By: Dr.

Md Mahabul Islam
 Why need Statistical Mechanics:

too many particles (: e.g. 10^23

Statistical Mechanics
Few Particles Many degrees of freedom
Newtonian mechanics or Schrodinger equn
small no of degrees of freedom.

Statistical Mechanics

Classical Statistical Mechanics Quantum Statistical Mechanics

Bose-Einstein Distribution
Maxwell-Boltzmann Distribution
Fermi-Dirac Distribution
Macrostate and Microstate
• Macrostate refers to the state of the system as a whole. The quantities like
pressure, volume and temperature are macroscopic. They do not give the
position momentum values of constituent particles.
• Microstate refers to the state of the system by specifying its position coordinates
and momentum coordinates of all particles in the system.
• It is difficult to describe the microstate of a system practically because of the large
number involved.
• For a given macrostate, a large number of microstates may be possible. The
number of microstates corresponding to a macrostate is called Thermodynamic
Probability.

The total number of accessible (i.e., consistent with the constrained conditions of
the given system) microstates corresponding to a system (macrostate) is known as
the thermodynamic probability and denoted by a symbol Ω(N,V,E).
entropy of the system, S = k loge Ω
Phase Space:

• The phase space is the space of all possible states of a system; the state of a
mechanical system is defined by the constituent positions and momenta
• To describe the motion of a single particle you will need 6 variables, 3 positions
and 3 momenta.
• In general, it is 6 dimensional space constitutes of 3 position and 3 momenta
cooordinates

*****density of states : the number of states per unit energy range*****

Let us calculate this for a single particle of mass m and volume V. The
elementary phase volume for a single particle can be written as
dqx dqy dqz dpx dpy dpz. = h3
So the total volume of the phase-space is
∫ ∫ ∫ ∫ ∫ ∫ dqx dqy dqz dpx dpy dpz
But ∫ ∫ ∫ dqx dqy dqz = ∫ ∫ ∫ dxdydz = given volume V of the particle
Now the volume of the momentum space containing momentum between
p and p+dp will be given by the volume of a spherical shell of radius p and
thickness dp. Therefore,
∫ ∫ ∫ dpx dpy pz,= 4 πp2dp
Thus the volume of phase-space = V. 4 π p2dp

Therefore, total number of phase cells (microstates) in the momentum

range from p to p+dp is
g(p)dp = V.4 π p2 dp/ h3
If the energy corresponding to momentum p is E, E = p2/2m, or p =
(2mE)1/2Thus total number of microstates in the energy range from E to
E+dE is
� �
�
g(E)dE = � � ��� � ��
� �
��
For particles having two allowed values of spin quantum number ms (for example
electron), the number of available quantum states is 2 times
� �
�
g(E)dE = � � ��� � ��
� �
��
 Maxwell-Boltzmann (MB) Statistics

The basic postulates of MB statistics are:-

(i)The associated particles are identical and distinguishable.
(ii) Each energy state can contain any number of particles.
(iii)Total number of particles in the entire system is constant.
(iv)Total energy of all the particles in the entire system is
constant.
(v)Particles are spinless.
Examples: gas molecules at high temperature and low
pressure.
 Bose- Einstein (BE) Statistics

The basic postulates of BE statistics are:-:

(i)The associated particles are identical and indistinguishable.
(ii)Each energy state can contain any number of particles, do
not obey Pauli exclusion principle.
(iii)Total energy and total number of particles of the entire
system is constant
(iv) The particles have zero or integral spin,i.e. 0 ℏ , 1 ℏ ,2
ℏ ..5 ℏ etc, where ℏ is the unit of spin.
(v)The wave function of the system is symmetric under the
positional exchange of any two particles.
Examples: photon, phonon, all mesons ( p,k,h ) etc., these are
known as Bosons.
 Fermi-Dirac (FD) Statistics

The basic postulates of FD statistics are:-

(i)Particles are identical and indistinguishable.
(ii)Total energy and total number of particles of the entire
system is constant
(iii)Particles have half-integral spin, i.e 1/2 ℏ ,3/2 ℏ ..5/3 ℏ etc,
where ℏ is the unit of spin
(iv)Particles obey Pauli’s exclusion principle, i.e. no two particles
in a single system can have the same value for each of the four
quantum numbers. In other words, a single energy state can
contain at best a single particle with appropriate spin.
(v)The wave function of the system is anti-symmetric under the
positional exchange of any two particles.
Examples: electron, proton, neutron, all hyperons (Λ,Σ,Ξ,Ω) etc.,
these are known as Fermions.
Consider a system composed of N distinguishable (for MB)/indistinguishable(for
BE and FD), non-interacting particles. Let out of these N particles N1, N2,….., Ni
particles are to be distributed in energy levels E1,E2,….,Ei respectively and these
energy levels have g1,g2,… ,gi number of quantum states correspondingly
Therefore, the total number of ways W by which all the N particles could be
distributed among the quantum states is
� � � �
�! � � + �� − 1 ! �� !
��� = �� � � ��� = ��� =
�� ! � � ! �� − 1 ! � � ! �� − � � !
� � � �

�� �
M-B distribution function � �� = =
�� � �+���

�� �
F-D distribution function � �� = =
�� � �+��� +�

�� �
B-E distribution function � �� = =
�� � �+��� −�
 Statistical Mechanics

• By: Dr. Md Mahabul Islam

 Application of Fermi-Dirac statistics
Fermi distribution at zero and non-zero temperature
�� �
F-D distribution function � �� = =
�� � �+��� +�

α= -EF/kT and β = 1/kT where EF is the Fermi energy of the system (i.e
maximum energy at absolute zero) and k is Boltzmann constant = 1.38 x
10-23 joule/Kelvin
�
� ε� = �� −�� /��
� +�
Case I : T = 0 K

f(εi) = 1/(e-∞+1) = 1when Ei < EF

= 1/(e∞+1) = 0 when Ei > EF T1 <T2<T3

Case – 2 ( T> 0 K)

If Ei = EF, ƒ(Ei) = 1/(e0 +1) = ½

https://demonstrations.wolfram.com/PlotsOfTheFermiDiracDistribution
 v At T=0 , every low-energy state is occupied, right up to the Fermi level,
but no states are filled at energies greater than EF

Fermi energy is the highest occupied level at absolute zero.

Fermi level is the chemical potential. It is the energy level with 50% chance of
being occupied at finite temperature T.
The Fermi energy does not depend on temperature; the Fermi level does depend
on temperature.

Illustration of the
Illustration of the
Fermi function Fermi function for
for zero temperatures above
zero. Some electrons
temperature. All drift above the Fermi
electrons are level. Their density at
stacked neatly higher energies is
proportional to the
below the Fermi Fermi function.
level.
 Fermi energy for electron gas in metals

consider an electron gas consisting of N electrons occupying volume V

the total number of electrons in the electron gas having energy between E to E+dE
� � ��
can be written by N(E)dE = f(E) g(E) dE = ��−��
� �� +�
it is obvious that at T = 0K, all the single-particle states upto energy EF are filled up.
Thus at T = 0K,
� � ��
N(E)dE = −∞ = � � ��
� +�

�� ��
�= � � �� = � � ��
0 0
��
1 3 1
= 3 8 2 ��� 2 �2 ��
ℎ 0
1 3 3
��, � = 3 16 2 ��� �� 2 2
3ℎ
This the expression for the total number of electrons in the metal at T = 0K.
�
�
� �� �
�� =
�� ��

�
�� �� �
n = N/V =no of electron per unit volume the� �� =
�� �
 Total energy at absolute zero temperature
The total energy of electrons at absolute zero (T = 0K) is given by
�� ��
�0 ��� = �� � �� = �� � ��
0 0
��
1 3 3
= 3 8 2 ���2 �2 ��
ℎ 0

1 3 5 �
= 3 16 2 ��� �� = ���
2 2
5ℎ �
which shows quantum effect because, classically the total energy of a system at absolute
zero is nothing but zero.
The average energy per electron at T = 0K can be written as
�
< �� > = �� ��� /� = ��
�
which shows that at absolute zero temperature, the average energy per electron is
equal to 3/5 times the Fermi energy .
 Classical Limit of Quantum Statistics

in general the distribution function for all the three statistics can be written as,
�� 1
� �� = =
�� � �+��� + �
Where � = 0 ��� �� �����,
And � =− 1 ��� �� �����,
Lastly � = 1 ��� �� �����,

quantum statistics (BE and FD) would tend to the classical one (MB)
�
only when � �+��� ≫ �, ���� � ≪ �
��
under high temperature and low particle density the quantum statistics
tend to the classical one.
Fermi Temperature (TF):
Temperature equivalent of Fermi energy (EF) and it is defined as, TF = EF/k