Moumita Indra (MI)

Statistical Mechanics

Classical Statistics Quantum statistics

[Maxwell-Boltzmann
Statistics]
Bose-Einstein Fermi-Dirac
Statistics Statistics
Macroscopic systems: Large scale system. (Solid, liquid, gas)
Macroscopic parameter: They characterized system as a whole and not individual particles.
Example: temperature (T), pressure (P), volume (V) , Energy (E) etc.
Microscopic systems: Small scale system. (Atom, molecule etc.)
Microscopic parameter: They characterized microscopic constituents of macroscopic system
individual particles. Example: position vector, momentum etc.
Equilibrium: When macroscopic parameters of an isolated system do not change with time the system
is said to be in equilibrium. i.e. No change in P, V, T, N, E defines equilibrium state.
Statistical approach: When the system consists of large number of particles which are
indistinguishable we have to use statistical approach.
• We have to consider internal structures.
• Number of particles of system should be large enough to get the accurate result in this approach.
 Macrostate & Microstate:
A macroscopic system is made up of a large number of microscopic constituents. They are may
be different ways of arranging these microscopic constituents so as to get the same macrostate.

All these different ways specify a particular microstate corresponding to the given macrostate.

Example:
Consider a two-level
system of two particles.

Accessible microstates:

Out of all the possible microstates the system can exists in only those microstates which are
compatible with the available information of the system (say the total energy of the system).
Such microstates are called accessible to the system.
Example of accessible microstates:

For an isolated macroscopic

system in equilibrium all
accessible microstates are
equally probable.

This is known as
equiprobability postulate
or principle of equal
a-priori probability.

• No direct proof
• This postulate leads to
the entire statistical
physics
 Statistical weight or degeneracy:

If a system has g r number of energy levels, all having same energy value Er we can say that
the energy level Er is g r fold degenerate
Or, Statistical weight of Er is g r
Or, degree of degeneracy is g r

Example:
According’s to Bohr’s theory
Energy of the n-th state of
H-atom is :
2
1 1  ze 
En     
4 0 2a0  n 

where z  atomic number  1 (for H - atom)
a 0 is the Bohr radius
n  1,2,3,... is the principle quantum number
 Statistical weight
or degeneracy:

Consider a system consisting of

3 particles. Each particle can stay
in either of that two energy states.

Construct the possible

arrangements of 3 particles energy
states.
Identify macrostate, microstate
and statistical weight.
 Macrostate & Microstates in coin tossing:

Probability of each microstates: 1/4

Probability of macrostate (H,H) : 1/4

Probability of macrostate (T,T) : 1/4
Probability of macrostate (H,T) : 1/4+1/4 = 1/2

Most probable macrostates: (H,T)

4 distinguishable coins
are tossed for a large
number of times, what
will be the macrostate,
microstate ?

Total number of
microstates = 16
Thermodynamic probability :
Thermodynamic probability of a particular macrostate is defined as the number of microstates
corresponding to that macrostate
r
Pr   0  Total no of microstates
 r  Number of microstates in a given macrostate
Pr  Probability of that macrostate

As distinguished from mathematical probability, which is always expressed by a proper fraction,

the thermodynamic probability is expressed by total number of microstates , usually very
large number, not a fraction.

Thermodynamic probability & entropy:

According to Boltzmann equation we can relate thermodynamic entropy (S) in terms of thermodynamic
probability ( 0 ) as,
S  k B ln  0 here, k B  1.38 10 23 J / K  Boltzmann constant

This relation connects macroscopic parameter to a microscopic parameter.

It follows therefore that if the thermodynamic probability of a system increases, its entropy S must
increase too.
 Position or configuration space: The position of a point particle in 3D space is
determined by 3 coordinates x, y, z .

Momentum space: The state of motion of that particle in 3D can be described by the
velocity components v x , v y , v z .
It is more convenient to use the corresponding momenta p x , p y , p z of that particle.

Phase space: To describe the position and the

state of motion of the particle, we need to set up a six-
dimensional (6D) space called the phase space.

The 6 coordinates are marked out along six mutually

perpendicular axes.

The set of q1 , q2 ,..., q f , p1 , p2 ,..., p f  specifies a definite point in the phase space.

where q   1 to f  denotes generalized coordinates and p   1 to f  denotes

generalized momenta for a system having f number of degrees of freedom.
Smallest cell in phase space: We can divide phase space into large number of cells. Narrower
the cell size, greater the precession with which we can specify the state of the system.
All these cells are equiprobable destination of the particle i.e. a particle in a given cell can go to any
adjacent cell with equal probability.

Minimum size of the cells:

h is arbitrarily small.
qp  h  cell area Classically it tends to zero
Quantum mechanically h=Planck’s constant.

Microstate in phase space:

A state or microstate is defined by

specifying the coordinates of a
particle lying between

q  q  q, p  p  p 
i.e. by mentioning the cell in phase
space.
Number of microstates in 2D, 3D phase space:

Aq , Ap denotes the
area of the configuration
space and momentum
space respectively

Vq , V p denotes the
volume of the configuration
space and momentum space
respectively
 Phase trajectory for 1D Harmonic Oscillator:

Phase trajectory for a harmonic oscillator is

an ellipse.
2 E 2E
Area of the ellipse Aphase   2mE 
space k 
k
  angular frequency of the oscillator
m
 Density of states (DOS) :

Number of microstates with energy less than or equal to E

= Number of phase cells having energy less than or equal to E
= n(E )

Number of microstates within energy range E and E+dE

= E    E dE  nE dE

d
dE
dnE  n
Here  E  is the density distribution function:  E    lim
dE E 0 E
 dnE 
DOS for 1D:  E  
dE

 E 1D  E 1/ 2
DOS for free particle in 2D:

 E 2 D  constant
DOS for free particle in 3D:

 E 3 D  E 1/ 2
 Ensemble approach of Gibbs:
In statistical mechanics, an ensemble (also statistical ensemble) is an idealization consisting of a large
number of virtual copies (sometimes infinitely many) of a system, considered all at once, each of
which represents a possible state that the real system might be in. We take the mean of a quantity that is
a function of the microstate of a system, is known as ensemble average.
 q, p  
dN
is known as
d
density distribution function

 dN    q, p d
represents total number
of microstates
 MB statistics:
Assumptions:
• The particles of the system are distinguishable.
• Any number of particles can occupy a single cell in the phase space.
• The cell can be of any size.
• Particles are spin-less.
Examples: Gas molecules at high temperature and low pressure.

If the system is isolated total number of particles are constant. n   ni  constant

i

If the particles are non-interacting the total energy is constant. E   ni Ei  constant

i

Total number of ways in which ni particles can be distributed in g i states is given by,

  n! i
g i n
i

(ni )!
This is the Maxwell-Boltzmann (MB) distribution law for n distinguishable particles. This is
sometimes called classical statistics.
 FD statistics:
Assumptions:
• The particles of the system are identical and indistinguishable.
• Any number of particles cannot occupy a cell in the phase space. Only one particle per cell is allowed
• The cell size cannot be less than h 3 where h is the Planck’s constant.
• FD statistics is applicable to particles with odd half –integral spin angular momentum.
• Wave function of the system is anti-symmetric under the positional exchange of any two particles.
Example: Electron, proton, neutron etc. These are known as Fermions.

If the system is isolated, total number of particles are constant. n   ni  constant

i

If the particles are non-interacting, the total energy is constant. E   ni Ei  constant

i

The number of arrangements of ni particles among gi quantum states in the i-th level is
( g i )!
i 
(ni )! g i  ni !

Total number of states:    i

i
 BE statistics:
Assumptions:
• The particles of the system are identical and indistinguishable.
• Any number of particles can occupy a single cell in the phase space.
• The cell size cannot be less than h 3 where h is the Planck’s constant.
• BE statistics is applicable to particles with integral spin angular momentum
• Wave function of the system is symmetric under the positional exchange of any two particles.
Example: Phonon, meson, photon etc. These are known as Bosons.

If the system is isolated total number of particles are constant. n   ni  constant

i

If the particles are non-interacting the total energy is constant. E   ni Ei  constant

i

The number of arrangements of ni particles among g i quantum states in the i-th level is
(ni  g i  1)!
i 
(ni )! g i  1!

Total number of states:    i

i
 COMPARISON OF DIFFERENT DISTRIBUTIONS :

The mean number of particles in a given state is known as distribution function of that state.
The distribution function for the three statistical system is given by

nFD   
1
   Fermi-Dirac distribution function
exp   1
 k BT 
1
nBE     Bose-Einstein distribution function
  
exp   1
 kBT 
1
nMB ( ) 
   Maxwell-Boltzmann distribution function
exp 
 B 
k T
 is the average energy
 is the chemical potential
T is the absolute temperature of the system
k B is the Boltzmann constant