Statistical Mechanics - Homework Assignment 2

Alejandro Gomez Espinosa

February 17, 2013

Pathria 2.7 Derive (i) an asymptotic expression for the number of ways in which a given energy E can
be distributed among a set of N one-dimensional harmonic oscillators, the energy eigenvalues of the
oscillators being
_
n +
1
2
_
, n = 0, 1, 2, 3.., and (ii) the corresponding expression for the volume of
the relevant region of the phase space of this system. Establish the correspondence between the two
results, showing that the conversion factor
0
is precisely h
N
.
To answer the rst question, let us rst dene the total energy of N harmonic oscillators:
E =

r
_
n
r
+
1
2
_
=
_
R +
N
2
_

subsequently:
R =
E

N
2
(1)
Then, to determine the number of distinct ways in which this energy can be distributed, let us use
eq. 3.8.25:
=
(R +N 1)!
R!(N 1)!

N1
(R +N)!
R!N!

RN
R
N
N!
Replacing (1) in the last result and, considering that R N, we found:

(E/)
N
N!
(2)
which is the asymptotic expression for the number of ways we can distribute the given energy.
Next, to calculate the volume of the phase space, let us recall the Hamiltonian of our system:
H =
N

r=1
p
2
r
2m
+
m
2
q
2
r
2
Making the following substitution x =
p

2m
and y = q
_
m
2
2
for convenience in the volume calcula-
tion:
V (E) =
_ _
0

N
r=1
HE
d
N
p d
N
q
=
_
4m
m
2
_
N/2
_ _
0

N
r=1
x
2
r
+x
2
r
E
d
N
x d
N
y

gomez@physics.rutgers.edu
1
where the last integral has the same form as the volume of an n-dimentional sphere compute in the
Appendix C. Therefore, using eq. C.7a from such Appendix for a two dimensional case:
V (E) =
_
2

_
N

N
E
N
N!
=
1
N!
_
2E

_
N
(3)
Finally, dividing (3) by (2), we nd the correspondence between the two results:
V

=
1
N!
_
2E

_
N
(E/)
N
N!
= (2)
N
= h
N
Pathria 2.8 Following the method of Appendix C, replacing equation (C.4) by the integral
_

0
e
r
r
2
dr = 2 (4)
show that
V
3N
=
_
...
_
0

N
i=1
r
i
R
N

i=1
_
4r
2
i
dr
i
_
=
(8R
3
)
N
(3N)!
(5)
Using this result, compute the volume of the relevant region of the phase space of an extreme rela-
tivistic gas ( = pc) of N particles moving in three dimensions. Hence, derive expressions for the
various thermodynamic propierties of this system and compare your results with those of Problem
1.7.
Using (4) and the procedure of Appendix C:
2
n
=
r
i
=
_
...
_
r
i
=
exp (

n
i=1
r
i
)
(4)
N

_
4r
2
i
dr
i
_
=
1
(4)
N
_

0
e
R
2
_
3NC
N
R
3N1
_
dR
=
3NC
N
(4)
N
_

0
e
R
2
R
3N1
dR
=
3NC
N
(4)
N
(3N 1)!
2
N
(4)
N
3N(3N 1)!
= C
N
(8)
N
(3N)!
= C
N
Replacing in eq. C.2:
V
3N
= C
N
R
3N
=
(8R
3
)
N
(3N)!
(6)
Then, to derive thermodynamic propierties of this system, let us calculate the multiplicity of the
microstates accessible to the system:
=

0
=
(8R
3
)
N
(3N)!
V
3N
h
3N
=
_
V R
h
_
3N
(8)
N
(3N)!
(7)
2
Using the energy in the case of the extreme relativistic gas:
E =
3N

i
p
i
c
E
c
=
3N

i
p
i
=

i
_
p
2
xi
+p
2
yi
+p
2
zi
We nd a relation for the entropy:
S = k ln = k ln
_
_
V R
h
_
3N
(8)
N
(3N)!
_
k ln
_
_
EV
hc
_
3N
(8)
N
(3N)!
_
(8)
Finally, let us compare our results with the ones found in Pathria 1.7.
P
T
=
_
S
V
_
N,E
=

V
_
k ln
_
_
EV
hc
_
3N
(8)
N
(3N)!
__
=

V
_
k
_
ln(EV )
3N
(8)
N
ln(hc(3N)!
__
=

V
_
k
_
N ln(8(EV )
3
) ln(hc(3N)!
__
=
kN
8(EV )
3
_
24E
3
V
2
_
=
3Nk
V
PV = 3NkT
Pathria 3.15 Show that the partition funtion Q
N
(V, T) of an extreme relativistic gas consisting of N
monatomic molecules with energy-momentum relationship = pc, c being the speed of light, is given
by
Q
N
(V, T) =
1
N!
_
8V
_
kT
hc
_
3
_
N
(9)
Study the thermodynamics of this system, checking in particular that
PV =
1
3
U,
U
N
= 3kT, =
4
3
(10)
Next, using the inversion formula (3.4.7), derive an expression for the density of states g(E) of this
system.
To calculate the partition function, we can use the result from 3.5.8. But in this case
H(q, p) =
N

i=1

i
=
N

i=1
p
i
c
3
then:
Q
N
(V, T) =
1
N!h
3N
_
V
_

0
e
pc/kT
_
4p
2
dp
_
_
N
=
1
N!
_
4V
h
3
_

0
e
pc/kT
p
2
dp
_
N
=
1
N!
_
4V
h
3
2
_
kT
c
_
3
_
N
=
1
N!
_
8V
_
kT
hc
_
3
_
N
(11)
Then, using (11), let us calculate the internal energy U:
U =

ln Q
=

ln
_
_
1
N!
_
8V
_
1
hc
_
3
_
N
_
_
= N

ln
_
8V
(N!)
1/N
_
1
hc
_
3
_
= N

ln
_
h
3
c
3
(N!)
1/N
8V

3
_
= N

_
ln
h
3
c
3
(N!)
1/N
8V
+ ln
3
_
= N

_
ln
h
3
c
3
(N!)
1/N
8V
+ 3 ln
_
=
3N

U
N
= 3kT (12)
To compute the pressure, we must rst dene Helmholtz free energy:
A(N, V, T) = kT ln Q
N
(V, T) = NkT
_
ln
h
3
c
3

3
(N!)
1/N
8
ln V
_
thus,
P =
_
A
V
_
N,T
=
NkT
V
=
N
V
and replacing (12):
P =
N
V
=
U
3V
(13)
Finally, to calculate :
C
V
=
_
U
T
_
V
= 3Nk (14)
4
C
P
=
_

T
(U +PV )
_
N,P
= 3Nk +Nk = 4Nk (15)
using (14) and (15) :
=
C
P
C
V
=
4NkT
3NkT
=
4
3
(16)
Pathria 3.30 The energy levels of a quantum-mechanical, one-dimensional, anharmonic oscillator may
be approximated as

n
=
_
n +
1
2
_
x
_
n +
1
2
_
2
; n = 0, 1, 2, ... (17)
The parameter x, usually 1, represents the degree of anharmonicity. Show that, to the rst order
in x and the fourth order in u(= /kT), the specic heat of a system of N such oscillators is given
by
C = Nk
__
1
1
12
u
2
+
1
240
u
4
_
+ 4x
_
1
u
+
1
80
u
3
__
(18)
Note that the correction term here increases with temperature.
Let us calculate the partition function for a single harmonic oscillator:
Q
1
() =

n=0
exp
_

_
_
n +
1
2
_
x
_
n +
1
2
_
2
__
=

n=0
exp
_
u
_
_
n +
1
2
_
x
_
n +
1
2
_
2
__
=

n=0
exp
_
u
_
n +
1
2
__
_
1 +ux
_
n +
1
2
_
2
+
ux
2
2
_
n +
1
2
_
2
+...
_
Keeping only the rst order in x:
Q
1
() =

n=0
exp
_
u
_
n +
1
2
__
_
1 +ux
_
n +
1
2
_
2
_
=

n=0
exp
_
u
_
n +
1
2
__
+ux
_
n +
1
2
_
2
exp
_
u
_
n +
1
2
__
=
e
u/2
1 e
u
+

n=0
ux
_
n +
1
2
_
2
exp
_
u
_
n +
1
2
__
=
_
1
u

u
24
+
7u
3
5760
+...
_
+ux
d
2
du
2

n=0
exp
_
u
_
n +
1
2
__
=
_
1
u

u
24
+
7u
3
5760
+...
_
+ux
_
2
u
3
+
7u
960

31u
3
48384
+...
_
where the last calculations were done using Mathematica. Therefore, the N-oscillator partition
function, keeping only until the fourth order in u, is given by:
Q
N
() = (Q
1
)
N
=
__
1
u

u
24
+
7u
3
5760
_
+ux
_
2
u
3
+
7u
960
__
N
(19)
5
Let us compute now the internal energy:
U =

(ln Q
N
) =

u
(ln Q
N
)
= kTu

u
ln
_
__
1
u

u
24
+
7u
3
5760
_
+ux
_
2
u
3
+
7u
960
__
N
_
= kTNu

u
ln
__
1
u

u
24
+
7u
3
5760
_
+ux
_
2
u
3
+
7u
960
__
= kTNu
_
1
u

u
12
+
u
3
240
_
+ 4ux
_
1
u
2
+
u
2
80
_
= kTN
_
1
u
2
12
+
u
4
240
_
+ 4ux
_
1
u
+
u
3
80
_
Finally, let us calculate the specic heat of the system:
C =
U
T
= kN
_
1
u
2
12
+
u
4
240
_
+ 4ux
_
1
u
+
u
3
80
_
(20)
6