151 Third Exam

Damian Dailisan

Harmonic Oscillator

1.1

Continuous

For the classical treatment of continuous energies, the Hamiltonian of 1 harmonic oscillator in 1 dimension is
1
p2
+ m 2 q 2
2m 2
We solve for the corresponding Canonical partition function in one dimension
H=

Zi =
Zi =
Zi =
Zi =

Z
1
eHi dpdq
h
Z
Z
p2
1
1
2 2
2m
dp e 2 m q dq
e
h

1/2 
1/2
1 2m
2
h

m 2
2
h

(1)

(2)
(3)
(4)
(5)

where (4) is obtained by using a gaussian integral. However, since we have N atoms that
are distinguishable, the total partition function is
Z=

ZiN


=

2
h

N
.

(6)

Now that we have Z, we can calculate the energy by

F = kT ln Z
(F )
U=

ln Z
U =

N
U=

(7)
(8)
(9)
(10)

and hence, the energy of N classical harmonic oscillators is simply

U = N kB T .

(11)

Knowing the relationship of the heat capacity and energy, we obtain the CV as follows:
1

CV =

U
T

(12)

CV = N k B

1.2

(13)

Discrete

For a harmonic oscillator with discrete energies, as in the quantum treatment, the discretized energies are given by
1
n = h
(n + ), n = 0, 1, 2, . . .
2
For one such harmonic oscillator, the partition function is given by
X

Zi =

en

(14)

(15)

Zi = eh/2

ehn

(16)

Let us make a substitution of x = eh . The we can express the summation as

X

ehn =

xn ,

(17)

x = (1 x)1 ,

(18)

1
,
1 eh

(19)

ehn =

where the subtitution of the summation is valid since x  1 so now, we may express Z
as
eh/2
,
1 eh
1
.
Zi = h/2
e
eh/2
Zi =

(20)
(21)

By the definition of the hyperbolic cosecant function, we may simplify the above result
by using

cschx =

ex

2
,
ex

hence,

(22)

1
Zi = csch(h/2)
2

(23)

Since we have N distinguishable oscillators, then

Z=

ZiN


=

1
csch(h/2)
2
2

N
.

(24)

From (9), the energy is

hcsch(
h/2) coth(
h/2)
N
4
csch(h/2)
2

U = 1

U=

(25)

Nh

coth
2
2kB T

(26)

Now, let us examine two extreme conditions for U , namely high temperature when
T h
, and low temperature when T  h
. First we re-express U in terms of exponentials:
h

Nh
e 2kB T + e 2kB T
U=
.
(27)
2 e 2khBT e 2khBT
At high temperatures, T  h
. We may expand the exponential about 0 since the
exponent will be small. The expansion is as follows:

ex =

X
xn
n

n!

(28)

e 1 + x.

(29)

Using the above, we will get the energy for high temperatures to be
U N kB T .

(30)

At high temperatures, T  h
. We can express the energy differently as

Nh
1 + e kB T
U=
.
2 1 e khBT

(31)

It follows from T  h
that the exponent is large, hence the term e kB T is small. Using
the binomial expansion at the denominator (1 + x)n = 1 + nx for x  1, we get the
expression
U=




Nh

h
h
1 + e kB T
1 e kB T .
2

Nh

2h
U=
1 e kB T .
2

(32)
(33)

Following from (12), we can now get the heat capacity for the system of hamonic
oscillators with discretized energies as,

CV =

Nh

h
(csch2
)
2
2kB T 2kB T 2

N
CV =
4kB

T
3

2

csch2

2kB T

(34)

(35)

Ising Model

For N atoms with spin 1/2, the Hamiltonian of their magnetic interaction is given by
H = H

N
X

where j = 1.

(36)

There are two posible states, that is spin up or spin down. If we have N such atoms,
then the number of states is as follows:
N!
,
NU !ND !
N = NU + ND ,

(37)

(E, N ) =

(38)

where NU is the number of atoms with spin up and ND is the number of atoms with spin
down. The total energy is given by
E = H(NU ND ),
E = H(2NU N ),


1
E
NU =
N
,
2
H


E
1
N+
,
ND =
2
H

(39)
(40)
(41)
(42)

so now the microcanonical partition function is

(E, N ) =

1
2

N!
 
E
N H
! 12 N +

E
H

(43)
!

From the microcanonical partition function, we can obtain the Entropy as hown in
the equation
S = kB ln (E, N ),





1
E
1
E
S = kB ln N ! ln
N
! ln
N+
! .
2
H
2
H

(44)
(45)

We can use Stirlings approximation ln N ! N ln N N and get



 
 
 

N
E
N
E
N
E
N
E

ln

+
ln
+
.
S = kB N ln N
2
2H
2
2H
2
2H
2
2H

(46)

We can obtain the canonical partition of the system of N atoms by first considering
one atom only. Following H for on such atom, we have
Zi =

eHj ,

(47)

Zi = eH + eH ,

(48)

Zi = 2 cosh(H).

(49)

Generic Potentials

Let us consider a potential of a more generic term, one where the potential is dependent
on q n rather than q 2 as in our harmonic oscillator. In this case, n assumes even integer
values. For a system of N atoms in one dimension, the Hamiltonian is given by
1
p2
+ m 2 q n
H=
2m 2
We solve for the corresponding Canonical partition function as follows:
Z
1
Zi =
eHi dpdq
h
Z
Z
p2
1
1
2 n
2m
e 2 m q dq.
Zi =
dp
e
h

(50)

(51)
(52)

We will now make a simple substitution xn = 12 m 2 q n such that dx = 12 m 2 dq. The
integral now becomes
1
Zi =
h

2m

1/2 

2
m 2

1/n Z

ex dx,

(53)

and if we make another substitution u = xn , du = nu11/k dx, we can now have an integral
of the following form:
Z

xn

2
dx =
n

u1/n1 eu du,
0 
Z
1
u1/n1 eu du =
,
n
0
 
Z
1
2
xn
,
e dx =
n
n

(54)
(55)
(56)

where we used the definition of the gamma function to evaluate the integral in (55). Since
we have N atoms, the total partition function will then be
Z=

ZiN

1
= N
h

2m

N/2 

2
m 2

N/n 

 N
1
.
n

(57)

Now that we have Z, we can calculate the energy by once again the following
ln Z
,



1
N
N Z

U =
,
Z
2
n

U =

(58)
(59)

and hence, the energy we obtain is simply


U=

N
N
+
2
n
5


kB T .

(60)

Paramagnetism: Vector Spins

In Section 2 we discussed paramagnetism using the Ising model approach. Here, we will
try to solve the more general form for vector spins. The Hamiltonian for one atom is
given by
~ = H cos i .
Hi = ~ H

(61)

From the Hamiltonian we may already obtain the partition function and get
Z

eHi d,
Z 2 Z
Zi =
d
eH cos i sin d,

Zi =

(62)
(63)

2
(64)
eH eH .
H
(eH eH )
Substituting sinh H =
and considering our system has N such indistin2
guishable atoms, we get the partition function
Zi =

1
ZN
Z= i =
N!
N!

4
sinh (H)
H

N
.

(65)

Ultrarelativistic Gas

Consider N particles in 3 dimensions, each with energy given by

p
E = p2 c2 + m2 c4 ,
where p2 = p2x + p2y + p2z .

(66)
(67)

In the ultrarelativistic limit, we have pc  mc2 such that we have E pc. We can solve
for the partition function of the system by integrating over phase space for one particle:
Z
1
Zi = 3 eE d3 pd3 q,
(68)
h
Z
V
Zi = 3
epc 4p2 dp.
(69)
h 0
where we have shifted to spherical coordinates to simplify the integration. This integral
is fairly trivial to solve by integrating by parts, from which we will get
8V
.
(70)
3 c3 h3
Taking into account that we have N particles and indistinguishability, the partition function is thus
Zi =

ZN
1
Z= i =
N!
N!
6

8V
3 c3 h3

N
.

(71)