Chapter six

Quantum Statistics of Ideal Gases and

System of Interaction Particles
 Contents
● Identical particles and symmetry
requirement
● Formulation of statistical problems
● The quantum distribution functions
● Maxwell-Boltzmann statistics
● Photon statistics
● Bose-Einstein statistics
● Fermi-Dirac statistics
● Quantum statistics in the classical limit
● Lattice vibration and normal
mode
● Debye approximation
● Calculation of the partition
function for low densities
● Equation of state and virial
coefficients
● Alternative derivation of the van
Der Waals equation
 Identical particles and symmetry requirement
❖ Consider an ideal gas consisting of N identical structureless particles enclosed within
a container of volume V.
❖ Let Qi denotes collectively all the coordinates of ith particle and si be an index labeling
the possible quantum state of this single particle.
❖ The state of the whole gas is described by the set of quantum numbers

which characterize the wave function 𝛹 of the gas in this state.

 Identical particles and symmetry requirement
❖ The symmetry requirement corresponding to the wave function is discussed by
considering the case what will happen to the wave function if the position of the two
particle is exchanged.
❖ The symmetry of the wave functions corresponding to the system can be discussed
ussing the following cases:
➢ Classical case
➢ Quantum mechanics
 Classical case: Maxwell-Boltzmann statistics (MB)
❖ The particles are considered to be distinguishable, and any number of particles can
be in the same single-particle state s.
❖ No symmetry requirements on the wave function when two particles are
interchanged and the description is not correct quantum mechanically, but is
interesting for purposes of comparison.

Quantum mechanics
❖ The quantum mechanical description is actually applicable.
❖ When quantum mechanics is applied to a system of identical particles, it imposes
definite symmetry requirement on the wave function under interchange of any two
identical particles.
❖ The net result is that one does not obtain a new state of the whole gas by simply
interchanging two such particles.
❖ When counting the distinct possible states accessible to the whole gas, the particles
must be considered as intrinsically indistinguishable.
❖ In enumerating these possible states of the gas, it does not matter which particle is in
which particle state, but only how many particles there are in each single-particle
state s.
❖ The symmetry requirements can be regarded as fundamental quantum-mechanical
postulates and are intimately connected with the spin of the particles.
❖ There are two possible cases which may arise: either (a) the particles have integral
spin or (b) the particles have half-integral spin.
a. Partices with integral spin (Bose-Einstein statistics):
❖ Each particle has a total spin angular momentum (measured in units of ħ) is
integral, i.e., 0, 1,2, . . . (examples might be He4 atoms or photons).
❖ Then the fundamental quantum-mechanical symmetry requirement is that the total
wave function 𝛹 be symmetric (i.e., that it remain unchanged) under interchange of
any two particles (i.e., interchange of both their spatial and spin coordinates).

❖ Thus interchange of two particles does not lead to a new state of the whole gas.
❖ The particles must be considered as genuinely indistinguishable in enumerating the
distinct states of the gas.
❖ No restriction on how many particles can be in anyone single-particle state s.
❖ Particles satisfying the symmetry requirement equation are said to obey
Bose-Einstein statistics (BE statistics) and are sometimes called bosons.
b. Particles with half-integral spin (Fermi-Dirac statistics):
❖ Each particle has a total spin angular momentum (measured in units of ħ) is
half-integral, i.e.,½, 3/2 (eg. might be electrons or He3 atoms).
❖ Then the fundamental quantum-mechanical symmetry requirement is that the total
wave function 𝛹 be antisymmetric (i.e., that it change sign) under interchange of
any two particles, i.e.,

❖ Interchange of two particles does not lead to a new state of the gas.
❖ The change of sign in the above expression does imply one additional consequence:
Suppose that two particles i and j, both in the same single-particle state s, are
interchanged.
❖ But since the fundamental symmetry requirement must also be valid, then

❖ Thus in the Fermi-Dirac case there exists no state of the whole gas for which two or
more particles are in the same single-particle state.
❖ This is the so-called Pauli exclusion principle.
❖ In enumerating the distinct states of the gas can never be more than one particle in
any given single-particle state.
Illustration
❖ Consider a gas of only two particles A and B. Assume that each particle can be in one
of three possible quantum states, s = 1, 2, 3.
❖ Let us enumerate the possible states of the whole gas.
❖ This is the same as asking in how many distinct ways one can put two particles into
three single-particle states (labeled 1,2,3).
❖ To illustrate it in the following cases:
➢ Maxwell-Boltzmann statistics
➢ Bose-Einstein statistics
➢ Fermi-Dirac statistics
 1 2 3
Maxwell-Boltzmann statistics:
AB … …
● The particles are to be considered
… AB …
distinguishable.
… … AB
● Any number of particles can be in any one
state. A B …

● Each of the two particles can be placed in any B A …

one of the three states. A … B

● So there exist a total of 32 =9 possible states B … A

for the whole gas. … A B

… B A
Bose-Einstein statistics:
1 2 3
● The particles to be considered indistinguishable
AA … …
● Any number of particles can be in any one state.
… AA …
● The indistinguishability implies that B=A, so
… … AA
that the three states in the MB case which
A A
differed only is interchange of A and B are now
A A
no longer to be considered as distinct.
● There are three distinct ways of placing the A A

particles in different states.

● Therefore, there exist a total of 3+3=6 possible
states for the whole gas.
Fermi-Dirac statistics:
1 2 3

● The particles are to be considered as A A …

indistinguishable. A … A
● No more than one particle can be in anyone state. … A A

● The three states in the BE case where two particles were in the same state
must be eliminated in this case.
● There exist now only a total of 3 possible states for the whole gas.
This example shows one further qualitative feature of interest. Let
❖ In the BE case there is a greater relative tendency for particles to bunch together in
the same state than in classical statistics.
❖ In the FD case there is a greater relative tendency for particles to remam apart in
different states than there is in classical statistics.
 Formulation of statistical problems
❖ Consider a gas of identical particles in a volume V in equilibrium at temperature T.
❖ We use the following notations:
➢ Label the possible quantum state of a single particle by r (or s)
➢ Denote the energy of a particle in state r, ϵr
➢ Denote the number of particles in state r, by nr
➢ Label the possible quantum state of the whole gas by R.
❖ The assumption of negligibly small interaction between the particles allows us to
write for the total energy of the gas, when it is in some state R where there are n1
particles in state r=1, n2 particles in state r=2, etc., the additive expression
 Formulation of statistical problems

❖ Here the sum is over all the possible states R of the whole gas, i.e.,
essentially over all the various possible values of the numbers n1, n2 n3, ….
❖ Since the exponential term is the relative probability of finding the gas in a
particular state where there are n1 particles in state 1, n2 particles in state 2,
etc., one can ,write for the mean number of particles in a state s
Formulation of statistical problems
Thus the mean number of particles in a given single-particle in
state s can also be expressed in terms of the partition function Z.
Reading Assignmentg from reif text book
Chapter 9 Chapter 10
● Lattice vibration and normal mode
● The quantum distribution functions
● Debye approximation
● Maxwell-Boltzmann statistics
● Calculation of the partition function
● Photon statistics
for low densities
● Bose-Einstein statistics
● Equation of state and virial
● Fermi-Dirac statistics
coefficients
● Quantum statistics in the classical limit
● Alternative derivation of the van
Der Waals equation