Statistical mechanics can be applied to systems

such as

The subject which deals with the
relationship between the overall behavior
of the system and the properties of the
particles is called Statistical Mechanics.
molecules in a gas
photons in a cavity
free electrons in a metal
Macro state
Any state of a system as described by actual or
hypothetical observations of its macroscopic
statistical properties is known as Macro state
and it is specified by ( N, V and E ) .
NOTE
For N particle system , there may be always
possible N+1 Macro states.
Micro state
The state of system as specified by the actual
properties of each individual, elemental
components, in the ultimate detail permitted
by the uncertainty principle is known as
Microstate .
NOTE
For N particle system , there may be always
possible 2
n
Micro states.
Phase space
The three dimensional space in which the
location of a particle is completely specified by
the three position co-ordinates, is known as
Position space.
Small volume in a position space dV = dx dy dz
The three dimensional space in which the
momentum of a particle is completely specified by
the three momentum co-ordinates P
x


P
y
and P
z

is known as Momentum space.


Small volume in a momentum space
d = dp
x
dp
y
dp
z
The combination of the position space and
momentum space is known as
Phase space.
Small volume in a phase space d = dV d
Phase space volume
Consider Let p
m
be the maximum value of the
momentum of the particles in the system.

Let p
x
,

p
y
, p
z
represents the three mutually
perpendicular axes in the momentum space
as shown in figure.
Draw a sphere with an origin O as centre
and the maximum momentum p
m
as radius.
p
z

0
p
x

p
y

p
m

All the points within this sphere will have their
momentum lying between 0 and p
m
.
The momentum space volume =

volume of the sphere of radius p
m
.

Momentum volume is given by

= 4/3 p
m
3


Similarly phase space volume is given by

= V

= 4/3 p
m
3

V

where,
V position space volume

The set of possible states for a system
of N particles is referred as ensemble
in statistical mechanics.
ENSEMBLE
(OR)
A collection of large number of microscopically
identical but essentially independent systems is
called ensemble.
NOTE:
An ensemble satisfies the same macroscopic
condition.
Example:
In an ensemble the systems play the role of as
the non-interactive molecules do in a gas.
There are 3-types of ensembles, those are
1) MICRO CANONICAL ENSEMBLE
2) CANONICAL ENSEMBLE
3) GRAND CANONICAL ENSEMBLE
1) MICRO CANONICAL ENSEMBLE
It is the collection of a large number of essentially
independent systems having the same energy (E),
volume(V) and the number of particles(N).
We assume that all the particles are identical and the individual
systems of micro canonical ensemble are separated by rigid,
well insulated walls such that the values of E, V & N for
a particular system are not affected by the presence of
other systems.
NOTE:
E,V,N E,V,N E,V,N
E,V,N E,V,N E,V,N
E,V,N E,V,N E,V,N
2) CANONICAL ENSEMBLE
It is the collection of a large number of essentially
independent systems having the same temperature
(T),volume(V) and the same number of identical
particles(N).
NOTE:
The equality of temperature of all the systems can be
achieved by bringing each in thermal contact at temperature(T).

The individual systems of a canonical ensemble are separated by
rigid, impermeable but conducting walls as a result all the
systems will arrive at the common temperature(T).

T,V,N T,V,N T,V,N
T,V,N
T,V,N T,V,N
T,V,N T,V,N
T,V,N
3) GRAND CANONICAL ENSEMBLE
It is the collection of a large number of essentially
independent systems having the same temperature
(T),volume(V) and the chemical potential ().
NOTE:
The individual systems of a grand canonical ensemble are
separated by rigid & conducting walls.
Since the separating walls are conducting, the exchange of heat
energy takes place between the systems of particles such a way
that all the systems arrive at a common temperature (T) &
chemical potential ().
T,V, T,V, T,V,
T,V,
T,V, T,V,
T,V,N T,V,
T,V,
Statistical distribution
Statistical mechanics determines the most probable
way of distribution of total energy E among the N
particles of a system in thermal equilibrium at absolute
temperature T .
In statistical mechanics one finds the number of ways
W in which the N number of particles of energy E
can be arranged among the available states is given by.
N(E) = g(E) f(E)
Where
g(E) is the number of states of energy
And f(E) is the probability of occupancy of
each state of energy E .
E
We have two different types of statistical functions.
1. Classical Statistics
2. Quantum Statistics
a) Maxwell - Boltzmann distribution
a) Bose - Einstein distribution
b) Fermi - Dirac distribution
(Classical statistics)
Let us consider a system consisting of
molecules of an ideal gas under ordinary
conditions of temperature and pressure.
Assumptions:
The particles are identical and distinguishable.
Maxwell Boltzmann
Since cells are extremely small, each cell can have
either one particle or no. of particles though there
is no limit on the number of particles which can
occupy a phase space cell.
The volume of each phase space cell chosen is
extremely small and hence chosen volume has
very large number of cells.
The state of each particle is specified
instantaneous position and momentum
co-ordinates.
Energy levels are continuous.
The system is isolated which means
that both the total number of particles
of the system and their total energy
remain constant.
MAXWELL - BOLTZMANN
DISTRIBUTION
This distribution is applied to a macroscopic system
consisting of a large number n of identical but
distinguishable particles, such as gas molecules in a
container.

This distribution tells us the way of distribution of total
energy E of the system among the various identical
particles.

Let us consider that the entire system is divided into
groups of particles, such that in every group the
particles have nearly the same energy.
Let the number of particles in the 1
st
, 2
nd
, 3
rd

,.,i
th
,. groups be n
1
,n
2
,n
3
,..n
i
,..
Respectively.

Also assume that the energies of each particle in
the 1
st
group is E
1
, in the 2
nd
group is E
2
and so on.

Let the degeneracy parameter denoted by g [or
the number of electron states] in the 1
st
, 2
nd

,3
rd
,,i
th
, groups be g
1
,g
2
,g
3
,.g
i
,. and so
on respectively.

In a given system the total number of particles is
constant.
Hence its
derivative
] 1 .....[ 0 = E
i
n o
The total energy of the particles present in
different groups is equal to the energy of the
system(E).
const n E n E n E n E n E E e i
i i i i
= = + + + + + =

.... ..... ., .
3 3 2 2 1 1
Hence its derivative
] 2 .....[ 0 = E
i i
n E o
The probability of given distribution W is given by the product
of two factors.

The first factor is, the number of ways in which the groups of
n
1
,n
2
,n
3
,ni
,
particles can be chosen.

To obtain this, first we choose n1 particles which are to be
placed in the first group. This is done in 1 n
c
n
)! ( !
!
. .
1 1
n n n
n
e i

The remaining total number of particles is (n-n

1
). Now
we arrange n
2
particles in the second group. This is
done in
2
) (
1
n
C
n n
)! ( !
)! (
. .
2 1 2
1
n n n n
n n
e i

The number of ways in which the particles in all groups

are chosen is
......
)! ( !
)! (
)! ( !
!
2 1
1
1 1
1
X

=
n n n n
n n
n n n
n
w
1 2 3
!
! ! !...... !....
!
!
i
i i
n
n n n n
n
n t
=
=
i
t
is the multiplication factor
The second factor is the distribution of particles over the
different states and is independent of each other.
Of the n
i
particles in the i
th
group the first particle can
occupy any one of the g
i
states. So there are g
i
ways ,
and each of the subsequent particles can also occupy
the remaining states in gi ways. So, the total number of
the ways the ni particles are distributed among the gi
states is gi
ni
ways.
The probability distribution or the total number of ways
in which n particles can be distributed among the
various energy states is W
2
i i
n
i i
n
i
n n n
g g g g g W ) ( .... ) .....( ) ( ) ( ) (
3 2 1
3 2 1 2
t = =
The number of different ways by which n particles of the
system are to be distributed among the available electron
states is
]
!
[ !
) (
!
!
) ........( ) ( ) ( ) (
!..... ! !
!
3 2 1
3 2 1
3 2 1
2 1
i
n
i
i
n
i i
i i
n
i
n n n
n
g
n
g
n
n
g g g g
n n n
n
W W W
i
i
i
t
t
t
=
=
=
=
Where
i
represents the multiplication factor.

Taking natural logarithms on both sides of equation
in above.

! ln ! ln ln
! ln ! ln ln ln
, ln ! ln
ln ! ln ! ln ln
i
i
i i
i
i
i
i
i
i
i
i i i i
g n n n n n
g n n n n n n W
x x x x
ion approximat Striling Applying
g n n n W


+ =
+ =
=
E + E =
For the most probable distribution, W is maximum provided
n and E are constants.
Differentiate equation and equate to zero for the maximum
value of W.
] 3 ].......[ 0 [ . 0
) (ln
1
) (ln
1
0 ln
max
= E =
+ =
+ = =


i
i
i i i
i
i
i
i
i i i
i
i
i
n
n g n
n
n
n g n
n
n W
o
o o
o o o

Multiplying equation (1) with - and equation (2) with

and adding to the (3) equation and there by
sides both on onential Taking
E
g
n
or
E g n
or
n E g n
i
i
i
i i i
i i i
i
i
exp
) ln(
0 ln ln
. 0 ] ln ln [
| o
| o
o | o
=
= +
= +

i
E
i
i
e e
g
n
| o
=
The above equation is called Maxwell-Boltzmann law. The value of
has been extracted separately and is equal to 1/k
B
T.

Where K
B
is called Boltzmann constant and T is called absolute
temperature.
T K
E
i
i
i MB
B
i
e e
g
n
E f
o
1
) ( = =
2) Quantum Statistics
According to quantum statistics the particles of
the system are indistinguishable, their wave
functions do overlap and such system of
particles fall into two categories

Bose - Einstein distribution

Fermi - Dirac distribution.

According to Bose-Einstein statistics the particles of
any physical system are identical, indistinguishable
and have integral spin, and further those are called
as Bosons.

Assumptions:
The Bosons of the system are identical and
indistinguishable.
Sir J.Bose A . Einstein
The Bosons have integral spin angular
momentum in units of h/2.
Bosons obey uncertainty principle.
Any number of bosons can occupy a single
cell in phase space.
Bosons do not obey the Pauli's
exclusion principle
Energy states are discrete.
Wave functions representing the bosons
are symmetric
i.e. (1,2) = (2,1)
The probability of Boson occupies a state
of energy E is given by
1 )} ( exp{
1
) (
+
=
kT
E
E f
BE
o
This is called Bose Einstein distribution
function.
The quantity is a constant and depends on
the property of the system and temperature T.
Let us divided a box into g
i
sections & the particles
are distributed among these sections.
Once this has been done, the remaining (g
i
-1) compartments
& n
i
particles, the number of ways doing this will equal to
(n
i
+ g
i
-1)!
Thus the total number of ways realizing the distribution
will be g
i
(n
i
+ g
i
1)! ------- (1)
There are n
i
permutations which corresponds to the
same conservative function we thus obtain the
required number of ways as
g
i
(n
i
+ g
i
-1)!/g
i
! n
i
!
(OR)
(n
i
+ g
i
-1)!/n
i
! (g
i
-1)!
G = (n
1
+ g
1
-1)!/n
1
! (g
1
-1)! . (n
2
+ g
2
-1)!/n
2
! (g
2
-1)!..... (n
i
+ g
i
-1)!/n
i
! (g
i
-1)!
=
i
(n
i
+ g
i
-1)!/n
i
! (g
i
-1)! ----- (2)
We have the probability W of the system for occurring
with the specified distribution to the total number of
Eigen states.
W =
i
(ni + gi -1)!
n
i
!(gi -1)!
X constant ---- (3)
Taking the log of eq(3), we have
log W = log (n
i
+g
i
-1)! log n
i
! log (g
i
-1)! + constant ------- (4)
Using the stirling approximation eq(4) becomes as
log W = (n
i
+g
i
) log( n
i
+ g
i
) n
i
log n
i
gi log g
i
+ constant (5)
log w =
i


(n
i
+g
i
) log(n
i
+ g
i
) n
i
logn
i
g
i
log g
i
)
Where,
n
i
, g
i
>> 1. Hence 1 is neglected
log w =
i
n
i
log(n
i
+ g
i
) + (n
i
+ g
i
) n
i
n
i
log n
i
) - n
i
/n
i
n
i

( n
i
+ g
i
)

log w =
i
n
i
log(n
i
+ g
i
)

n
i
log n
i
)


log w = -
i
log n
i
/ (n
i
+ g
i
)

n
i
---- (6)


The condition for maximum probability gives as
log n
i
/ (n
i
+ g
i
) n
i
= 0 ---- (7)
The auxillary condition to be satisfied

(OR)
n = n
i
= 0 --- (8)
E = E
i
n
i
= 0 --- (9)
Multiplying eq(8) by & eq(9) by & adding
the resultant expression to eq(7) , we get
log n
i
/ (n
i
+ g
i
) + + E
i
n
i
= 0 ---- (10)
n
i
is independent of each other.

Therefore
log n
i
/ (n
i
+ g
i
) + + E
i
= 0
1 + g
i
/ n
i
= e
+ E
i
g
i
/ n
i
= e
+ E
i
- 1

ni = gi / (e
+E
i

- 1) ---- (11)
This represents the most probable distribution
of the elements for a system obeying
Bose Einstein statistics.
Therefore,
According to Fermi - Dirac statistics the
particles of any physical system are
indistinguishable and have half integral
spin. These particles are known as Fermions.
Assumptions:
Fermions are identical and indistinguishable.
They obey Pauli s exclusion principle
Fermi
Dirac
Fermions have half integral spin.
Wave function representing fermions
are anti symmetric
) 1 , 2 ( ) 2 , 1 ( =
i.e.
Uncertainty principle is applicable.
Energy states are discrete.
The distribution function & Fermi level is valid
only in equilibrium.
The distribution function changes only with
temperature.
It is valid for all fermions.
Electrons & holes follow the Fermi Dirac
statistics and hence they are called
Fermions.
The value of F(E) never exceeds unity.
The probability finding energy for electron is
F
e
(E) = P
e
(E) =
1
1 + e
(E E
F
) / K
B
T
The probability finding energy for hole is
P
h
(E) = 1 - P
e
(E) =
1 + e
(E
F
E) / K
B
T
1
Explanation(F D statistics)
P(E)
E
O
At
T = 0 K
E
F

Figure-1
1.0
P(E)
E
O
At
T = 0 K
E
F

Figure-2
1.0
E
1
E
3
E
2
T
1
T
2
T
3
Where,
E
3
> E
2
> E
1
> E
F

T
3
> T
2
> T
1
> T


From figure the following points are noted.
When the material is at a temperature higher than
0 K, it receives the thermal energy from surroundings
and they excited.
As a result, they move into higher energy levels
which were unoccupied at 0 K. The occupation
obeys a statistical distribution called Fermi Dirac
distribution law.
According to this law, the probability F(E) or P(E)
that a given energy state E is occupied at a
temperature T is given by
Where,
F(E) = P(E) = Fermi Dirac probability function
K
B
= Boltzmann constant
F(E) = P(E) =
1
1 + e
(E E
F
) / K
B
T
--------- (1)
And E
f
is called Fermi energy and is a constant for a
given system.
The maximum energy
possessed by an electron at
absolute temperature is
known as Fermi energy( E
F
).
From equation (1) we may discuss the following 2 cases.
CASE:1
If E > E
F
,
then the exponential term becomes infinite and F(E) = 0
i.e. there is no probability of finding an occupied state of
energy greater than E
F
at absolute zero.
Hence, Fermi energy is the maximum energy that any
electron may occupy at 0 K
As temperature increases the electrons are occupied
the higher energy states which are unoccupied at 0 K
as shown in figure(2).
CASE:2
If E = E
F
,
then the F(E) = P(E) = at any temperature.
Hence, Fermi level represents the energy state with
50% probability of being filled.
Electrons in a crystal(metal) obey the Fermi Dirac
(F-D) distribution (statistics)
Let E
1
, E
2
, E
3
E
i
be the energy of the particles,
g
1
, g
2
, g
3
---- g
i
be the energy states & n
1
, n
2
, ---- n
i
.


The number ways in which n
i
particles can
be put in g
i
number of states are given by
g
i
(g
i
-1)(g
i
-2)(g
i
-3)-----(g
i
n
i
+1)
(OR)
g
i
!/(g
i
n
i
)! ----- (1)
Dividing the eq(1) with n
i
! ,

we get number of Eigen
energy states


g
i
! / n
i
! (g
i
n
i
)! ------- (2)
Thus, for the whole system, the total number of Eigen
energy states can be written as
G =
i
g
i
!/n
i
!( g
i
n
i
)! ---- (3)
(OR)
The probability W of a specific state is
proportional to the total number of energy (G)
W G
Substituting the eq(3) in eq(4), we get,
W = CG --- (4)
Where,
C -- constant
gi!
n
i
! (g
i
-n
i
)!
X constant --- (5)

i
W =
Taking log on both sides of eq(5), we get,
g
i
!
n
i
! (g
i
-n
i
)!
+ constant

i
log

log W =
log W =
i
log g
i
! log (n
i
! (g
i
-n
i
)! + log C
log W =
i
log g
i
! log n
i
! + log (g
i
-n
i
)! + log C
log W =
i
log(g
1
, g
2
,-- g
i
) log(n
1
, n
2
-- n
i
) + log (g
1
-n
1
)----

---log (g
i
n
i
) + log C
log W =
i
g
i
log g
i
n
i
log n
i
(gi n
i
) log (g
i
n
i
) + log c
log W =
i
(n
i
g
i
) log (g
i
n
i
) + g
i
log g
i


n
i
log n
i
+ log c --- (6)
Differentiating eq(6) w.r.t. n
i
, we get,
(log w) =
i
(n
i
0) log( g
i
- n
i
) + (n
i
- g
i
) 1 (0 n
i
)


+ 0 - n
i
/n
i
n
i
log n
i
n
i
+ 0
(g
i
n
i
)
(log w) =
i
(n
i
log( g
i
- n
i
) + (n
i
- g
i
) 1 n
i
- n
i


log n
i
n
i

n
i
g
i

(log w) =
i
n
i
log( g
i
n
i
) log n
i
n
i

Therefore,
(log w) = -
i
log n
i
- log( g
i
n
i
) n
i



log n
i

( g
i
n
i
)
-
i
(log w) =
n
i
--- (7)
For maximum probability,
(log w) = 0
Hence, eq(7) becomes as
( g
i
n
i
)

i

n
i
= 0 --------(8)
log n
i

To evaluate the distribution function, two auxillary conditions
has to be introduce in eq(8)
n = n
i
= 0 --- (9) 1-----
E = E
i
n
i
= 0 --- (10)
2-----
Multiplying eq(9) by & eq(10) by & adding
the resultant expression to eq(8) , we get
( g
i
n
i
)

i

n
i
= 0
log n
i

n
i
+ n
i
+ E
i
(OR)
( g
i
n
i
)

i

n
i
= 0
log n
i

+ + E
i
Since,
Since, n
i
is arbitrary it is 0
Therefore,
( g
i
n
i
)
= 0
log n
i

+ + E
i
(OR)
( g
i
n
i
)
log n
i

= - ( + E
i
)

( g
i
n
i
)
n
i

= e
-( + Ei )
- n
i
( 1 - g
i
/ n
i


)
n
i


e
( + Ei )
1
=
g
i
/ n
i
- 1


1

e
( + Ei )
1
=
(OR)
g
i
/ n
i
- 1


=
e
( + E
i
)
(OR)
g
i
/ n
i



=
1 + e
( + E
i
)
Therefore, the Fermi Dirac function can be written as
F (E) = n
i
/g
i
=
1
1 +
e
+ E
i