Homework #12 Solutions

6 problems
1. A particular (made-up) system is in thermal and diusive equilibrium with a reservoir with temperature T
and chemical potential ; the particles that make up the system and reservoir are indistinguishable. The system
can contain at most two particles, and the state of the system is simply determined by the number of particles it
contains: n = 0, 1, 2; there is no degeneracy. The energy of the system is E(n) = an
2
, where a > 0 is a constant.
(a) Find the grand partition function.
(b) Find the average number of particles n this box contains, as a function of T, , and a.
(c) If is negative (as it usually is), nd the limit of n at high temperatures (T ) and low temperatures
(T 0). Explain why these limits make sense.
(a) There are three states: zero, one, or two particles in the system.
Z =

n
e
(n)
=
2

n=0
e
(an
2
n)
= 1 + e
(a)
+ e
2(2a)
(b) The probability of state n is the ratio of its Gibbs function to the grand partition function: P(n) =
1
Z
e
(an
2
n)
. And the average number of particles in the state is
n =

n
nP(n)
=
1
Z

n
ne
(an
2
n)
=
e
(a)
+ 2e
2(2a)
1 + e
(a)
+ e
2(2a)
(c) As the temperature approaches innity, approaches zero, and all of the exponentials approach one;
thus the average number of particles in the system approaches
n
1 + 2
1 + 1 + 1
=
3
3
= 1
At very high temperatures, the particles can basically have any energy they want, and so all three states
are equally accessible: there will be equal numbers of times when the system has 0 particles, 1 particle, or 2
particles, and the average will indeed be 1.
As the temperature approaches zero, approaches innity, and all the exponentials approach e

= 0
(because a < 0 etc). Thus the average number of particles is n
0
1
= 0.
Having no particles in the system is the lowest energy state here, and when the temperature is very low the
system cant get out of its ground state.
2. Consider a system consisting of a single hydrogen atom/ion, which has two possible states: unoccupied (no
electron present) and occupied (one electron present, in the ground state). The hydrogen is in thermal and
diusive equilibrium with a sea of electrons at temperature T. It takes energy I = 13.6 eV to ionize a hydrogen
atom.
(a) Assume that the electrons are a monatomic ideal gas, and ignore the internal degrees of freedom of electrons
(like, for example, their spin states). Find the chemical potential of the ideal gas; you can keep your answer in
terms of the quantum volume v
Q
introduced in Chapter 6.
(b) Calculate the ratio of the probabilities of the excited and ground states; this is the Saha equation.
(a) If the electrons are a monatomic ideal gas with no internal degrees of freedom (so that Z
int
= 1), then
their chemical potential is the chemical potential of an ideal gas:
= kT ln

V Z
int
N
gas
v
q

= kT ln

V
Nv
Q

If we include the spin states, then the chemical potential is reduced by kT ln 2 (assuming no magnetic
eld).
(b) The two states are unoccupied (N = 0, = 0) and occupied (N = 1, = 13.6 eV I) where I is the
ionization energy. The Gibbs factors of these two states are e
(N)
= 1 and e
(IN)
= e
(I+)
. The
ratio of the probabilities of these two states is the ratio of the Gibbs free energies:
P
unocc
P
occ
=
1
e
(I+)
=
e
I
e

Given the chemical potential above,

= ln

V
Nv
Q

= e

=
V
Nv
Q
and so
P
unocc
P
occ
=
V
Nv
Q
e
I/kT
Another way of writing this is in terms of the pressure of the electron gas, which is given by the ideal gas
law P
e
V = NkT, so
V
N
=
kT
Pe
. This gives us the usual form of something called the Saha equation
P
unocc
P
occ
=
kT
P
e
v
Q
e
I/kT
3. Suppose you have a box in which each particle may occupy any of 10 single-particle states. For simplicity,
assume that each of these states has energy zero.
(a) What is the partition function of this system if the box contains only one particle?
(b) What is the partition function of this system if the box contains two distinguishable particles?
(c) What is the partition function of this system if the box contains two identical bosons?
(d) What is the partition function of this system if the box contains two identical fermions?
(e) Calculate (7.16) Z =
1
N!
Z
N
1
to nd the partition function for two indistinguishable, non-interacting particles.
(f) What is the probability of nding both particles in the same single-particle state, for the three cases of
distinguishable particles, identical bosons, and identical fermions?
Since all energy states are energy zero, all Boltzmann factors are e
(0)
= 1, and so Z =

s
e
Es
is
simply the number of available states, or .
2
(a) One particle can be in any of the ten energy levels, so Z = = 10.
(b) The two distinguishable particles can each choose from 10 energy levels, so Z = = 10
2
= 100.
(c) For two identical bosons, there are 10 ways to put both in the same energy level, and there are

10
2

= 45
ways of putting them in dierent energy levels, so Z = 10 + 45 = 55.
(d) For two identical fermions, the result is the same as (c) except for the 10 states with both in the same
energy level; thus Z = 45.
(e) Using the formula with N = 2, and Z
1
= 10 (Z
1
is the number of states for the single particle), we have
Z =
1
N!
Z
N
1
=
1
2!
10
2
= 50
(f) For distinguishable particles, 10 (out of 100) of the system states have both particles in the same state,
so the probability is 10%. For identical bosons, there are still 10 such system states, but only 55 system
states total, so the probability is higher, 10/55 = 18%. For identical fermions, you cant have two particles
in the same single-probability state, so the probability is zero.
4. For a system of fermions at room temperature, compute the probability of a single-particle state being
occupied if its energy is 0.01 eV less than .
The probability of a state being occupied (which is equal to the average occupancy in the case of fermions)
is given by the Fermi-Dirac distribution function,
1
e
()
+ 1
. At room temperature, kT = 0.026 eV. If the
energy of the state is 0.01 eV less than , then = 0.01 eV, and so the probability is
P =
1
e
(0.01 eV)/(0.026 eV)
+ 1
=
1
1.68
= 59%
5. For a system of bosons at room temperature, compute the average occupancy n of a single-particle state, and
the probability that the state contains 0, 1, 2, and 3 bosons, if the energy of the state is 0.001 eV greater than .
This is similar to the previous problem. The energy of the state is = + 0.001 eV, so ( )/kT =
0.001 eV
0.026 eV
= 0.0385. The average occupancy is given by the Bose-Einstein distribution:
n =
1
e
()/kT
1
=
1
e
0.0385
1
=
1
0.0392
= 25.5
The probability that the state is occupied by n particles is given by Eq. (7.20):
P(n) =
1
Z
e
n()/kT
= (1 e
()/kT
)e
n()/kT
(where I used Equation 7.24, the grand partition function of bosons. Since e
()/kT
= e
0.0385
= 0.962,
and so
P(n) = (1 0.962)(0.962)
n
= 0.0377(0.962)
n
and so
P(0) = 3.77% and P(1) = 3.63% and P(2) = 3.49% and P(3) = 3.36%
3
6. Imagine that there exists a third type of particle, which can share a single-particle state with one other particle
of the same type, but no more than one. Thus the number of these particles in any state can be 0, 1, or 2. Derive
the distribution function for the average occupancy n of a state by particules of this type, and plot the occupancy
as a function of the states energy, for three dierent temperatures.
If up to two particles of a given type can occupy a state of energy , then the grand partition function is
Z = e
0
+ e
()/kT
+ e
2()/kT
= 1 + e
x
+ e
2x
where x = ( )/kT. Therefore the average number of particles in the state is
n =
1
Z
Z
x
=
1
1 + e
x
+ e
2x

x
(1 + e
x
+ e
2x
) =
e
x
+ 2e
2x
1 + e
x
+ e
2x
Not as pretty as bosons and fermions; maybe its lucky that these particles dont exist. Heres a graph of n
for three dierent choices of T; we see the same basic shape that we had for fermions, only maxing out at 2
for low energy levels instead of at 1.
4