Statistical mechanics

• Statistical mechanics is the branch of

physics that attempts to relate the
macroscopic properties of an assembly of
particles to the microscopic properties of
the particle themselves

• How the overall behaviour of a system of

many particles is related to the properties
of the particles themselves.
Statistical mechanics/distributions

Classical Quantum
statistics Statistics
Maxwell–Boltzmann statistics Bose–Einstein statistics
Fermi–Dirac statistics
 Classical statistics

 In classical mechanics all the particles (fundamental and

composite particles, atoms, molecules, etc.) in the system are
considered distinguishable.

 This means that one can label and track each individual particle
in a system.

 As a consequence, changing the position of any two particles in

the system leads to a completely different configuration of the
entire system.

 Classical statistics is called Maxwell–Boltzmann statistics.

Now, the number of particles 𝑛 (𝜖) with the energy 𝜖 is given by the
expression :

When a continuous rather than a discrete distribution of

energies is involved, g(ϵ) is replaced by g(ϵ) dϵ, the number of
states with energies between 𝜖 and 𝜖 + 𝑑𝜖.
Maxwell-Boltzmann Statistics
Classical particles such as gas molecules obey them

The Maxwell-Boltzmann distribution function states that the average

number of particles fMB(ϵ) in a state of energy ϵ in a system of
particles at the absolute temperature T is

The value of A depends on the number of particles in the system

and plays a role here analogous to that of the normalization
constant of a wave function. As usual, k is Boltzmann’s constant,
whose value is

Now, the number n(ϵ) of identical, distinguishable particles in an

assembly at the temperature T that have the energy :
 Where

Now,
Fig.1 Maxwell-Boltzmann energy Fig.2 The distributions of molecular
distribution for the molecules of speeds in oxygen at 73 K, in
an ideal gas. The average oxygen at 273 K, and in hydrogen
molecular energy is at 273 K.
 Quantum Statistics
Bosons and fermions have different distribution functions
We Know:

• Maxwell-Boltzmann distribution function holds for systems of

particles that can be distinguished one from another, which
means particles whose wave functions do not overlap very much.
• Molecules in a gas fit this description and obey Maxwell-
Boltzmann statistics
• If the wave functions do overlap appreciably, the situation
changes because the particles cannot now be distinguished,
although they can still be counted.
• For indistinguishability of particles the wave functions overlap
e.g. fermions and bosons.
 Pauli exclusion principle
 The Pauli exclusion principle is the quantum mechanical principle
that states that two identical fermions (particles with half-integer
spin) cannot occupy the same quantum state simultaneously.

 In the case of electrons, it can be stated as follows: it is impossible

for two electrons of a poly-electron atom to have the same values
of the four quantum numbers: n, the principal quantum number, ℓ,
the angular momentum quantum number, mℓ, the magnetic
quantum number, and ms, the spin quantum number.
Name Symbol Orbital meaning Value examples
principal quantum
n shell n = 1, 2, 3, …
number
subshell (s orbital is listed as 0, p orbital for n = 3:
angular momentum ℓ
as 1 etc.) ℓ = 0, 1, 2 (s, p, d)
magnetic quantum energy shift (orientation of the subshell's for ℓ = 2:
mℓ
number shape) mℓ = −2, −1, 0, 1, 2
for an electron s =
spin of the electron (−½ = "spin down", ½
Spin quantum number ms ½,
= "spin up")
so m = −½, ½
 Bose-Einstein and Fermi- Dirac distributions
As far as Quantum Physics is concerned there are two category of
basic particles
Fermions Bosons
Electron Photons
Proton Phonons
neutron

Statistical distributions
• It determines the most probable way in which a certain total amount
of energy E is distributed among the N members of a system of
particles in thermal equilibrium at the absolute temperature T.
• Thus we can establish how many particles are likely to have the
energy ϵ1, how many to have the energy ϵ2, and so on.
Bosons
 Particles with 0 or integral spins are bosons.
 Bosons do not obey the exclusion principle
 The wave function of a system of bosons is not affected by the
exchange of any pair of them. A wave function of this kind is
called symmetric.
 Any number of bosons can exist in the same quantum state of
the system.
Fermions
1 3 5 7
 Particles with odd half-integral spins ( , , , etc) are
2 2 2 2
fermions.
 Fermions obey the exclusion principle
 The wave function of a system of fermions changes sign upon
the exchange of any pair of them. A wave function of this kind
is called antisymmetric.
 Only one fermion can exist in a particular quantum state of the
system
• 𝛼 is a quantity depends on the properties of the particular system
• It may be a function of 𝑇.
• Its value is determined by the normalization condition that the sum over
all energy states of 𝑛(𝜖) = 𝑔(𝜖)𝑓(𝜖) be equal to the total number of
particles in the system

 The −1 term in the denominator of 1st Eq. expresses the increased likelihood
of multiple occupancy of an energy state by bosons compared with the
likelihood for distinguishable particles such as molecules.
 The +1 term in the denominator of 2nd Eq. is a consequence of the pauli
exclusion principle: No matter what the values of 𝛼, 𝜖, and 𝑇, 𝑓 (𝜖) can
never exceed 1.
 Bose-Einstein Condensate
 Under ordinary conditions, the wave packets that correspond to
individual atoms in a gas of atoms are sufficiently small in size
relative to their average spacing for the atoms to move
independently and be distinguishable.
 If the temperature of the gas is reduced, the wave packets grow
larger as the atoms lose momentum, in accord with the uncertainty
principle.
 When the gas becomes very cold, the dimensions of the wave
packets exceed the average atomic spacing so that the wave
packets overlap.
 If the atoms are bosons, the eventual result is that all the atoms fall
into the lowest possible energy state and their separate wave
packets merge into a single wave packet.
 The atoms in such a Bose-Einstein condensate are barely moving,
are indistinguishable, and form one entity—a superatom.
13
 Fig. 3 A comparison of the three distribution functions for the same
value of 𝛼.
 The Bose- Einstein function is always higher than the Maxwell-
Boltzmann one, which is a pure exponential.
 The Fermi-Dirac function is always lower than M.B.
 The functions give the probability of occupancy of a state of energy
at the absolute temperature T.
 In both F-D and B-E cases, when 𝜖 ≫ 𝑘𝑇, the functions
𝑓(𝜖) approach that of M-B statistics.
F-D distribution function is given by
1
Now 𝑓𝐹𝐷 (𝜖) = When, 𝜖𝐹 = −𝛼𝑘𝑇
2
• This energy, called the Fermi energy, is a very important quantity
in a system of fermions, such as the electron gas in a metal.
• In terms of 𝜖𝐹 the Fermi-Dirac distribution function becomes

1
𝑓𝐹𝐷 (𝜖) = 𝜖−𝜖𝐹 /𝑘𝑇
𝑒 +1

To appreciate the significance of the Fermi energy, let us consider a

system of fermions at 𝑇 = 0 and investigate the occupancy of states
whose energies are less than 𝜖𝐹 and greater than 𝜖𝐹 .
16
Fermi-Dirac Distribution continue…..

~ kBT

𝜖 = 𝜖𝐹

 At 𝑇 = 0, all the states with 𝜖 < 𝜖𝐹 have the occupancy = 1,

all the states with 𝝐 > 𝝐𝑭 have the occupancy = 0 (i.e., they
are unoccupied).
 With increasing 𝑇, the step-like function is “smeared” over the
energy range ~ 𝑘𝐵𝑇.
Table .1 The Three Statistical Distribution Functions