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STATISTICAL

MECHANICS
Introduction
The subject which deals with the relationship
between the overall behavior of the system and the
properties of the particles is called Statistical
Mechanics.
Statistical Mechanics can be applied to classical
systems such as Molecules in gas as well as
Photons in a Cavity and Free Electrons in a
Metal.
Physical System
Consider a system composed of N identical, non
interacting particles in a volume V .
let n
1
particles posses energy E
1
,
n
2

particles posses energy E


2

. and so on.
Total energy of the system

=
=
+ + + =
i
i i
n N
and
E n E
E n E n E n E .....
3 3 2 2 1 1
Macro States and Microstates of Systems
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 ) .
The state of system as specified by the actual properties of
each individual, elemental components and it is permitted
by the uncertainty principle is known as Micro State .
For N particle system , there may be always possible
N+1 Macro States and 2
n
Micro States.
Phase Space
1.The three dimensional space in which the location of a particle is
completely specified by the three position coordinates, is known as
Position Space.
2.The three dimensional space in which the momentum of a
particle is completely specified by the three momentum
coordinates P
x,
P
y
and P
z
is known as Momentum Space.
3.The combination of the position space and momentum space is
known as Phase Space.
z y x
dp dp dp d = I Space Momentum a in volume Small
dxdydz dV = space Position a in volume Small
I = dVd dt Space Phase a in volume Small
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.
All the points within this sphere will have their
Momenta lying between 0 and p
m
.
p
z
0
p
x
p
y
p
m
) volume space position a is V where (
.....
3
4
volume space phase
3
4
volume momentum
. p radius of sphere the of volume
volume space momentum The
3
3
m
V p
V
p
m
m
t t
t
t
=
I =
= I
=
t
t
d
V
n
I
=
=
cells of number 3.Total
cell one of volume
space phase in volume available Total
space phase in cells of number total 2.The
. cell a called is space phase in d volume small 1.The
Ensemble
An Ensemble is defined as a collection of very large
number of Assemblies which are essentially independent
of one another. There are three types of ensembles.
1.Microcanonical ensemble
2.Canonical ensemble
3.Grand canonical ensemble
Micro Canonical
Ensemble
Canonical
Ensemble
Grand Canonical
Ensemble
All assemblies
1. Same Volume ,
2. Same number of
particles N,
3. Same energy E.
All assemblies
1.Same Volume ,
2.Same Number of
particles N,
3. Same
temperature T.
All assemblies
1. Same Volume ,
2. Same temperature
T and Same
Chemical potential
.
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 E and
f(E) is the probability of occupancy of each state of
energy E .
Classical Statistics
( Maxwell Blotzmann distribution)
Statistical Distribution
Quantum Statistics
Bose - Einstein distribution
Fermi - Dirac distribution
Classical Statistics
(Maxwell - Blotzmann Distribution)
Let us consider a system consisting of molecules of an
ideal gas under ordinary conditions of temperature and
pressure.
Such a system is governed by the laws of Classical
Maxwell- Blotzmann Statistics.
Assumptions:
1. The particles are identical and distinguishable.
2. The volume of each phase space cell chosen is
extremely small and hence chosen volume has very
large number of cells.
3. Since cells are extremely small, each cell can have either one
particle or no particle though there is no limit on the number of
particles which can occupy a phase space cell.
4. The system is isolated which means that both the total number
of particles of the system and their total energy remain constant.
5. The state of each particle is specified instantaneous position and
momentum co-ordinates.
6. Energy levels are Continuous.
Equation for MB Distribution
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 [ the number
of molecular 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.
. .... ..... ., .
3 2 1
const n n n n n n e i
i i
= E = + + + + + =
Hence its derivative
] 1 .....[ 0 = E
i
n o
The total energy of the system is given by
const n E E
n E n E n E n E E
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
,n
i,
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 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 2
1
1
2
n n n n
n n
n n
n
C

The number of ways in which the particles in all groups are chosen is
factor tion multiplica is where
n
n
w
n n n n n
n
w
n n n n
n n
n n n
n
w
i
i i
t
t
)
!
!
(
)
!........ ! ! ! !
!
(
)......
)! ( !
)! (
)(
)! ( !
!
(
1
5 4 3 2 1
1
2 1 2
1
1 1
1
=
=

=
i
t
i
i
n
i i
n
i
n n n
g W
g g g g W
) (
... ) .....( ) ( ) ( ) (
2
3 2 1 2
3 2 1
t =
=
The number of different ways by which n particles of the system
are to be distributed among the available molecular states is
]
!
[ !
) (
!
!
2 1
i
n
i
i
n
i i
i i
n
g
n W
g
n
n
W
W W W
i
i
t
t
t
=
=
=
Taking natural logarithms on both sides of equation in above.
! lng n ! lnn n nlnn
! lng n lnn! n n nlnn lnW
x, xlnx lnx!
ion approximat Striling Applying
lng n ! lnn lnn! lnW
i
i
i i
i
i
i
i
i
i
i
i i i i


+ =
+ =
=
+ =
For the Most probable distribution.
] 3 ].......[ 0 [
) (ln
1
ln
) (ln
1
ln
0 ln
max
max
max
= E
+ =
+ =
=


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

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


and adding to the (3) equation and there by
T K
E
i MB
B
T K
E
i
i
E
i
i
B
i
B
i
i
e e
E f
T k
where
e e
g
n
e e
g
n
o
o
| o
|
1
) (
)
1
(
1
sides both on l exponentia Taking
E )
g
n
ln(
0 E lng lnn
0. ] E lng lnn [
i
i
i
i i i
i i i
i
i
=
= =
=
=
= +
= +

This distribution tell us the way of distribution of total energy E


of the system among the various identical particles.
Failures of Classical Statistics
1. The observed energy distribution of electrons in
Metals.
2. The observed energy distribution of Photons inside the
cavity.
3. The behavior of Heliumat low temperatures.
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
1.Bose - Einstein Distribution
2.Fermi - Dirac Distribution.
Bose Einstein Statistics
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
1. The Bosons of the system are identical and indistinguishable.
2. The Bosons have integral spin angular momentum in units of
h/2.
3. Bosons obey uncertainty principle.
4. Any number of bosons can occupy a single cell in phase space.
5. Bosons do not obey the Poulis Exclusion principle.
6. Wave functions representing the bosons are Symmetric
i.e, (1,2) = (2,1)
7. Energy states are discrete.
8.The probability of boson occupies a state of energy E is given by
1 ) exp(
1
) (

=
kT
E E
E f
f
BE
Fermi - Dirac Statistics
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
1. Fermions are identical and indistinguishable.
2. They obey Pauli s exclusion principle.
3. Fermions have half integral spin.
4. Wave function representing fermions are anti symmetric
) 1 , 2 ( ) 2 , 1 ( =
6. Uncertainty principle is applicable.
7. Energy states are discrete.
8. The probability of a fermions occupies a state of energy E is
given by
) exp( 1
1
) (
kT
E E
E F
f

+
=
Fermi Dirac Distribution
Consider the system contains n number of
indistinguishable particles carrying different energies
E
1
, E
2
.E
i
....
Let us considered ,the System be divided into groups.
If the i
th
group contains n
i
number of particles, distributed
g
i
no of quantum states, all these particles have nearly the
same energy E
i
.
The total number of ways of arranging n
i
particles in g
i
states..
! )! (
!
i i i
i
i
n n g
g
w

=
There fore the total distribution for the complete system
is given as
)} ln( ) ( ln ln { ln
)]} ( ) ln( ) [( ) ln ( ) ln {( ln
ln ! ln but
) 2 }.......( )! ln( ! ln ! {ln ln
)
! )! (
!
ln( ln
) 1 ..( .......... ..........
! )! (
!
i i i i i i i i i
i i i i i i i i i i i i i
i i i i i
i i i
i
i
i i i
i
i
n g n g n n g g W
n g n g n g n n n g g g W
x x x x
n g n g W
n n g
g
W
n n g
g
W
=
=
=
=

=

=
) 5 .........( 0
) 4 ( .......... 0
equation of dervative the on, distributi probable most for
hence constant, are E system, the of energy total the and
, system the , n particles of number total the m, equilibriu At
) 3 .....( .......... 0 } ln ) {ln(
0 )} ln( ) (
) (
) (
ln {
0 )} ln( ) ( ln ln {
0 ln
equation of derivative the on, distributi probable most For
= c =
= c =
= c
= c + c

c c

=
c
c
=
c
c
i i i
i i
i i i i i
i i i i
i i
i i
i i i
i
i
i
i i i i i i i i i
i
i
n E dE
n dn
n n n g
n g n n
n g
n g
n n n
n
n
n g n g n n g g
n
W
n
T
and
T
t k
E E
e g
n
e
n
g
e
n
g
e
n
n g
E
n
n g
E
n
n g
E n g n
n E n g n
B
f
E
i
i
E
i
i
E
i
i
E
i
i i
i
i
i i
i
i
i i
i i i i
i i i i i i
i
i
i i
B B
F
k
1
k
E -
where
.......... energy.... that of states quantum the of each
in particles of number average the represents
) exp( 1
1
1
1
1
1
) (
) (
ln
0
) (
ln
0 ) ln( ln
0 ) ) ln( ln [
3. equation to add and - by 5 and - by 4 equation multiply
s, multiplier ed undetermin method Lagrange the , Applying
= =

+
= + =
= =

+ =

= +
= +
+
+
+ +
| o
| o
| o
| o
o | o
| o
| o
| o
| o | o
Fermi Distribution function
Let us consider how the electrons in a real material distribute among
the different possible energy states.
The assembly of electrons considered as electron gas behaving like
a system of Fermi particles obeying Fermi - Dirac statistics.
Accordingly, the probability F(E) of an electron occupying an
energy level E is given by
Where E
f
is called Fermi energy and is a constant for a given
system.
) exp( 1
1
) (
kT
E E
E F
f

+
=
This means that at 0k, all quantum states with energy below E
f
are completely occupied and those above E
f
are unoccupied.
0 ) ( ,
1 ) ( ,
0
= >
= <
=
E F E E
E F E E
for
K T
At
f
f
0 E
f
E
F(E)
0.5
T=0K
T
3
>T
2
>T
1
>0K
T1 T2 T3
At any temperature other than 0k,if E = E
f
, F(E)=1/2.
Hence, the Fermi level is that state at which the
probability of electron occupation is at by temperature
above 0K and also it is the highest level of the filled
energy states at 0K.
Fermi energy is the energy of the state at which the
probability of electron occupation is at by temperature
above 0K.
Density of Energy States
The Number of Electrons present per unit volume in an energy
level at a given temperature is equal to the product of states ( no
of energy levels per unit volume ) and Fermi Dirac distribution
function ( the probability to find an electron ).
) ( ) ( E F dE E g n
band energy
c
}
=
Where g(E) density of states and F(E) is the probability
function.
Therefore, to calculate the number of electrons in an energy
level at a given temperature, it is must to know the number of
energy states per unit volume ( Density of states ).
3
3
4
n n t =
Therefore the number of energy states within a sphere of radius n
Since n
1
,n
2
and n
3
can have only
positive integer values, we have
to consider only one octant of
the sphere.
}
3
4
{
8
1
3
n t =
n
n
x
n
y
n
z
dn
E
E+ dE
The number of energy states with particular energy value E is
depending on how many combinations of the quantum numbers
resulting in the same value n.
In order to calculate the number of states within a small
energy interval E and E + dE, we have to construct two
spheres with radii n and n + dn and calculate the space
occupied within these two sphere.
Thus the number of energy states having energy values
between E and E + dE is given by
dn n dE E g
n dn n dE E g
2
3 3
2
) (
) }(
3
4
{
8
1
) }(
3
4
{
8
1
) (
t
t t
=
+ =
The expression for the energy
of electron in potential well
is given by
2
1
2
1
2
2
2
1
2
1
2
2
2
2
2
2
2
2
2
1
2
2
2
2
2
2
2 2
}
8
{
2
1
}
8
{
2
1 8
8
}
2
1
{
8
2
) 1 ( .,
)
8
(
) 1 ........(
8
8
E
dE
h
mL
dn
E
dE
mL
h
h
mL
dE
h
mL
n
dn
dE
h
mL
ndn
eq ting differntia
h
E mL
n
h
E mL
n
mL
h n
E
n
(

=
(

=
=
=
=
=
=
Substituting the values of n
2
and dn from in eqn.. (1)
dE E L m
h
dE E
h
mL
dE E g
2
1
3
2
3
3
2
1
2
3
2
2
) 2 (
4
]
8
[
4
2 ) (
t
t
=
=
Density of energy states is given by number of energy states
per unit volume.
Density of states
dE E m
h
dE E g
2
1
2
3
3
) 2 (
4
) (
t
=

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