Tabish Qureshi

Statistical Mechanics: Problems 9.1

1. Problem: Consider a collection of N noninteracting spins ( s  1), in a magnetic field B ,
such that the Hamiltonian is given by Ŝ z B . Using canonical ensemble, find the average
magnetization of the gas.
Solution: Suppose the magnetic field is in the z-direction. The Hamiltonian em for one
spin is given by Ĥ  −g S µ B ~ ~ ~  −g S µ B B Ŝ z /~. The energy eigenvalues are given
B · S/
by Ĥ |mi  E m |mi , where E m  −g S µ B Bm , m  −1, 0, +1. Energy of N spins can
then be written as

E m1,m2...mN  −g S µ B B ( m1 + m 2 + m 3 ... + m N )
where m 1 , m 2 ... can take values −1, 0, +1 each. Summing over microstates would
amount to summing over these values. The canonical partition function can then be
written as
+1
X +1
X +1
X
exp β g S µ B B ( m 1 + m 2 + m3 ... + m N )


Z ···
m 1 −1 m 2 −1 m N −1
+1
X +1
X +1 Y
X N
 ··· e β gS µB Bm i
m 1 −1 m 2 −1 m N −1 i1
N
Y +1
X
 e β gS µB Bm i
i1 m i −1
N
 1 + 2 cosh ( β g S µ B B )

(1)

Magnetization in any microstate is given just by the sum of the magnetic moments of all
spins, M ( m 1 , m 2 ...m N )  −g S µ B ( m 1 + m 2 + m 3 ... + m N ) . Average magnetization can
be calculated by taking the ensemble average of this quantity:
+1 +1
1 X X
hMi  ··· M ( m 1 , m2 ...m N ) e −βBM ( m1 ,m2 ...m N )
Z
m 1 −1 m N −1

The partition function can also be written in terms of magnetization as

+1
X +1
X
Z ··· e −βBM ( m1 ,m2 ...m N )
m 1 −1 m N −1

It should be noticed that the sum in the above equation can also be obtained by taking a
derivative of Z with respect to B , and multiplying with −1/β :
+1 +1
1 ∂ X
!
1 X
hMi − ··· e −βBM ( m1 ,m2 ...m N )
Z β ∂B
m 1 −1 m N −1
1 ∂ log Z
− (2)
β ∂B
Plugging the expression for Z from (1) in the above equation, we get
2N g S µ B sinh ( β g S µ B B )
hMi− (3)
1 + 2 cosh ( β g S µ B B )
 Tabish Qureshi

2
2. Problem: Let there be quantum mechanical rotator with a Hamiltonian Ĥ  L̂2I . As-
suming that the rotator can take only two angular momentum values l  0 and l  1,
calculate the average energy in canonical ensemble.
Solution: Eigenvalues of the Hamiltionian can be obtained by using the simultaneous
eigenstates of L̂ 2 and L̂ z , which are denoted by |lmi . These states are also eigenstates
of Ĥ ,
~2 l ( l + 1 )
Ĥ |lmi  |lmi
2I
There are 2l + 1 values of m corresponding to each value of l . Eigenvalues do not
depend on m , and hence energy-levels are (2l + 1) -fold degenerate. The partition
function can thus be written as
1
−β~2 l ( l + 1)
X !
Z (2l + 1) exp
2I
l0
1 + 3 exp (−β ~2 /I ) (4)

Average energy is given by

∂ log Z
hEi−
∂β
∂
− log (1 + 3 exp (−β~2 /I ))
∂β
(3~2 /I ) exp (−β~2 /I )

1 + 3 exp (−β ~2 /I )
3~2 /I
 (5)
exp ( β~2 /I ) + 3

3. Problem: An ideal gas of N spinless atoms occupies a volume V at temperature T. Each

atom has only two energy levels separated by an energy ∆. Find the chemical potential,
free energy, average energy.
Let the two energy levels have energy  1 and  2 , with  2 −  1  ∆. For one particle, the
partition function can be written as Z  e −β1 + e −β2 . The atoms being, non-interacting,
one can write the partition function for N particles as
 N
Z  e −β1 + e −β2

Helmholtz free energy is given by

 
F  −kT log Z  −N kT log e −β1 + e −β2

The chemical potential is given by

∂F
!  
µ  −kT log e −β1 + e −β2
∂N T,V

Average energy is given by

∂ log Z  1 e −β1 +  2 e −β2  1 +  2 e −β∆

hEi  −  
∂β e −β1 + e −β2 1 + e −β∆



 Tabish Qureshi

4. Problem: A simple harmonic one-dimensional oscillator has energy levels E n  ( n +

1/2)~ ω , where ω is the characteristic oscillator (angular) frequency and n  0, 1, 2, . . .
(a) Suppose the oscillator is in thermal contact with a heat reservoir kT at temperature
T. Find the mean energy of the oscillator as a function of the temperature T, for the
cases ~kTω  1 and ~kTω  1
(b) For a two-dimensional oscillator, n  n x + n y , where E n x  ( n x + 1/2)~ ω x and
E n y  ( n y + 1/2)~ ω y , n x  0, 1, 2, . . . and n y  0, 1, 2, . . . , what is the partition
function for this case for any value of temperature? Reduce it to the degenerate case
ωx  ω y .
Answer (a): The partition function can be written as
∞
X ∞
X
−β ( n+1/2)~ ω −β~ ω/2
Z e e e −βn ~ω
n0 n0
1 1 1
e −β~ω/2  
1 − e −β~ω e β~ω/2 − e −β~ω/2 2 sinh ( β ~ ω/2)
The average energy can now be easily calculated

∂ log Z ~ ω
hEi  −  coth ( β ~ ω/2) (6)
∂β 2

For β ~ ω  1, which is the high-temperature limit, coth ( β ~ ω/2) ≈ 2/β ~ ω . The average
energy takes the form hEi ≈ kT . For β ~ ω  1, which is the very-low-temperature limit,
coth ( β ~ ω/2) ≈ 1. The average energy takes the form hEi ≈ ~2ω , which is precisely the
zero-point energy of the oscillator.
Answer (b): The partition function can be written as
∞ X
X ∞
Z e −β ( n x +1/2)~ωx −β ( n y +1/2)~ω y
n x 0 n y 0
∞
X ∞
X
−β ( n x +1/2)~ ω x
 e e −β ( n y +1/2)~ω y
n x 0 n y 0
1

4 sinh ( β~ ω x /2) sinh ( β ~ ω y /2)

When ω x  ω y  ω , the above relation reduces to

1
Z
4 sinh2 ( β~ ω/2)

This is exactly the same as the partition function of two independent, similar, one-
dimensional harmonic oscillators.