
U (T, ) =
coth
2
2
2
2kB T
given in (1.15.7), the expression for CV in (2.20.1) gives
D

Z
CV =
0





~
N ~
coth
g () d
T
2
2
0




Z D 
N ~
~
=
coth
g () d
T
2
2kB T
0


Z D
~
n~2
csch2
=
g () d
2
4k
T
2k
B
BT
0

U
g () d =
T

(2.20.2)
(2.20.3)

For C , Th
i sothe expression for the energy of the system from (1.15.7) implies that as T ,
~
N ~
kB T ; therefore, C can be given as
2 coth
2
Z

C =
0

U
g () d =
T

(kB T )
g () d
T

(2.20.4)

= kB

g () d

(2.20.5)

Now, the shaded area under the curve can be found using the expression
Z

{C CV } dT
0

Applying the expression for C in (2.20.4) and the expression for CV in (2.20.2) to this expression for shaded area
in the graph yields
Z





Z D
N ~
~
(kB T )
g () d
coth
g () d dT
T
T
2
2kB T
0
0
0




Z D Z 
N ~
~

kB T
coth
dT g () d
=
T
2
2kB T
0
0

T =+
Z D 
N ~
~
=
kB T
coth
g () d
2
2kB T T =0
0
Z D 



N ~
~
= lim
kB T
coth
g () d
(2.20.6)
T +
2
2kB T
0
Z

Z

{C CV } dT =
0

92

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-21): Discuss the heat capacities of one-dimensional and two-dimensional crystals by
following the three-dimensional Debye model discussed in example 3.
Solution 2-21): By examining the expression in (2.19.5) for the Helmholtz Free Energy of a three-dimensional
solid,

F = kB T

X
j






Z D 
j ~
~
ln 2 sinh
F = kB T
ln 2 sinh
g () d,
2kB T
2kB T
0

(2.19.5)

it is clear that the expression for Helmholtz Free Energy of the system, and thus the partition function of the
system, is not affected by the change in dimension due to the fact that the summation is over oscillatory
frequencies and not dimensions. Now, if the expression for the spectral function in (2.19.6) is considered for the two
dimensional case, the integral for the spectral function of a two-dimensional cyrstal becomes


ZZ
g2 (q) =

q<

L
dqx
2



L
dqy
2

q+dq

=
q

L2
L2
q dq
q
d
dq
=
4 2
2

2 +q 2 <q+dq
qx
y

Making the change of variable q 1/c2l + 2/c2t to this expression for the spectral function
L2
L2
q dq =
g2 () =
2
2

2
1
+ 2
c2l
ct


d

(2.21.1)

Applying
the above expression for the spectral function (in the two-dimensional case) to the condition
R D2
g
()
d = 3N , where D2 is the Debye Frequency for the two-dimensional case, gives
0
Z
3N =

D2

D2

L2
2

2c2l + c2t
4 c2l c2t

Z
g2 () d =

1
2
+ 2
c2l
ct

2
d = L2 D
2

2c2l + c2t
4c2l c2t

which implies

3N = L

2
D
2

2
D
=
2

12n c2l c2t

L2 (2c2l + c2t )

(2.21.2)

2
Using Mathematica to apply the expression for D
in (2.21.2) to the expression for the spectral function (in the
2
two-dimensional case) given in (2.21.1) gives

g2 () =

L2
2

1
1
+ 2
c2l
ct


d =

6N
d
2
D
2

(2.21.3)

Applying the expression for the spectral function (in the two-dimensional case) given in (2.21.3) to the expression
for the Helmholtz Free Energy given in (2.19.5) yields
Z
F2 = kB T
0

D2






Z D2 
~
~
6N
ln 2 sinh
g () d = kB T
ln 2 sinh
d
2
2kB T
2kB T
D
0
2

(2.21.4)

Using Mathematica to apply this expression for the Helmholtz Free Energy (for the two-dimensional case) given in
(2.21.4) to the expression for the internal energy of the system, U , given in (2.19.2) gives

93

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

U2 = T 2

F
T


V,N

D2





~
6N
ln 2 sinh
d
2
2kB T
D
0
2
V,N


 Z D



2

~
6N
= T 2
d
kB
ln 2 sinh
2
T
2kB T
D
0
2
V,N
Z D

 


2

~
6N

= T 2 kB
d
ln 2 sinh
2
T
2kB T
D
0
2
V,N


Z D2
~
3N 2 ~
coth
=
2
D
2kB T
0
2
= T 2

1
T

kB T

(2.21.5)

Before proceeding to the heat capacity, CV , steps similar to the the ones above are applied for the one-dimensional
case. Thus, the spectral function from (2.19.6) becomes
Z

L
L
dqx =
dq
2
2

g1 (q) =
q<qx <q+dq

for the one-dimensional case. Making the change of variable q (1/cl + 1/ct ) in this spectral function gives
L
L
dq =
2
2

g1 () =

1
2
+
cl
ct


d

Applying the above expression for the spectral function to the condition
Debye Frequency for the one-dimensional case, gives
Z
3N =

D1

D1

g () d =
0

L
2

1
2
+
cl
ct

R D1
0

(2.21.6)
g () d = 3N , where D1 is the

LD1
d =
2

1
2
+
cl
ct

which implies

3N =

LD1
2

1
2
+
cl
ct


D1 =

6n cl ct
L (2cl + ct )

(2.21.7)

Using Mathematica to apply the expression for D1 in (2.21.7) to the expression for the spectral function (in the
one-dimensional case) given in (2.21.6) gives

g1 () =

L
2

1
2
+
cl
ct


d =

3N
d
D1

(2.21.8)

Applying the expression for the spectral function (in the one-dimensional case) to the expression for the Helmholtz
Free Energy given in (2.19.5) gives
Z
F1 = kB T
0

D2






Z D2 
3N
~
~
ln 2 sinh
g () d = kB T
ln 2 sinh
d
2kB T
2k
T

B
D1
0

(2.21.9)

Using Mathematica to apply this expression for the Helmholtz Free Energy (for the one-dimensional case) given in
(2.21.10) to the expression for the internal energy, U , of the system given in (2.19.2) yields

94

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

U1 = T 2

F1
T


V,N

D2





~
3N
ln 2 sinh
d
2kB T
D1
0
V,N

 Z D




2
3N
~

d
kB
ln 2 sinh
= T 2
T
2kB T
D1
0
V,N
Z D

 


1

~
3N
= T 2 kB
d
ln 2 sinh
T
2k
T

B
D1
0
V,N


Z D1
3n~
~
=
coth
d
2D1
2kB T
0
= T 2

1
T


Z
kB T

(2.21.10)

Now, the expression for the internal energy of the two-dimensional system, U2 , given in (2.21.5) and the expression
for the internal energy of the one-dimensional system, U1 , given in (2.21.10) are independently applied to the
expression for the CV given in (2.19.1). This gives the heat capacity, CV2 , of the two-dimensional system and the
heat capacity, CV1 , of the one-dimensional system, respectively, as

CV2 =


CV1 =

U2
T

U1
T

D2



~
3N 2 ~
coth
d
2
D
2kB T
0
2



1
Z D2
~
3n 3 ~2
=
cosh

1
d
2
k B T 2 D
2kB T
0
2


Z kB T~D2
3 2
T
3nkB
3
d
=
2
~2 D
cosh [] 1
0
2
Z

V,N




~
coth
d
2kB T
0


Z D1
~
3n 2 ~2
2
csch
=
d
4kB T 2 D1
2kB T
0

 
Z kB T~D1
2
n
3kB
2
2
=
csch
d
2D1 ~
2
0
Z

=
V,N

D1

(2.21.11)

(2.21.12)

by making the substitution kB T /~ = d kB T d/~. Finally, the integrals for CV2 and CV1 , given in
(2.21.11) and (2.21.12) respectively, are not easily integrable in terms of elementary functions; however, for low
temperatures, the upper integral limits are essentially infinite. Thus, the integrals in (2.21.11) and (2.21.12) can be
approximated as

kB T D
2
~

CV2 =
0

Z
CV1 =
0

kB T D
1
~





Z
3 2
3 2
3
3nkB
T
3
3nkB
T
3
36nT 2 kB
[3]
d

C
=
d
=
V
2
2
2
2
2
2
~2 D2
cosh [] 1
~
cosh
[]

~
0
D2
D2






Z

2
2
2 2

3kB
n
3kB
n
nT kB

2 csch2
d CV1 =
2 csch2
d =
(2.21.13)
2D1 ~
2
2
~
2

~
D
D
0
1
1

where [3] is the Zeta Function evaluated at 3, [3] = 1.20206 . . . .

95

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 2-22): The potential energy of interatomic bonds in a solid of volume V (the energy
assumed by the solid when all atoms are at rest in their respective equilibrium positions) is denoted
by (V ). The normal frequencies vibration performed by atoms near their equilibrium positions are
expressed by j (V ), (withj = 1, 2, . . . , 3N 6 where N is the number of atoms composing the solid). It
is assumed that the change of the normal frequencies accompanying the change in the volume V can
be expressed by
ln j
=
ln V

(j = 1, 2, . . . , 3N 6)

for all normal frequencies with a common constant R+ (Gruneisens Assumption). Show that the
pressure of the solid is given by

p=

U
d
+
dV
V

Explain the physical meaning of the first and second term. (This equation of state is know as
Mie-Gruneisens equation.) U is part of the internal energy depending on atomic vibrations.
Let if be assumed that
2

(V ) =

(V V0 )
20 V0

(0 and V0 are constants)

Usually, is of the order of 1 3 and 0 CV T /V0  1. (CV is the heat capacity at constant volume and
T is the absolute temperature.) Considering these relations, discuss the thermal expansion of solids
at constant pressure p = 0.
Solution 2-22): Since the solid has 3N 6 modes of oscillations, the energy of the system can be given as

E (V, n1 , n2 , . . . , n3N 6 ) = (V ) +

3N
6 
X
j=1

1
nj +
2


~ j (V )

(2.22.1)

where the (V ) term represents the energy of the solid when no oscillations are occurring (zero-point energy) and



P3N 6 
the j=1
nj + 21 ~ j (V ) represents the vibrational energy. Thus, the partition function of the system can be
given as

Z=

X
n1 =0 n2 =0

= e(V )

e E(V,n1 ,n2 ,...,n3N 6 ) =

n3N 6 =0

n1 =0 n2 =0

=e

(V )

(V )
BT

nj =0

P3N 6
j=1

{(nj + 12 )~ j (V )}

n3N 6 =0

n3N 6 =0
(nj + 21 )~ j (V )

e
=e

nj =0
(

1 )
3N
6 
Y
~ j (V )
2 sinh
2 kB T
j=1

since evaluating the sum

e(V )

n
o
1
1
1
e (n1 + 2 )~ 1 (V ) e (n2 + 2 )~ 2 (V ) e (n3N 6 + 2 )~ 3N 6 (V )

(V )

j=1

=e

n1 =0 n2 =0

3N
6 X

3N
6
Y
j=1

(

~ j (V )
2 sinh
2

1 )

(2.22.2)

e (nj + 2 )~ j (V ) using Mathematica yields

1

96

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

(nj + 21 )~ j (V )

nj =0



1
~ j (V )
= 2 sinh
2

Noting that the Helmholtz Free Energy of a system is defined, in terms of the Partition Function of the system, as
F = kB T ln Z. Thus, using the expression for the partition function of the system in (2.22.2), the Helmholtz Free
Energy of the system can be given as

1 )
~ j (V )

F = kB T ln Z = kB T ln e
2 sinh
2 kB T
j=1
"


1 #

(V )
~ j (V )
= kB T
kB T ln 2 sinh
kB T
2



3N
6
X
~ j (V )
= (V ) + kB T
ln sinh
2
j=1
(V )
k T
B

3N
6
Y

(

(2.22.3)

Noting that the pressure of a system can be calculated, in general, using p = (F/V )T,N allows the pressure of
this system to be expressed, using the expression for F given in (2.22.3), as


p=

F
V


T,N




3N
6
X

~ j (V )
=
(V ) + kB T
ln sinh
V
2
j=1
T,N




3N
6
(V )
X
~ j (V )
=
kB T
ln sinh
V
V
2
j=1

T,N

d (V ) ~

dV
2

3N
6 
X
j=1


coth

~ j (V )
2

j (V )
V


(2.22.4)

Noting that Gruneisens Assumption implies that

ln j (V )
d ln j (V )
=
=
=V
ln V
d ln V

d ln j (V )
dV

V
=
j (V )

dj (V )
dV

V
=
j (V )

j (V )
V

which further implies that

j (V )
j (V )
=
V
V

(2.22.5)

Thus, by applying this expression for Gruneisens Assumption, the expression for the pressure of the system given
in (2.22.4) can be rewritten as

p=




3N 6 
~ j (V ) j (V )
d (V ) ~ X

coth
dV
2 j=1
2
V



3N 6 
d (V )
X ~ j (V )
~ j (V )
=
+
coth
dV
V j=1
2
2
97

(2.22.6)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Referencing the expression in (1.15.7 a) from Problem 1-15, it is clear that the energy due to the vibrations of the
atoms in the solid, U , can be given as

U=





3N
6 
X
H~
~
j (V ) ~
j (V ) ~
coth
U =
coth
2
2
2
2kB T
j=1

(2.22.7)

which allows the expression for p in (2.22.6) to be rewritten as



3N 6 
d (V )
X ~ j (V )
~ j (V )
d (V )
U
p=
+
coth
=
+
dV
V j=1
2
2
dV
V

(2.22.8)

as desired. To find the expression

for the coefficient of volume expansion at constant pressure, , it is noted that


.
To
proceed,
the expression for the pressure in must be differentiated with respect to
is defined by = V1 V
T p,N
T . Before preforming this differentiation, the expression for (V ) given in the problem statement,
2
0)
(V ) = (V2V
, is applied to the expression for the pressure given in (2.22.8) to give
0 V0
d (V )
U
d
p=
+ =
dV
V
dV

"

(V V0 )
20 V0

#
+

V V0
U
U
=
+
V
0 V0
V

Differentiating this expression with respect to T at constant p and N , while noting that V (T ) and U (V (T ) , T ) are
both functions of temperature, gives


p

V V0
U
=0=

+
T
T
0 V0
V p,N




1
V (T )
V

U (V (T ) , T )
=
+ U (V (T ) , T )
+ 2
V (T )
0 V0 T
V (T )
T
T
!
"
#




V U
V
V

U
1
U
+ 2 V
+
=
0 V0 T
V
T
T V T,N
T
#
" 



V U
U V
V
1 U
+

=
+
0 V0
V T
V
V T,N
V2
#
" 



V
U
1 U
U
=

+
+
0 V0
V T
V T,N
V

(2.22.9)

To proceed with, expressions for U/T and U/V are required. Using the expression for U given in (2.22.7),
U/T and U/V can be given, respectively, as





3N 6 
3N 6 
X j (V ) ~
j (V ) ~
X j (V (T )) ~
j (V (T )) ~
U
=
coth
=
coth
T
T j=1
2
2kB T
T j=1
2
2kB T
=

3N
6 
X
j=1

3N
6 
X
j=1

3N
6 
X
j=1

~
2

V
T

j
V




coth









~j
j (V (T )) ~
~j
~
V j
+
sinh2
T

j
2kB T
2
2kB T
2kB T 2
T V





 

~  j 
j ~
~2 j
j ~ 
j
2

V coth

T
V

sinh
j
2
V
2kB T
4kB T 2
2kB T
V





~j
j ~
~2 j
j ~
2

coth
+
sinh
(T j + j )
2
2kB T
4kB T 2
2kB T

98

(2.22.10)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

and

3N
6 
X

U

=
V
V
=

j=1


j (V ) ~
j (V ) ~
coth
2
2kB T



3N
6  
X
~ j
2

j=1

j ~
coth
2kB T





j ~
j ~
~
j
2

sinh
2
2kB T
2kB T
V

3N
6 
X






j ~
j ~2
j ~  j 
~  j 
2
coth
=

sinh

2 V
2kB T
4kB T
2kB T
V
j=1
(
)




3N
6
X
j2 ~2
~  j 
j ~
j ~
=

coth
+
sinh2
2 V
2kB T
4kB T V
2kB T
j=1
Additionally, noting that the specific heat capacity of the system, CV , can be given, in general, as CV =
therefore, for this system, CV can be given as

CV =

U
T


=
V

3N
6
X
j=1


)
~2 j2
j ~
2
sinh
4kB T 2
2kB T

(2.22.11)
U
T V

(2.22.12)

V
by recalling the expression for U
T in (2.22.10) and noting that T = 0 since V is considered to be constant which
implies that the terms dependent on go to zero. Using the expression for CV in (2.22.12) and the expression for
U in (2.22.7), the expression for U
T given in (2.22.10) becomes

(
)




3N
6
X
~2 j2
~j
j ~
j ~
U
2
=

coth
+
sinh
(T + 1) = CV (T + 1) U
T
2
2kB T
4kB T 2
2kB T
j=1
Similarly, the expression for

U
V

(2.22.13)

given in (2.22.11) becomes

(



3N
6
X
j ~
j ~
T
U
=

coth
+
V
V
2
2k
T
V
B
j=1


!)
~2 j2

~
T CV
U
j
sinh2
=

4kB T 2
2kB T
V
V

Now, the expression for U

T given in (2.22.13) and the expression for
p
expression for T
given in (2.22.9) gives

U
V

(2.22.14)

given in (2.22.14) are both applied to the

" 
#



V
1 U
U
U
0=
+
+

0 V0
V T
V T,N
V




V
CV (T + 1) U
T CV
U
U
=
+
+

0 V0
V
V
V
V


V
CV T
CV
U
CV T
U
U
=
+
+

0 V0
V
V
V
V
V
V


CV T
CV
U
U
V
+ 2
+
2

=
0 V0
V
V
V
V

V
U
U
CV
CV T
+ 2 2
+
=
+ 2 2
0 V0
V
V
V
V
99

(2.22.15)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

0
+ VU for U , using Mathematica , yields
Solving the expression p = VV
0 V0

U=

V
(V + V0 (p0 1))
V0 0

Applying this expression for U to the expression in (2.22.15), using Mathematica , gives





Cv

V 2 2 + + 1 + V0 2 2 + 1 (p0 1) =
(1 + 2T )
0 V0
V
Finally, this expression is solved for , using Mathematica , to obtain

(2 2

Cv V0 2 0
+ + 1) 2Cv T V0 3 0 + V V0 (2 2 + 1) (p0 1)

100

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Chapter 3 - Solutions
Problem 3-1): Assuming the ideal gas formula for argon, calcuate the Helmholtz Free Energy,
internal energy, entropy, and chemical potential per molecule. The atomic weight of argon is 39.94.
Solution 3-1): The partition function of a single molecule of Argon can be given as
1
Z= 3
~

dpx

dpy


= Lx Ly Lz

dpz

2mkB T
~2

Lx

3/2

Ly

dqx

dqy

2mkB T
~2

=V

Ly

dqz e

2
2
p2
x +py +pz
2m

3/2

by using Mathematica to evaluate the integrals and by noting that Lx Ly Lz = V . This allows the Helmholtz Free
Energy of the system to be given as
" 

3/2 #

2mkB T
3
2/3 2mkB T
F = kB T ln [Z] = kB T ln V
= kB T ln V
~2
2
~2
which, in turn, allows the internal energy of the system to be expressed as
U = T

F
T


=

3
kB T
2

Applying these expressions for F and U to the definition of the Helmholtz Free Energy, F = U T S, and solving
for S yields
U T S =F


3
3
2mkB T
kB T T S = kB T ln V 2/3
2
2
~2


3
3
2mkB T
kB S = kB ln V 2/3
2
2
~2



3
2mkB T
S = kB 1 + ln V 2/3
2
~2
Finally, the expressions for U and S and the expression V = kB T / p are applied to the definition of the Gibbs Free
Energy, G = U + pV T S, to obtain
G = U + pV T S



3
2mkB T
3
kB T + pV T kB 1 + ln V 2/3
2
2
~2
"
#!
2/3
kB T 2/3 2mkB T
3
3
G = kB T + kB T T kB 1 + ln
2
2
~2
p2/3
"
#!
5/3
2mkB T 5/3
5
3
G = kB T T kB 1 + ln V 2/3
2
2
~2 p2/3
"
#!
5/3
2mkB T 5/3
G = kB T 1 ln V 2/3
~2 p2/3
G=

101

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

which implies that

"
= kB T

1 ln V

5/3

2/3

2mkB T 5/3
~2 p2/3

#!

since, for one molecule, = G/N = G/1 = G. Finally, these expressions for F , U , S, and are numerically
evaluated using Mathematica
F = 8.9628 1013 erg
U = 6.2129 1014 erg
S = 3.1947 1015 erg deg1
= 8.5486 1013 erg

102

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 3-2): The energy difference between the lowest electronic state 1 S0 and the first excited
state 3 S1 of the He atom is 159 843 cm1 . Evaluate the fraction of excited atoms in He gas at 6000 K.
Solution 3-2): The fraction of atoms in a given state is proportional to the probability of the system being in that
state. The probability of a system being in the lth state can be given as

P (l) =

gl el /kB T
j (T )

(3.2.1)

where j (T ) is the internal partition function of the system and gl is the degeneracy of the lth state. Noting the
expression in Eqn (3.3) in Kubo and considering only the first two states of the system, the ground state 1 S0 and
the excited state 3 S1 , allows the internal partition function of the system to be written as
j (T ) =

gl el /kB T = g0 e0 /kB T + g1 e1 /kB T = 1 + 3e1 /kB T

since the degeneracies and energies for the ground and excited states are, respectively, g0 = 1 and g1 = 3 and 0 = 0
and 1 = 159843 cm1 . Therefore, the expression for the probability of the system being in the lth state given in
(3.2.1) becomes

P (1) =

3 el /kB T
g1 e1 /kB T
=
j (T )
1 + 3e1 /kB T

(3.2.2)

In units of cm1 /K, Boltzmanns Constant, kB , can be expressed as kB = 0.6950356 cm1 /K. Applying
T = 6000 K and and 1 = 159843 cm1 to the expression in (3.2.2) and numerically evaluating the result using
Mathematica gives

P (1) =

g1 e1 /kB T
3 el /kB T
= 6.77248 1017
=
j (T )
1 + 3e1 /kB T

103

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 3-3): The rotational motion of a diatomic molecule is specified by two angular variables ,
and the corresponding canonical conjugate momenta p , p . Assuming the form of the kinetic
energy of the rotational motion to be

rot =

1 2
1
p2
p +
2I
2I sin2

derive the classical formula for the rotational partition function

r (T ) =

2IkB T
~2

and calculate the corresponding entropy and specific heat.

Solution 3-2): To find the rotational partition function, the integral

Zrot =

1
~2

d
0

d
0




1 2
1
1
2
p +
p
dp exp

kB T 2I
2I sin2

Z
dp

is evaluated using Mathematica to give

Zrot =

2IkB 3 T
~3

This expression for the rotational partition function allows the rotational contribution to the Helmholtz Free
Energy to be expressed as

Frot = kB T ln

2IkB 3 T
~3

which, in turn, allows the entropy and internal energy of the system to be given, respectively, as

Srot
Urot




Frot
2IkB 3 T
=
= kB 1 + ln
T
~3



Frot
= T 2
= kB T
T
T

using Mathematica to evaluate all three expressions. Finally, the rotational contribution to the heat capacity of the
system can be expressed as

Cv =

Urot
= kB
T

104

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 3-4): Let the Hamiltonian of a rotator with principle moments of inertial (A, B, C) be

H=

p2
1
1
2
2
[(p

cos

p
)
cos

sin

sin

p
]
+
[(p

cos

p
)
sin

sin

cos

p
]
+

2C
2A sin2
2B sin2

Here, , , and are the Eulerian angles as shown in the figure. Derive the rotational partition
function for the polyatomic molecule in the classical approximation.
Solution 3-4): To find the rotational partition function for this system, the integral

r (T ) = Zrot =

dp dp dp d d d eH/kB T

(3.4.1)

must be evaluated; however, Mathematica cannot evaluate this integral in its present form. To proceed, the
expression for the Hamiltonian, H, given in the problem statement is broken up by combining like terms in the
momenta, p , p , & p , such that
H = Hp2 + Hp2 + Hp2 + Hp ,p + Hp ,p + Hp ,p
where Hp2 , Hp2 , Hp2 , Hp ,p , Hp ,p , and Hp ,p are given as

Hp2
Hp2
Hp2
Hp ,p
Hp ,p
Hp ,p

p2 A B + C cot2 B cos2 + A sin2

=
2ABC


p2 A cos2 + B sin2
=
2AB


2
2
p csc B cos2 + A sin2
=
2AB
(B A) p p cos cot sin
=
AB


p p cot csc B cos2 + A sin2
=
AB
(A B) p p cos csc sin
=
AB

This allows the expression for Zrot from (3.4.1) to be rewritten and evaluated, using Mathematica to evaluate the
integrals and simplify each result, to yield

r (T ) = Zrot =

dp dp dp d d d {
0

=
0

Z
d

!#)

kB T

Z

d
Z

Hp2 + Hp2 + Hp2 + Hp ,p + Hp ,p + Hp ,p

exp

"

Z

d
0

dp e

Hp2 /kB T

Z

n H /k T
2
B
dp e p
eHp ,p /kB T eHp ,p /kB T

105

dp e p

o

/kB T

eHp ,p /kB T

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Z
r (T ) = Zrot =

d
s

Z
=

16

dp e

Hp2 /kB T

Z


dp e

"

Hp2 /kB T

eHp ,p /kB T

(A B) (p cot p csc ) sin2 [2]

exp
8 A B kB T A cos2 + B sin2


dp e

2 A B kB T

~3 A B csc2
#))))

Hp2 /kB T

#)))))

p2 (A + B + (B A) cos [2]) cot2

4 A B kB T

Z

exp

16

Z

A B kB T
A + B + (A B) cos

Z

~6

Z

1
= 3
~

"

Z
d

Z


3/2
sin2 2 kB T A1/3 B 1/3 C 1/3 csc2/3
d d d

3 T3

2 A B C 7 kB
=
3
~

8 2 A kB T
~2

1/2 

8 2 A kB T
~2

8 2 B kB T
~2

1/2 

1/2 

3 T3
2 A B C 7 kB
~3

8 2 B kB T
~2

8 2 C kB T
~2

1/2 

8 2 C kB T
~2

1/2
(3.4.2)

1/2
(3.4.2 a)

(3.4.2 b)

which are the desired results, where Mathematica was used to evaluate the equivalence the the expressions given in
(3.4.2) or (3.4.2 a) and (3.4.2 b).

106

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 3-5): The observed values of the rotational specific heat of a HD molecule are given in the
figure. Explain the reason for the appearance of a maximum in this curve using the hight
temperature formula of the rotational partition function.
Solution 3-5): The contribution to the heat capacity from rotational motion, Crot , is expressed, in general, as

Crot =






Urot

Frot
(kB ln [r (T )])
=
T 2
=
T2
T
T
T
T
T
T

(3.5.1)

To proceed, an expression for r (T ) is required. Defining r and as r = ~2 /8 2 IkB and = r /T allows the
rotational partition function of the system to be expressed as

r (T ) =


X


(2l + 1) exp l (l + 1)

l=0

~
8 2 IkB T



n
o
X
(2l + 1) el(l+1)r /T
=
l=0

r () =

n
o
X
(2l + 1) el(l+1)
l=0

The Euler-MacLaurin summation formula can be expressed as

n
X

f (i) =
0

i=0


p 
X


B2k
2k1
2k1
f (x) dx B1 (f (n) + f (0)) +
f
(n) f
(0) + R
(2k)!

(3.5.2)

k=1

where R is an error term (which is small for the proper choice of p), B1 is the first Bernouli Number and, similarly,
B2k is the 2kth Bernouli Number. In applying the Euler-MacLaurin summation formula to the rotational partition
function, r (), from above, f (x) becomes f (l) = = (2l + 1) el(l+1) and allows the rotation partition formula to
be rewritten, approximately, as
Z
r ()

l(l+1)

(2l + 1) e


dl + B1

l(l+1)

lim (2l + 1) e

(2l + 1) e

l(l+1) 

(3.5.3)
l=0


 2k1 h
p 
i
i 
X

B2k
2k1 h
l(l+1)
l(l+1)
lim
(2l
+
1)
e

(2l
+
1)
e
(2k)! l l2k1
l2k1
l=0

k=1

Using Mathematica to evaluate the first two terms in terms in (3.5.3) gives
Z

(2l + 1) el(l+1) dl =


B1


h
i

lim (2l + 1) el(l+1) (2l + 1) el(l+1) 


l=0

= B1 (0 + 1) =

1
2

Choosing p = 4 and using Mathematica to evaluate the sum and derivatives in the third term gives

107

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions


 2k1 h
4 
i
i 
X
2k1 h
B2k

l(l+1)
l(l+1)

(2l
+
1)
e
(2l
+
1)
e
=
lim
(2k)! l l2k1
l2k1
l=0

k=1

4 2
3
4
5
6
7
= +
+
+
+

6 15 315 315 560 1512 21600 1209600

Using Mathematica to apply these expressions for the terms in (3.5.2) to (3.5.2) yields

r ()

1
1

4 2
3
4
5
6
7
+ +
+
+
+

3 15 315 315 560 1512 21600 1209600

Using this expression for the rotational partition function, the Helmholtz Free Energy of the system due to
rotational motion, Frot , can be expressed as
1

4 2
3
4
5
6
7
1
+ +
+
+
+

kB T ln [r ()] = kB T ln
3 15 315 315 560 1512 21600 1209600


Frot

= kB T ln [] kB T

= kB T ln

2
8 3
59 4
kB T
kB T
kB T
3
90
2835
56700


 
 
 
r
r
kB 2r
8kB 3r
59kB 4r
kB

T
3
90 T
2835 T 2
2835 T 3

where the last statement is obtained using Mathematica to expand this expression for Frot as a Talyor Series, with
respect to , about = 0 and then making the substitution r /T . This allows the internal energy of the
system due to rotation, Urot , to be given as

Urot = T 2


 
 
 
 
 
Frot
1
r
r
kB 2r
8kB 3r
59kB 4r
= T 2
kB T ln
kB

T
T T
T
3
90 T
2835 T 2
2835 T 3

= kB T kB

r
kB

3
45

2r
T

8kB
945

3r
T2

551kB
56700

4r
T3

using Mathematica to evaluate the derivatives and simplify the resulting expression. This expression for Urot allows
the contribution to the heat capacity of the system due to rotational motion, Cv,rot , to be expressed as

Cv,rot


 
 
 
Urot

r
kB 2r
8kB 3r
551kB 4r
=
=
kB T kB

T
T
3
45 T
945 T 2
56700 T 3
kB
= kB +
45

2r
T2

16kB
+
945

3r
T3

551kB
+
18900

108

4r
T4

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 3-6): Find the ratio of the number of ortho-hydrogen molecules to that of para-hydrogen
molecules in a high temperature H2 gas. How about the D2 gas?
Solution 3-6): Noting the expressions in Eqn (3.10 a) and Eqn (3.10 b) from Kubo allows the nuclear rotation
internal partition functions for Fermi and Bose particles can be given, respectively, as

jFnucrot = sn (2sn + 1) reven + (sn + 1) (2sn + 1) rodd

(3.6.1)

jBnucrot = (sn + 1) (2sn + 1) reven + sn (2sn + 1) rodd

(3.6.2)

where reven and rodd can be given as



l (l + 1) ~2
(2l + 1) exp 2
8 IkB T
l=0,2,4,...




X
r
(2l + 1) exp l (l + 1)
=
T

reven =

l=0,2,4,...

= 1 + 5e6

rodd =

r
T

+ 9e20

r
T

+ 13e42

r
T

+ 17e72

r
T

+ 21e110

r
T

(3.6.3)

X
l=1,3,...

X
l=1,3,5,...

= 3e2

r
T



l (l + 1) ~2
(2l + 1) exp 2
8 IkB T



r
(2l + 1) exp l (l + 1)
T

+ 7e12

r
T

+ 11e30

r
T

+ 15e56

r
T

+ 19e90

r
T

+ 23e132

r
T

(3.6.4)

Since ortho-nuclear hydrogen corresponds to the odd rotational partition function and para-nuclear hydrogen
corresponds to the even rotational partition function and since H2 is a Fermion, the two terms in the expression in
(3.6.1) are compared

(sn + 1) (2sn + 1) rodd : sn (2sn + 1) reven

|
{z
} |
{z
}
Ortho-Hydrogen

Para-Hydrogen

3 rodd : 1 reven

(3.6.5)

To proceed, the expressions for rodd and reven given, respectively, in (3.6.3) and (3.6.4) must be compared. Using
Mathematica it is clear that at T , the system becomes

limT

rodd
reven

limT

rodd
reven

limT

rodd
reven

11
v1
13

21
v1

23

31

v1
33

for increasing degrees of expansion for rodd /reven . This can be represented graphically as

109

(3.6.6)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Figure 3.6-1 : Plot of rodd /reven and reven /rodd for increasing
degrees of expansion for rodd and reven .

Figure 3.6-2 : Plot of rodd reven and reven rodd for increasing
degrees of expansion for rodd and reven .
Applying the result represented in (3.6.6), Figure 3.6-1, and Figure 3.6-2 to the expression in (3.6.5) finally gives,
for H2 , the ratio of the number of Ortho-Hydrogen to Para-Hydrogen molecules as
(sn + 1) (2sn + 1) rodd : sn (2sn + 1) reven
|
{z
} |
{z
}
Ortho-Hydrogen

Para-Hydrogen

rodd
3
:1
reven
3:1
110

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Since ortho-nuclear deuterium corresponds to the even rotational partition function and para-nuclear deuterium
corresponds to the odd rotational partition function, for D2 , the equivalent expression to the one for H2 in (3.6.5) is
(sn + 1) (2sn + 1) reven : sn (2sn + 1) rodd
{z
} |
{z
}
|

(3.6.7)

Para-Deuterium

Ortho-Deuterium

Since D2 is a Boson, it has spin 1, so the expression in (3.6.7) becomes

(sn + 1) (2sn + 1) reven : sn (2sn + 1) rodd
{z
} |
{z
}
|
Para-Deuterium

Ortho-Deuterium

(1 + 1) (2 + 1) : (2 + 1)
2:1
by using the result represented in (3.6.6), Figure 3.6-1, and Figure 3.6-2 to the expression in (3.6.7).

111

(3.6.8)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 3-7): The rate of ortho-para conversion of hydrogen molecules is so slow that
ortho-hydrogen and para-hydrogen cam be separated as though they are different kinds of gases.
Calculate the specific heat at low temperatures and show that para-hydrogen gas has the larger
specific heat.
Solution 3-7): Since the only difference between ortho-nuclear and para-nuclear hydrogen is in their rotational
partition functions, the expressions for rodd and reven used in Problem 3-6 and given, respectively, in (3.6.3) and
(3.6.4) are referenced
reven = 1 + 5e6
rodd = 3e2

r
T

r
T

+ 9e20

+ 7e12

r
T

r
T

+ 13e42

+ 11e30

r
T

r
T

+ 17e72

+ 15e56

r
T

r
T

+ 21e110

+ 19e90

r
T

r
T

+ 23e132

(3.6.3)
r
T

(3.6.4)

Since we are considering the system at low temperature, only the first few terms of the expressions for rodd and
reven in (3.6.3) and (3.6.4) are kept. Thus, rodd and reven are approximated as
r
r
reven
= 1 + 5e6 T + 9e20 T

(3.7.1)

r
r
r
rodd
= 3e2 T + 7e12 T + 11e30 T

(3.7.2)

Since the Helmholtz Free Energy of a system can be given as F = kB T ln [Z], the Helmholtz Free Energy of
para-nuclear Hydrogen, Feven , can be given as
h
i
r
r
Feven = kB T ln [reven ] = kB T ln 1 + 5e6 T + 9e20 T
by noting that the partition function of para-nuclear hydrogen is represented by the even rotational partition
function given in (3.7.1). Similarly, Helmholtz Free Energy of ortho-nuclear Hydrogen, Fodd , can be given as
h
i
r
r
r
Fodd = kB T ln [rodd ] = kB T ln 3e2 T + 7e12 T + 11e30 T
by noting that the partition function of ortho-hydrogen is represented by the odd rotational partition function
given in (3.7.2). Using the expression for Feven , the relation

U = T

F
T


(3.7.3)

and Mathematica allows the internal energy of the ortho-nuclear Hydrogen, Uodd , to be given as

Ueven = Uortho = T

Feven
T


= 30 kB r

6 + e14
9 + 5e14

r
T

r
T

+ e20

r
T

Similarly, using the relation in (3.7.3), the expression for Fodd , and Mathematica allows the internal energy of the
para-nuclear Hydrogen, Ueven , to be given as

Uodd = Upara = T

Fodd
T


= 14 kB r

112

1
22 + 5e18 T
+
7 11 + 7e18 Tr + 3e28 Tr

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Now, using the expression the internal energy of ortho-nuclear Hydrogen, Ueven , the relation

Cv =

U
T

(3.7.4)

and Mathematica allows the heat capacity of ortho-nuclear hydrogen to be given as

Cv,even = Cv,ortho

Ueven
180 kB 2r e14
=
=
T
T2

r
T

49 + 20e6
9 + 5e14

r
T

r
T

+ e20

r
T

+ 3e20

r
T

Similarly, using the expression the internal energy of para-nuclear Hydrogen, Uodd , the relation in (3.7.3) and
Mathematica allows the heat capacity of para-nuclear hydrogen to be given as

Cv,odd = Cv,para

Uodd
84 kB 2r e18
=
=
T
T2

r
T

297 + 308e10
11 + 7e18

r
T

r
T

+ 25e28

+ 3e28

r
T

r
T

Finally, to show that, at low temperatures, the heat capacity of para-hydrogen is larger than the heat capacity of
ortho-hydrogen we plot Cv,para and Cv,ortho versus temperature using Mathematica to give

Figure 3.7-1 : Plot of Cv,para (top) and Cv,ortho (bottom) vs. T

By examining Figure 3.7-1, it is clear that, at low T , Cv,para > Cv,ortho , as desired.

113

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 3-13): Derive the formula for the pressure, p, of a real gas using the virial theorem

p=

 

Z n
o
1
kB T
1
1 eu(r)/kB T 4r2 dr + o
1+
v
2v 0
v

(v = V /N )

where the inter-molecular potential, u (r), is assumed to be the function of the distance r only.
Solution 3-13): If the intermolecular potential u (r) is assumed to be such that

U=

N N 1
1XX
u (rij )
2 j=1 i=1

(3.13.1)

i6=j

If the expression in (2.6.4) from Problem 2-6 is rewritten as

3N

pV = N kB T

= N kB T

1 X U
1 X U
qj
~rj
= N kB T
3 j=1 qj
3 j=1 ~rj


N N 1

1XX
~rj
[u (rij )]
6 j=1 i=1
~rj
i6=j



du
N (N 1)
~r
= N kB T
6
d~r

du 
To proceed, an expression for ~r d~r is required. From the definition of average value
Z

du U/kB T
r12
e
d~r1 d~rN
Z dr12
eU/kB T d~r1 . . . d~rN
Z
Z
du u(r12 )/kB T
2
V
d~r1 d~r2 r12
e
dr12
Z
du u(r)/kB T
V 1 d~r ~r
e
dr
Z
du u(r)/kB T
V 1
4r2 dr r
e
dr
Z0
du u(r)/kB T
V 1
4r3 dr
e
dr
0



du
~r
=
d~r

(3.13.2)

d u(r)/kB T
u(r)/kB T
Using the integration by parts scheme w = 4r3 , w0 = 12r2 , v 0 = du
= kB T dr
e
,
dr e


u(r)/kB T
v = kB T e
1 allows the expression in (3.13.3) to be rewritten as



Z
du
du u(r)/kB T
~r
4r3 dr
V 1
e
d~r
dr
0
Z 


 
u(r)/kB T 
2
u(r)/kB T
1
V
kB T 1 e
r 1e
dr
 12kB T
0
0
Z 

kB T
12
r2 1 eu(r)/kB T dr
V
0
114

(3.13.3)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Applying this expression to the expression in (3.13.2) and noting the N  1 yields

Z
 
N (N 1)
kB T 2 
r 1 eu(r)/kB T dr
12
6
V
0

Z
 


kB T 2 
2
N kB T + 2 N N
r 1 eu(r)/kB T dr
V
0

Z
 

(N 1)
2
N kB T 1 + 2
r 1 eu(r)/kB T dr
V
0

Z
 

2N
N kB T 1 +
r2 1 eu(r)/kB T dr
V 0

pV N kB T +

which implies

Z
 
N kB T
2N 2 
u(r)/kB T
p
dr
r 1 e
1+
V
V 0

115

(3.13.4)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 3-15): The vibration of a diatomic molecule exhibits anharmonicity, when the amplitude
becomes very large, owing to the characteristic form of the potential shown in the figure. The
energy levels can be given approximately by

n =

1
n+
2


2
1
~
~ e n +
2

(n = 0, 1, 2, . . . )

when e is a parameter used to represent the degree of anharmonicity. Calculate the effect of
anharmonicity up the vibrational specific heat up to the first order in e .
Solution 3-15): The vibrational partition function of the system, v (T ), can be given as

"

1
v (T ) =
exp
kB T
n=0

1
n+
2


~ e

1
n+
2

!#

2
~

Expanding this expression for v (T ), in terms of e and disregarding all terms greater than first order in e yields

v (T ) =

n=0

4kB T (1 + 2n) e ~ k~T (n+ 12 )

e B
4kB T

Using Mathematica to evaluate the sum over n yields

1
v (T ) =
8kB T

~
csch
2kB T

 


~
2
e ~ 4kB T + 2e ~ csch
2kB T

(3.15.1)

Noting that the heat capacity can be given as




2
Cv =
kB T
[ln [v (T )]]
T
T
applying the expression in (3.15.1) and expanding in a series before each differentiation using Mathematica yields

~
2 ~2
csch2
4kB T 2
2kB T


Cv =

2 ~2 csch4

~
2kB T





 
~
~
~2 + ~ cosh
2kB T sinh
e
kB T
kB T
2 T3
4kB

116

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 3-18): Consider a gas composed of molecules interacting with the intermolecular potential
(a)
u (r) = /rn

n > 0 and R+

for

(b)
u (r) =

u0 R

for
for
for

r<a
a<r<b
r>b

Calculate the second virial coefficient and the Joule-Thomson coefficient. Discuss the
Joule-Thomson effect.
Solution 3-18): Using the expression from Eqn (3.23) in Kubo
e u(rij ) = 1 + fij

fij = e u(rij ) 1

and the expression from Eqn (3.26) in Kubo,

bl =

1
l!V

Z X nY

fij

d~r1 . . . d~rl

allows the second viral coefficient, b2 , to be found using the expression

Z Z

1
b2 =
2!V

1
fij d~r1 d~r2 =
2!V

Z Z

1
fij d~r1 d~r2 =
2!V

Z Z 


e u(rij ) 1 d~r1 d~r2

Converting this integral to be over position of one particle relative to the other, instead of the position of each
particle in relation to a common origin, and then converting that result to an integration in spherical coordinates
over all space allows B (T ) = V b2 to be given as
1
B (T ) = V
2V

Z 

u(~
r)

Z Z Z


1 2  u(r)
1 d~r =
e
1 r2 sin d d dr
2 0
0
0

(3.18.1)

For the potential from Part A, the cases were n > 3 and 0 n 3 are considered separately. Applying u (r) =
= /rn to the expression in (3.18.1), evaluating the integrals over and , and then simplifying the result yields
allows B (T ), for Part A, to be expressed as

B (T ) =

1
2

Z
0

Z
0

Z

n
e /r 1 r2 sin d d dr = 2

1 e /r

r2 dr

(3.18.2)

To proceed, the integration by parts scheme

w = 1 e /r

2
v = r3
3
v 0 = 2r2

w0 = n rn1 e /r

is used, where Mathematica is used to evaluate the derivative going from w to w0 and the integral going from v 0 to
v, to allows the integral in (3.18.2) to be rewritten as
117

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions


Z

r= 2
n
2
3
/r n
B (T ) = r 1 e
+ n
r2n e /r dr
3
3
0
r=0
 2


3
/r n r=
To proceed with the expression in (3.18.3), the 3 r 1 e
term must be evaluated. To
r=0


2
3
/r n
accomplish this, 3 r 1 e
is plotted for the case 0 < n 3 and the case n > 3 to give

Figure 3.18-1 : Plot of 23 r3 1 e /r

Figure 3.18-2 : Plot of 32 r3 1 e /r

(3.18.3)

vs r for n = 1, 2, 3

vs r for n > 3
n

From the plots in Figure 3.18-1 and Figure 3.18-2, it is clear that 32 r3 1 e /r diverges for the n = 1, 2, 3
n

case and converges for 23 r3 1 e /r for the n > 3 case. Thus, the n = 1, 2, 3 case is ignored. Further, the
plot in figure in (3.18-2) implies that
118

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions




n
2
lim r3 1 e /r
=0
r0
3

and




n
2
lim r3 1 e /r
=0
r
3

which allows the expression in (3.18.3) to be rewritten as

2
B (T ) = n
3

r2n e /r

dr

(3.18.4)

1/n

Making the change of variable r (x/ )

x rn implies the differential relationship

1/n
and the change in integration bounds r = 0 x = and r = x = 0 as evidenced in
dr = n1x x
the figure below

Figure 3.18-3 : Plot of x = rn for various values of n > 3

Thus the expression in (3.18.4) to be rewritten as
2
B (T ) = n
3

2n /r n

2
dr =
3x

((x)1/n )

1/n

(x)

n  x 3/n

dx

Using Mathematica allows this integral to be evaluated to give



2
n3
3/n
B (T ) = ( )

3
n

for n > 3

(3.18.5)

which is the second virial coefficient for Part A. For Part B, the intermolecular potential

u0 R
u (r) =

for
for
for

r<a
a<r<b
r>b

u (r) =

u0 R+

is applied to the expression in (3.18.1) and integrated of and to yield

119

for
for
for

r<a
a<r<b
r>b

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

"Z

B (T ) = 2

1 r dr +

u0

1 r dr +

1 r dr

(3.18.6)

Noting that e = 0 and e 0 = 1, allows the expression in (3.18.6) to be rewritten as

" Z
B (T ) = 2

r dr +

u0

1 r2 dr +

r2 dr +

(1 1) r dr
b

" Z
= 2

e u0 1 r2 dr

Finally, this expression in evaluated using Mathematica to give

B (T ) =

2
eu0 a3 + b3 eu0 1
3

(3.18.7)

which is the second virial coefficient for Part B. Since the Joule-Thomson coefficient is given by


T
p


H

1
=
Cp

dB
B
T
dT


(3.18.8)

Making the substitution 1/kB T in the expressions in (3.18.5) and (3.18.7) yields
2
B (T ) =
3

kB T

3/n

n3


for n > 3

(3.18.5 a)

for the intermolecular potential in Part A and




2
eu0 /kB T a3 + b3 eu0 /kB T 1
3

B (T ) =

(3.18.7 a)

for the intermolecular potential in Part B. Applying the expressions for B (T ) in (3.18.5 a) and (3.18.7 a) to the
expression for the Joule-Thomson coefficient in (3.18.8) and using Mathematica yields


T
p


=
H

2 (3 + n)
n2 C p

kB T

3/n



3

n

as the Joule-Thomson coefficient for Part A and



T
p


=
H





2
b3 a3 (kB T u0 ) eu0 /kB T b3 kB T
3Cp kB T

as the Joule-Thomson coefficient for Part B.

120

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 3-22): Give an explicit formula for the cluster integral b3 , from Eqn (3.26) in Kubo, and
derive the relation

b3 =

1 2 1
+ 2
2 1 3

where 1 and 2 are the irreducible cluster integrals defined by

1 =

1
V

ZZ
f12 d~r1 d~r2

and

2 =

1
2V

ZZZ
f12 f23 f31 d~r1 d~r2 d~r3

Solution 3-22): Three molecules can be connected by the bond fij in the following ways

Figure 3.22-1 : Plot of the bonds represented by

1
3! V

Figure 3.22-3 : Plot of the bonds represented by

ZZZ

1
3! V

f21 f23 d~r1 d~r2 d~r3

Figure 3.22-2 : Plot of the bonds represented by

1
3! V

ZZZ
f12 f13 d~r1 d~r2 d~r3

Figure 3.22-4 : Plot of the bonds represented by

ZZZ

1
3! V

f31 f32 d~r1 d~r2 d~r3

121

ZZZ
f12 f23 f31 d~r1 d~r2 d~r3

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Using the expression from Eqn (3.26) in Kubo

bl =

1
l!V

nY

fij

d~r1 . . . d~rl

all bonding combinations

for the l = 3 case gives

b3 =

1
3!V

ZZZ
[f21 f23 + f12 f13 + f31 f32 + f12 f23 f31 ] d~r1 d~r2 d~r3

which can be rewritten as

 Z

 Z

Z Z
f21 d~r1
f23 d~r3 d~r2 +
f12 d~r2
f13 d~r3 d~r1 +
Z
 Z


ZZZ
f12 d~r2
f13 d~r3 d~r1 +
+
f12 f23 f31 d~r1 d~r2 d~r3
 ZZZ

ZZZ
1
3
f12 f13 d~r1 d~r2 d~r3 +
f12 f23 f31 d~r1 d~r2 d~r3
=
6V

b3 =

1
3!V

Z Z

Recalling that 1 and 2 are the irreducible cluster integrals defined by

1 =

1
V

ZZ
f12 d~r1 d~r2 =

1
V

ZZ
f23 d~r2 d~r3 =

1
V

ZZ
f13 d~r1 d~r3

and

2 =

1
2V

ZZZ
f12 f23 f31 d~r1 d~r2 d~r3

and noting that 12 can be rewritten as

ZZZ
ZZZ
ZZZ
1
1
1
f
f
d~
r
d~
r
d~
r
=
f
f
d~
r
d~
r
d~
r
=
f31 f32 d~r1 d~r2 d~r3
12
13
1
2
3
21
23
1
2
3
V2
V2
V2
ZZZ
ZZZ
ZZZ
1
1
1
= 2
f12 f13 d~r12 d~r13 d~r23 = 2
f21 f23 d~r21 d~r23 d~r13 = 2
f31 f32 d~r31 d~r32 d~r12
V
V
V
ZZZ
ZZZ
ZZZ
1
1
1
f12 f13 d~r12 d~r13 =
f21 f23 d~r21 d~r23 =
f31 f32 d~r31 d~r32
=
V
V
V

12 =

allows the expression in (3.22.1) to be rewritten as

b3 =

 1
1 
1
3V 12 + 2V 2 = 12 + 2
6V
2
3

as desired.

122

(3.22.1)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Chapter 4 - Solutions
Problem 4-1): Let the density of states of the electrons in some sample be assumed to be a constant
D for > 0 ( D = 0 for < 0 ) and the total number of electrons be equal to N .
(i) Calculate the Fermi Potential, 0 , at 0 K.
(ii) Derive the condition that the system is non-degenerate.
(iii) Show that the specific heat is proportional to T when the system is highly degenerate.
Solution 4-1): Since the number of particles in the system, N , can be given as
0

Z
N=

f () D () d = 0 D
0

where D () = D is the constant density of states at some energy and 0 is the Fermi Potential. This allows the
Fermi potential can be given as

0 =

N
D ()

To derive the condition for the non-degenerate case, it is noted that n

 1 must hold. For Fermi particles, n
is
given as

n
=

1
e( )

(4.1.1)

+1

The condition n
 1 must hold for any energy, , in (4.1.1). Applying the condition for non-degeneracy, n
 1,
to the expression for n
in (4.1.1) yields
1n

1

1
e( )

+1

e( )  0
e  e

(4.1.2)

Since , R+ it is clear that e [0, 1]. Therefore, the expression in (4.1.2) implies that
e  e
e  1

(4.1.2 a)

Using the expression in Eqn (4.3) in Kubo, where f () = n

() and D () = D allows the chemical potential of the
system to be defined as
Z
N=

Z
f () D () d = D

Z
n
() d = D

d
e( ) + 1

Applying the non-degenerate condition in (4.1.2 a) to the above expression and integrating using Mathematica
yields
123

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Z
N =D

d
e( )

+1

e( ) d = D

This expression can be rewritten as

N =D

e
D
e =

which, when applied the the condition for non-degeneracy in (4.1.2 a) yields
e  e
D
1
N

e =

D
N

1

D
N

Using the expression in Eqn (4.2) in Kubo allows the internal energy of the system, U , to be given as

Z
U=

f () D () d
0

Applying the fact that D () = D and f () = n

(), as given in (4.1.1), to the above expression for U and then
evaluating the integral with Mathematica yields
Z
U=

Z
f () D () d = D

e() + 1

d =

D
e

Z
0

d
e + 1

(4.1.3)

Since the system is begin considered for the case where it is highly degenerate, n
v 1. Applying this to the
expression for n
in (4.1.1) yields
1vn

1
e( ) + 1
v0

1v
e( )

e v e

(4.1.4)

Again, since , R+ , it is clear that e [0, 1]. Therefore, the expression in (4.1.4) implies that
e v e
e v 1

(4.1.4 a)

Applying the condition from (4.1.4 a) to the expression for U in (4.1.3) yields

U=

D
e

Z
0

d = D
e + 1

Using Mathematica to evaluate the integral in (4.1.3 a) yields

124

Z
0

d
e + 1

(4.1.3 a)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Z
U =D
0

1
2 2 2
d =
D kB
T
e + 1
12

(4.1.3 b)

Since Cv = U/T , the expression for U in (4.1.3 b) allows Cv to be given as

Cv =

1
2 2
D kB
T
6

demonstrating the heat capacitys linear dependence on the temperature, as desired.

125

(4.1.5)

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 4-2): At finite temperatures, the Fermi distribution, f (), can be represented in a rough
approximation by a broken line, as shown in the figure. Give an elementary explanation of the
origin of linear specific heat at low temperatures by use of this approximation.
Solution 4-2):

126

Jonathan McFadden
Spring 2010

PHYS 7400
Kubo Solutions

Problem 4-3): Let some physical quantity I of a system of electrons be expressed by an integral
containing the Fermi distribution, f () :
Z
I=

Z
g () f () d =

() D () f () d

textbfwhere D () is the density of states. Derive the following formulae when the degeneracy is sufficiently strong:



I
T


=

I
=
T T


I
=
T N

127