# PBC Lecture Notes in Physics Series– Statistical Physics by Dr.

Abhijit Kar Gupta 1
Statistical Physics
(A set of lecture notes for undergraduate level students; for private circulation only)
Lecture Notes prepared by-
Dr. Abhijit Kar Gupta
Physics Department, Panskura Banamali College
Panskura R.S., East Midnapore, W.B., India, Pin-Code: 721152
e-mail: kg.abhi@gmail.com, Ph.(res.) 033-40644589

References:
1. Perspectives of Modern Physics
- Arthur Beiser (McGraw-Hill)
2. Fundamentals of Statistical and Thermal Physics
- Federick Reif (McGraw-Hill Book Company, Int. Ed.)
3. Fundamentals of Statistical Mechanics
- B.B. Laud (New Age Int. Publishers)
4. Statistical Physics (Lecture notes downloaded from Internet)
- Harvey Gould & Jan Tobochnik

Lecture-1

What is Statistical Physics?

- Statistical Physics describes a many-particle system.
- Statistical Mechanics combines statistical ideas with the laws of Mechanics.
- Statistical ideas involve the concept of probability. The laws of Mechanics refer
to the Classical Mechanical (Newtonian) laws or Quantum Mechanical laws
according to the characters of the particles involved.

The laws of Classical and quantum mechanics determine the behaviour of molecules at
the microscopic level. The goal of Statistical Mechanics is to begin with the microscopic
laws of Physics that govern the behaviour of the constituents of the system and deduce
the properties of the system as a whole. Statistical Mechanics is the bridge between the
microscopic and macroscopic worlds.

Note: Comparison of Statistical Physics and Thermodynamics

- Thermodynamics provides a framework for relating different macroscopic
properties of a system. Thermodynamics is concerned only with the
macroscopic variables and ignores the microscopic variables that
characterize individual molecules.

- Statistical Physics and Thermodynamics both assume that the average
macroscopic properties do not change with time. We call them
Equilibrium Statistical Physics or Equilibrium Thermodynamics.
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 2

The essential steps for the statistical description of a system of particles:

1. Specification of the state of the system:

We need a method to recognize a system of particles at a particular time. This means we
have to keep track of positions and momentums of all the particles of a large system
through some way in order to understand the emerging thermodynamic and other
physical properties of the entire system.
Consider a system of gas particles. The positions and momentums of the particles may
continuously change to give a new identification of the many body system. This
„identification‟ is a „state‟ of the system in the classical sense.

Quantum mechanically the state of a system of atoms, electrons or molecules is described
by a wave functionv , which is a function of a set of variables.

2. Statistical Ensemble:
Ensemble is a collection of a set of states (of the system of particles) under similar
external conditions.

Example

Let us throw 10 dice together. At one time we may have a set such that the 1
st
one shows
1 on the top face, 2
nd
one 5, the 3
rd
one 6 and so on. The set of all these 10 dice for one
such throwing event is what we may call a state of the system of 10 dice.
If we now repeat the performance under similar conditions, then the collection of all such
unique states form an ensemble.

3. Basic postulate of a priori probability:

When we do have a probabilistic event, we ask for the probability of occurrence of a
particular outcome. We do not have to do all the experiments to enumerate that. Instead,
we estimate this probability of occurrence of a single event through some fundamental
postulate (kind of adhoc assumption). This is the postulate of a priori probability.

Example

When we toss a coin, it is not possible to say which side of the coin will flip: „head‟ or
„tail‟. Our deterministic laws of Mechanics can not help. But our knowledge of the
physical situations in such a case leads us to expect a priori probability which is 1/2.

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 3
4. Probability Calculations:

Once the basic postulate of a priori probability is determined, we theoretically calculate
the probability (with the help of theory of probability) of the outcome of any experiment
on the many-particle system.

Lecture-2

Concept of Phase Space

Suppose a system of particles has n degrees of freedom. This means that all the particles
in the system can be described by n positional coordinates ( q ) and n linear momentum
coordinates ( p ). We can represent all these coordinates in a n 2 dimensional hyperspace
and we get a point. If the system evolves with time (that is the particles in it change their
positions and momentums), the representative point moves in that space. The space such
defined is called Phase space.

Example:

If a particle moves in one dimension then we can draw two Cartesian coordinate axes
labeled by q and p . We can then specify a point ( p q, ) in this two-dimensional space. At
another time when the position ( q ) and momentum ( p ) of the particle change, the point
moves in this space. Each point in this space (Phase space, as we call it) describes the
state of the system.

Fig.1

If the particle is free (moves without constraint), it can go anywhere and can have any
amount of energy or momentum. Therefore, the representative point ( p q, ) in the phase
space can move anywhere. The phase space has infinite extent.
However, the state of the system can never be determined with absolute accuracy. The
level of accuracy depends on the experimental measurements. Suppose our measurement
yields the position and momentum coordinates in certain ranges, q to q q o + and p to
q ÷
p
|

) , ( q p -
In this example,
the dimension of the phase space =2.
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 4
p p o + respectively. Then accordingly, we divide the phase space into small cells of
width q o and height p o and specify the state ( p q, ) which belongs to a particular cell.

Fig.2

Area of each cell is
0
h p q = o o , a constant which has a dimension of angular momentum.

The concept of phase space for a system of particles:

If a system has „ f ‟ degrees of freedom, then the system can be described by a set of f
positional coordinates
f
q q q ....... ,
2 1
and f momentums
f
p p p ......... ,
2 1
.
For a system of N free particles, N f 3 = .
Now we can construct a hypothetical phase space of f 2 -dimensions: f -number of axes
for positions and f -number of axes for momentums. Therefore, the set of numbers (the
coordinates,
f
q q q ....... ,
2 1
,
f
p p p ......... ,
2 1
) can be considered as a point in the f 2 -
dimensional phase space. Again, as before, the phase space is divided into cells according
to the accuracy of the measurement and we obtain the volume of a cell to be
q ÷
p
|

-
) , ( p q
NOTE:
The size of the cell depends upon the accuracy of measurement. More accurately w can
measure the state ( p q, ), the less will be the uncertainties q o and p o , the less will be
the size of a cell.
The lower limit of the size of each cell is determined by the Heisenberg Uncertainty
principle in Quantum Mechanics:
2

> p qo o , where
t 2
h
=  , h being the Planck‟s
constant.
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 5
f
f f
h p p p q q q
0 2 1 2 1
...... ..... = o o o o o o . Here the accuracy of measurement in any n -th
direction is
n
q o and
n
p o such that
0
h p q
n n
= o o .

Phase Space for a bounded system:
One dimensional Harmonic Oscillator

The energy of the oscillator is given by
2
2
2
1
2
kx
m
p
E + = ,
where x is the displacement, p is the momentum and k is the spring constant.
If the total energy E of the oscillator is a constant, then it describes an ellipse in the 2-
dimensional phase space made by x and p .
In practice, the accuracy of the measurement is such that position lies between x and
x x o + and momentum lies between p and p p o + . Therefore, the energy of the
oscillator lies between E and E E o + . Thus the phase space is confined in the region
between two ellipses corresponding to E and E E o + . So, there are many different sets
of ( p x, ) lying within the cells in the annular region.

Fig.3

Note that a given interval dx corresponds to a larger number of cells lying between the
two ellipses when A x ~ (near the maximum value of x ) than when 0 ~ x (near origin).
This indicates that we have the greater probability of finding the oscillator in the
microstates which are close A (amplitude) than close to origin. This result is supported
E E o +

E
dx dx
x
p
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 6
by the fact that the oscillator has small velocity near the extreme points A x ± ~ ( ); hence it
spends a longer time there than near equilibrium point ( 0 ~ x ), where it moves rapidly.

Lecture-3

Microstate:
Suppose the cells in the phase space are numbered with some index = n 1, 2, 3……. Then
the state of the system of particles is described by specifying a particular cell (having
some n -value) where the system is found. Each cell describes a microscopic state or
„microstate‟ of the system.

Quantum Mechanically, a quantum state is described by
n
v , where n = 1, 2,
3…..designate possible quantum numbers.

Macrostate:
The macroscopic state or „macrostate‟ of a system is defined by specifying the external
parameters of the system and any other conditions acting on the system. The external
parameters can be volume of the system or constant total energy (for an isolated system)
etc.
Corresponding to a given macrostate the system can be in any of the possible microstates.

Concept of Equilibrium:
An isolated system is said to be in equilibrium when the probability of finding the system
in any one state is independent of time. All macroscopic parameters describing the
system are then also time independent.
In other words, the system is equally likely to be found in any of the states accessible to
it.

Estimation of number of Microstates
Ideal Gas:

Consider an ideal monatomic gas of N molecules enclosed in a volume V . Because of
the interaction between the molecules is zero, the energy is only kinetic (Potential energy
0 = U ).

If the molecules are numbered as 1, 2, 3, ….. n and we associate the momentum of the
center of mass of the i -th molecule as
i
p , the energy of the system of noninteracting
molecules can be written as

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 7
2
1
2
1
¯
=
=
N
i
i
p
m
E ……………………………… (1)

Now we can construct the phase space by N 3 -position coordinates (
N
r r r ,...... ,
2 1
) and
N 3 -momentum coordinates (
N
p p p ,...... ,
2 1
). Each position and momentum vector has
three components in the three dimensional coordinate system.

The number of microstates ) (E O lying between the energies E and E E o + is then
equal to the number of cells in the phase space contained between E and E E o + . The
number of cells is proportional to the volume of the phase space.

) (E O · Volume of phase space.

Therefore, we now estimate the volume of phase space of the system:

Volume of phase space =
1
3
....... r d
í í
2
3
r d …….
2
3
r d
1
3
p d
2
3
p d ……
N
p d
3
, ……(2)

where the integration is done over all positions and momentum coordinates for which the
total energy lies between E and E E o + .

Since each integral over
i
r extends over the volume V of the container (each molecule,
being free, can move anywhere in the closed space),

V r d
i
=
í
3
…………………………… (3)

There are N such integrals. Therefore, the contribution in the expression (2) is .
N
V

Now we rewrite expression (1) where we explicitly show the momentum components.

( )
¯
=
+ + =
N
i
iz iy ix
p p p mE
1
2 2 2
2 ………………………………….. (4)
The sum in (4) contains N 3 square terms (N-particles, 3-components each). For
= E const., we may think of equation (4) as an equation for a sphere in N 3 -dimensional
hyperspace. Then we shall have the radius
2 / 1
) 2 ( ) ( mE E R = .
Note:
Here
i i i i
dz dy dx r d ÷
3
and

i i i i
dp dp dp p d ÷
3
. These are the three dimensional volume elements.
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 8
Volume of a sphere in N 3 -dimension is proportional to
N
R
3
(Note: the volume of a
sphere in 3-dimension is proportional to
3
r , where r is the radius).

Thus the Volume of phase space is proportional to
2 / 3
) 2 (
N N
mE V . So now we can write
the number of microstates,
2 / 3
) 2 ( ) (
N N
mE V E · O

2 / 3
) 2 ( ) (
N N
mE AV E = O ,

where A is a constant independent of V and E . The expression tells us how the number
of accessible microstates in an ideal monatomic gas depends on the volume and energy.
Since, N is generally of the order of Avogadro‟s number (~
23
10 ) and thus very large,
) (E O thus increases extremely rapidly with energy.

Lecture-4

Microcanonical Ensemble:
An ensemble representing an isolated system in equilibrium is called “microcanonical”
ensemble.
If the energy of an isolated system in a state r is denoted by
r
E , the probability
r
P of
finding the system in that state is given by

r
P = C (Const.) if E E E E
r
o + < < ,
= 0 Otherwise.

If a phase space is constructed for such a system corresponding to energy in the range
between E and E E o + , the system is equally likely to be found in any of the cells
(microstates). Thus the probability (
r
P ) is same for any of the cells.
The constant C can be determined from the normalization condition (the system must be
found in any of the cells): 1 =
¯
r
r
P , the sum is over all the accessible microstates in the
range between E and E E o + . If the system has total N -number of microstates, then we
have
N
P
r
1
= for any r in the energy range.

Note: Suppose A is not an isolated system and it interacts with another system B.
We can treat the combined system (A+B) to be isolated. Thus the microcanonical
ensemble can be formed for the combined system.

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 9
Canonical Ensemble:

Canonical ensemble is referred to a system when it interacts (thermally) with a heat
reservoir (called, Environment).

Probability of finding the system in any microstate r is

r
E
r
e C P
| ÷
= . ,

where C is the constant of proportionality. Now we use the Normalization condition,
1 =
¯
r
r
P .
We get 1 =
¯
÷
r
E
e C
|
.
¯
÷
=
r
E
r
e
C
|
1
.
The normalized probability is
¯
÷
÷
=
r
E
E
r
r
r
e
e
P
|
|
.
The parameter | has the dimension of inverse of energy. In Statistical Physics one
chooses
kT
1
= | , where k is Boltzmann constant and T is the equilibrium (absolute)
temperature of the system.

Note: (for interested students)
Derivation of the Probability:

Let us consider a small system A is in thermal interaction with a heat reservoir B. Here
we consider A << B, the degrees of freedom in A is much less than that of B.

If the interaction between the two systems is weak, the energies are additive. The energy
(
A
E ) of A is not fixed. Whereas the total energy of the combined system (A+B) has a
constant value in the range between
T
E and E E
T
o + .
Suppose, A is found to be in a state r of energy
A
r
E .
From the conservation of energy we can write:

T B A
r
E E E = + ,
where
B
E is the energy of the reservoir.
A
r
T B
E E E ÷ = .
We then have the number of accessible states to the reservoir is
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 10

) ( ) (
A
r
T B
E E E ÷ O = O
Now if the system A is in a definite state (the state is fixed), the number of states
accessible to the combined system (A+B) is also ) (
A
r
T
E E ÷ O .

In this situation, where A is fixed in a state r , the probability
r
P of occurrence of this is
simply proportional to the number of states accessible to the combined system (A+B).
Therefore,
C P
r
' = ) (
r
T
E E ÷ O , ………………………..(1)
where C' is a constant of proportionality. We now use
r
E in place of
A
r
E for
convenience.

Now make use of the fact that A << B and thus A << (A+B), the combined system.
Hence
r
E <<
T
E .
So, we can write the following Taylor expansion, considering
r
T B
E E E ÷ = ,

..... ..........
ln
) ( ln ) ( ln
r
E E
B
T
r
T
E
E
E E E
T B
=

c
O c
÷ O = ÷ O

The expansion is around
T B
E E = . The other higher order terms are neglected.
The derivative
T B
E E
B
E
=

c
O cln
| ÷ is evaluated at the fixed energy
T B
E E = and thus a
constant independent of energy
r
E of A.
Hence we can write the above expansion as

r
T
r
T
E E E E | ÷ O = ÷ O ) ( ln ) ( ln

or,
r
E T
r
T
e E E E
| ÷
O = ÷ O ) ( ) ( . …………………………….(2)
Here ) (
T
E O is a constant independent of r . Combining (1) and (2) we thus have
r
E
r
e C P
| ÷
= .

EXAMPLE: A molecule in an ideal gas.

Let us think of a single molecule which is at thermal equilibrium with all the other
molecules at (absolute) temperature T and enclosed in a volumeV . This system of a
single molecule can be thought of in a canonical ensemble.
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 11

Energy of the molecule, ) (
2
1
2 2 2
z y x
p p p E + + = .
Therefore, the probability that the molecule has momentum lying in the range
x
p
and
x x
dp p + ,
y
p and
y y
dp p + ,
z
p and
z z
dp p + is

z y x
p p p
z y x
dp dp dp e dp dp Pdp
z y x
) (
2 2 2
+ + ÷
·
|
,

Considering canonical probability (
E
e
| ÷
). Thus we can easily get a distribution for
velocities which are Maxwell distribution of molecular velocities.

Lecture-5

Calculation of Physical quantities in Canonical Ensemble:

Probability

¯
÷
÷
=
r
E
E
r
r
r
e
e
P
|
|
=
Z
e
r
E | ÷
,
where
¯
÷
=
r
E
r
e Z
|
is called Partition function.

kT
1
= | , dimension is inverse of energy.
k = Boltzmann constant
T = Absolute temp.

Average Energy:

¯
¯
¯
÷
÷
= =
r
E
r
r
E
r
r
r
r
r
e
E e
E P E
|
|
,
where the sums are over all accessible microstates r of the system.

To simplify, we use a trick.
r
r
E
E e
r
¯
÷|
= |
.
|

\
|
c
c
÷
¯ ¯
÷
r
E
r
r
e
|
|
= |
.
|

\
|
c
c
÷
¯
÷
r
E
r
e
|
|
=
| c
c
÷
Z

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 12
Hence, we obtain

E =
| c
c
÷
Z
Z
1
=
| c
c
÷
Z ln
.

Dispersion of Energy:

( ) ( )
2
2
2
2
2
2
2 E E E E E E E E E ÷ = + ÷ = ÷ ÷ A

Here

¯
¯
÷
÷
=
r
E
r
r
E
r
r
e
E e
E
|
| 2
2
.
We use the trick again to simplify:

|
.
|

\
|
|
|
.
|

\
|
c
c
÷ = |
.
|

\
|
c
c
÷ =
¯ ¯ ¯
÷ ÷ ÷
r
E
r
r
E
r
r
E
r r r
e E e E e
| | |
| |
2
2

Z
E
1
2
= |
.
|

\
|
|
|
.
|

\
|
c
c
÷
¯
÷
r
E
r
e
|
|
2

=
2
2
1
| c
c Z
Z

Therefore, we can write

( ) = ÷ = A
2
2 2
E E E
2
2
1
| c
c Z
Z
2
2
1
|
|
.
|

\
|
c
c
÷
|
Z
Z
=
2
2
ln
ln
1
| | | | | c
c
=
|
|
.
|

\
|
c
c
c
c
=
|
|
.
|

\
|
c
c
c
c Z
Z
Z
Z
.

We can also write the above in terms of average energy:

( ) .
ln
2
| | | c
c
÷ =
|
|
.
|

\
|
c
c
÷
c
c
÷ = A
E Z
E

When we use the relation
kT
1
= | , we get

( )
2
E A =
| c
c
÷
E
=
| c
c
c
c T
T
E
=
V
C kT
2
.

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 13
Therefore, the energy fluctuation in the canonical ensemble is proportional to the specific
heat.

Example #1
A system with two energy levels is in thermal equilibrium with a heat reservoir at
temperature 600 K. The energy difference between the levels is 0.1 eV. Find (i) the
probability that the system is in the higher energy level and (ii) the temperature at which
this probability will equal 0.25.

The system is in canonical ensemble.
(i)
1
1
1 +
=
+
=
÷
÷
E E
E
e e
e
P
| |
|
…………….(1)

600 10 38 . 1
10 6 . 1
16
13
× ×
×
= =
÷
÷
kT
E
E | ………….(2)

Putting (2) in (1) we get 126 . 0 = P

(ii)
1
1
25 . 0
/
+
=
kT E
e
, Put
T kT
E
× ×
×
=
÷
÷
16
13
10 38 . 1
10 6 . 1
and we obtain 1056 = T K.

Lecture-6

The Equipartition of Energy:

According to Classical Mechanics, for a system having f -generalized coordinates and
f -generalized momenta, the Energy can be written as

). ..... , , ..... , (
2 1 2 1 f f
p p p q q q E E =

Now let us assume that the energy obeys the following:

(i) Energy is additive.
This means the total energy E can be written as the sum of energies for all f -modes.
f i
E c c c c ....... ......
2 1
+ + + + = ,
where ,... ,
2 1
c c are the energies corresponding to the 1
st
mode, 2
nd
mode and so on. The
above expression can be written as
E E
i
' + = c ,
where the i -th mode is separated out and the rest is included in E' .

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 14
(ii) Energy is quadratic in momentum.

We can write
2
) (
i i i
p p ì c = , ì is a constant.

If the system is in equilibrium at the absolute temperature T , the energy should be
distributed according to the canonical ensemble.

Now the mean value of the energy
i
c for the i -th mode can be written as

f f
E
f f i
E
i
dp dp dp dq dq dq e
dp dp dp dq dq dq e
.... .....
.... ....
2 1 2 1
2 1 2 1
í
í
·
· ÷
÷
·
· ÷
÷
=
|
|
c
c

f f
E
f f i
E
dp dp dp dq dq dq e
dp dp dp dq dq dq e
i
i
.... .....
.... ....
2 1 2 1
) (
2 1 2 1
) (
í
í
·
· ÷
' + ÷
·
· ÷
' + ÷
=
c |
c |
c

f i i f
E
i
f i i f
E
i i
dp dp dp dp dq dq dq e dp e
dp dp dp dp dq dq dq e dp e
i
i
.... .... .....
... .... ....
1 1 1 2 1
1 1 1 2 1
+ ÷
·
· ÷
' ÷
·
· ÷
÷
·
· ÷
+ ÷
·
· ÷
' ÷ ÷
í í
í í
=
| |c
| |c
c

í
í
·
· ÷
÷
·
· ÷
÷
=
i
i i
dp e
dp e
i
i
|c
|c
c

í
í
·
· ÷
÷
·
· ÷
÷
c
c
÷
=
i
i
dp e
dp e
i
i
|c
|c
|

Suppose,
i
dp e X
i
í
·
· ÷
÷
=
|c

( )
X
X
i
|
c
c
c
÷
= = X ln
| c
c
÷

Now we evaluate the integral:

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 15
i
dp e X
i
í
·
· ÷
÷
=
|c
=
í
·
· ÷
÷
i
p
dp e
i
2

=
í
·
÷
0
2
2
i
p
dp e
i

We substitute
2
i
p y |ì = .

i i
dp p dy |ì 2 =
=
i
dp
y
2 / 1
2
|
|
.
|

\
|

|ì = ( )
i
dp y
2 / 1 2 / 1
2 |ì

i
dp = dy y
2 / 1
2
1
÷

X =
í
·
÷
0
2
2
i
p
dp e
i

= 2 dy y e
y 2 / 1
0
2
1
÷
·
÷
í

= dy y e
y ) 1 2 / 1 (
0
1
÷
·
÷
í

= ( ) 2 / 1
1
I

= t

1
=

t
.

Therefore, we can write

| | ì | t
|
c ln ln ln ÷ ÷
c
c
÷ =
i

=
|
.
|

\
|
÷
c
c
÷ |
|
ln
2
1
=
| 2
1
.

This is Equipartition theorem of Classical Statistical Mechanics.

Theorem:
The mean value of each independent quadratic term (corresponding to each mode) in the
energy of a canonical system is kT
2
1
.

Example: Harmonic Oscillator
Energy
2
2
2
1
2
kx
m
p
E + = .
The energy term has two square terms (two modes) in it. Therefore, the mean energy for
the oscillator is E = kT
2
1
2× = kT .
This result can be derived directly:

kT
i
2
1
= c
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 16
E =
í
í
·
· ÷
÷
·
· ÷
÷
dpdx e
Edpdx e
E
E
|
|
= . kT

Application: A molecule in an ideal gas.

Energy, ( )
2 2 2
2
1
z y x
p p p
m
+ + = c
The single molecule has three modes (the degrees of freedom).
According to equipartition theorem, the average energy for each mode is kT
2
1
.
.
2
3
2
1
. 3 kT kT = = c

One mole of gas contains N (Avogadro number ~
24
10 ) number of molecules.
Therefore, the mean energy per mole of gas is

NkT kT N N E
2
3
)
2
3
( = = = c .

The molar specific heat at constant volume is

R NK
T
E
C
V
V
2
3
2
3
= =
|
|
.
|

\
|
c
c
= , ' ' R is known as gas constant.

The fluctuation (dispersion) in energy can be calculated as

( )
2
E A =
V
C kT
2
= Nk kT
2
3
2
=
2 2
2
3
T Nk where we consider the ideal gas at equilibrium
is in canonical ensemble and we use the result derived earlier.

The relative fluctuation is
( ) | |
2 / 1
2 / 1
2 2
2 / 1
2
3
2
2
3
2
3
|
.
|

\
|
=
|
.
|

\
|
=
A
N
NkT
T Nk
E
E

The above shows that the relative fluctuation (in energy) becomes less and less important
as the system size increases. This is negligible when 1 >> N .

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 17
Lecture-7

Maxwell-Boltzmann (MB) Statistics:

MB statistics is applicable to Classical particles which are identical and distinguishable.
Consider a system of N -particles (molecules in general) which can be found in any of its
microstates having energy E .
Now the individual particles may have some discrete energy states
1
c ,
2
c ,
3
c ….and so
on so that there are
1
n particles of energy
1
c ,
2
n particles of energy
2
c ….up to
k
n
particles of energy
k
c .
Therefore, we can write

k i
n n n n + + + =
¯
..........
2 1
= N ………………………..(1) [ Conservation of particles]
i i
n c
¯
=
k k
n n n c c c + + + . ..........
2 2 1 1
= E ……………….(2) [ Conservation of Energy]

Let us assume that
i
g be the number of microstates each of which has the same
energy
i
c . Then the number of ways for a single particle to occupy any of the states is
i
g
(degeneracy).
The number of ways for two particles to have the same energy
i
c is then
i
g ×
i
g =
2
i
g .
The number of ways for
i
n particles to have the same energy
i
c =
i
n
i
g .
So the number of ways for
1
n particles to have energy
1
c ,
2
n particles to have energy
2
c
and so on is
1
P =
k
n
k
n n
g g g × × × ..........
2 1
2 1
= ( )
I
=
k
i
n
i
i
g
1
.

NOTE:
Suppose we have 2 distinguishable particles A and B and 3 Boxes.
Therefore, we have 2 = n and 3 = g .
Let us see how we do distribute them:

AB × ×
× AB ×
× × AB
A B ×
B A ×
× A B
× B A
A × B
B × A

Total number of ways = 9 =
2
3 =
n
g .
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 18
To calculate the all possible ways of how N particles are distributed among k -energy
states we need to consider the possible ways of selecting the group of particles.

The total number of ways the first group of
1
n -particles can be selected from the total N
particles is
)! ( !
!
1 1
1
n N n
N
C
n
N
÷
= .
Next
2
n -particles can be selected from the rest of ) (
1
n N ÷ particles in
2
1
) (
n
n N
C
÷
=
)! ( !
)! (
2 1 2
1
n n N n
n N
÷ ÷
÷
ways.
In this way we can select
1
n ,
2
n , …..
k
n particles out of total N particles in the
following ways:

2
P = ×
1
n
N
C
1
2 2 1
3
2 1
2
1
) ..... ( ) ( ) (
. ..........
÷
÷
÷ ÷ ÷ ÷ ÷
× × ×
k
k
n
n n n N
n
n n N
n
n N
C C C

=
! )! ...... (
)! ....... (
.. ..........
)! ( !
)! (
)! ( !
!
1 1 2 1
2 2 1
2 1 2
1
1 1 ÷ ÷
÷
÷ ÷
÷ ÷
× ×
÷ ÷
÷
×
÷
k k
k
n n n n N
n n n N
n n N n
n N
n N n
N

=
! ! !...... !
!
1 2 1 k k
n n n n
N
÷
=
I
=
k
i
i
n
N
1
!
!
.

Therefore, the total number of ways P of the distribution is

P =
2 1
P P ×
=
I
=
k
i
i
n
N
1
!
!
( )
I
=
k
i
n
i
i
g
1
. This is termed as Thermodynamic Probability.

Taking logarithm on both sides, we get
|
|
.
|

\
|
+
|
|
.
|

\
|
÷ =
I I
i
n
i
i
i
i
g n N P ln ! ln ! ln ln
=
¯ ¯
+ ÷
i i
i i i
g n n N ln ! ln ! ln …………………………..(3)
For large number of particles we can consider 1 >> N and also each 1 >>
i
n .
So, we use Sterling’s formula:
n n n n ÷ = ln ! ln , for 1 >> n .
Thus equation (3) becomes

¯ ¯ ¯
+ + ÷ ÷ =
i
i i
i
i
i
i i
g n n n n N N N P ln ln ln ln
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 19
=
¯ ¯
+ ÷
i
i i
i
i i
g n n n N N ln ln ln ……………………………..(4)
[Since N n
i
i
=
¯
]
Now if we have the distribution P to be the most probable one
max
P , then

0 ln ln ln ln
max
= + ÷ ÷ =
¯ ¯ ¯ i
i
i i
i
i i
i
i
n g n n n n P o o o o
[Here N and
i
g ‟s are constants.]
Now we have,
i
i
i
n
n
n o o
1
ln = .
0 ln = =
¯ ¯
i
i
i
i i
n n n o o [ Since = =
¯
i
i
n N const ]
So, we can write

0 ln ln = + ÷
¯ ¯
i
i i i
i
i
n g n n o o ………………………………………(5)
We have other two variational equations (from eqn. (1) and (2) )

0 ..........
2 1
= + + + =
¯ k
i
i
n n n n o o o o ……………………………….(6)
0 ........
2 2 1 1
= + + + =
¯ k k i
i
i
n n n n o c o c o c o c ………………………..(7)

We combine three variational equations (5), (6) and (7) by multiplying (6) by o ÷ , (7) by
| ÷ and add them up with (5):

( ) 0 ln ln = ÷ ÷ + ÷
¯ i
i
i i i
n g n o |c o ………………………………...(8)
[Note: This method is called the method of Lagrange’s undetermined multipliers]

In the above equation (8), we can choose o and | such that all the
i
n o ‟s become
independent. In such a case the quantities in the brackets must be zero for each i .
Hence,
0 ln ln = ÷ ÷ + ÷
i i i
g n |c o

i
e e g n
i i
|c o ÷ ÷
= …………………………………………………..(9)

We write

This is Maxwell-Boltzmann distribution; „
i
f ‟ is termed as MB-function.

i
e e
g
n
f
i
i
i
|c o ÷ ÷
= =
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 20
Further we can rewrite the distribution considering the following:

i
e e g N n
i
i
i
i
|c o ÷ ÷
¯ ¯
= =

i
e g e N
i
i
|c o ÷ ÷
¯
= ¬
¯
÷
÷
=
i
i
i
e g
N
e
|c
o

Hence the normalized MB-distribution becomes:

¯
÷
÷
=
i
i
i
i
i
e g
Ne
n
|c
|c
.

Lecture-8

The Maxwell-Boltzmann distribution in continuous form can be written as:

c c c c
|c o
d e e g d n
÷ ÷
= ) ( ) ( [Note eqn. (9) in Lecture 7]…………………(1)

We have to evaluate the constants o and | .
For the molecules in a gas we can easily take the continuous distribution as there are
usually a large number of molecules.

Equation (1) is the number of molecules whose energies lie between c and c c d + .
In terms of molecular momentum we can write
, ) ( ) (
2 /
2
dp e e p g dp p n
m p | o ÷ ÷
=
as we have .
2
2
m
p
= c

Now, dp p g ) ( is the number of cells in the phase space within the range of momentum
p and dp p + .

dp p g ) ( =
3
h
dp dp dxdydzdp
z y x
í
, where
3
h is the volume of each cell.

Here
í
=V dxdydz = Volume occupied by the gas in ordinary position space.
dp p dp dp dp
z y x
2
4t =
í
= Volume of the spherical shell of radius p and thickness dp
in momentum space.

Hence,
3
2
4
) (
h
dp Vp
dp p g
t
=
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 21
dp p n ) ( =
3
2 / 2
2
4
h
dp e e Vp
m p | o
t
÷ ÷
.
Next we note that

í
·
= =
0
) ( N dp p n Total number of molecules.

í
·
÷
÷
=
0
2 / 2
3
2 4
dp e p
h
V e
N
m p |
o
t
=
2 / 3
3
2
|
|
.
|

\
|
÷
|
t
o
m
h
V e

Hence,

2 / 3
3
2
|
.
|

\
|
=
÷
m V
Nh
e
t
|
o
.

Therefore we have the momentum distribution,
dp e p
m
N dp p n
m p 2 / 2
2 / 3
2
2
4 ) (
|
t
|
t
÷
|
.
|

\
|
= .
Since we have c m p 2
2
= and
c
c
m
md
dp
2
= , the corresponding energy distribution can
be written as
c c
t
|
c c
|c
d e
N
d n
÷
=
2 / 3
2
) ( .
To find the other constant we employ the last formula above and compute the total
energy E of the system of molecules.
Total energy, E =
í
·
0
) ( c c c d n
= c c
t
|
|c
d e
N
í
·
÷
0
2 / 3
2 / 3
2
=
|
N
2
3
.
According to Equipartion theorem, E = NkT
2
3
.
Therefore, we have = |
kT
1
.
Thus the MB-distribution law now looks like:
( )
c c
t
t
c c
c
d e
kT
N
d n
kT /
2 / 3
2
) (
÷
= .
This is the number of molecules with energies between c and c c d + in a sample of ideal
gas that consists a total of N molecules and whose absolute energy is T .

Home Work:

Find out the Maxwell-velocity distribution from the above formula.

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 22
Lecture-9

Quantum Statistics:
Applicable to quantum particles which are identical but indistinguishable.

Bose-Einstein (BE) Statistics:

Let us assume
i
g to be the number of states that have same energy
i
c .
i
g is the degeneracy.
We determine the number of ways to which
i
n indistinguishable particles can be
distributed in
i
g cells. Here the selection of
i
n particles from total N particles does not
count as the particles are indistinguishable.
Now, if
i
n particles are lined up in
i
g cells then the group of particles are separated by
( 1 ÷
i
g ) partitions. Therefore, the total number of ways of arranging
i
n particles in
i
g
cells can be found out by permuting ( 1 ÷ +
i i
g n ) objects among themselves.

Total number of permutations among ( 1 ÷ +
i i
g n ) objects is equal to ( 1 ÷ +
i i
g n )!
But out of these,
i
n ! permutations of the
i
n indistinguishable particles among themselves
and ( 1 ÷
i
g )! permutations among themselves are irrelevant.
Therefore, the possible distinguishably different arrangements of
i
n indistinguishable
particles among
i
g cells are
)! 1 ( !
)! 1 (
÷
÷ +
i i
i i
g n
g n
.
Hence, the „thermodynamic probability‟ P of the entire N particles is

P =
I
÷
÷ +
i i i
i i
g n
g n
)! 1 ( !
)! 1 (
.

Example:

4 = g , 10 = n

3 partitions. Particles are shown to be grouped in 2+3+4+1 ways.
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 23
Taking natural logarithm on both sides we get

| |
¯
÷ ÷ ÷ ÷ + =
i
i i i i
g n g n P )! 1 ln( ! ln )! 1 ln( ln
~ | |
¯
÷ ÷ ÷ + )! 1 ln( ! ln )! ln(
i i i i
g n g n
[ Since, (
i i
g n + )>>1 ]
We use Sterling‟s formula to have

| |
¯
÷ ÷ + ÷ + ÷ + + ~
i
i i i i i i i i i i
g n n n g n g n g n P )! 1 ln( ln ) ( ) ln( ) ( ln .
Conditions for the most probable distribution is
max
P P = . For that small changes
i
n o in
any of the
i
n ‟s do not affect the value of P .
Hence we can write
¯

÷ + + ÷ ÷ + +
+
+ = =
i
i i i i
i
i i i i i i
i i
i i
n n n n
n
n n n g n n
g n
g n P 0 ln
1
) ln(
) (
1
) ( 0 ln
max
o o o o o o o

[Note:
i
g ‟s do not change]
The result is :
| | 0 ln ) ln( = ÷ +
¯ i
i
i i i
n n g n o …………………(1)
Now we incorporate the conditions for the conservation of particles and conservation of
energy:

0 =
¯
i
i
n o …………………………………..(2)
0 =
¯ i
i
i
n o c ………………………….……..(3)
The above three equations (1), (2) and (3) can be combined to form one by the method of
Lagrange‟s method of undetermined multipliers. Let us multiply (2) by o ÷ and (3) by
| ÷ and then add them up with (1):
| | 0 ln ) ln( = ÷ ÷ ÷ +
¯ i
i
i i i i
n n g n o |c o

Since the
i
n o ‟s are independent, the quantity in the brackets must vanish for each value
of i . Hence,
0 ln = ÷ ÷
|
|
.
|

\
| +
i
i
i i
n
g n
|c o
¬
i
e e
n
g n
i
i i |c o
=
+

¬
1 ÷
=
i
e e
g
n
i
i
|c o
This is Bose-Einstein (BE) distribution law.
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 24
Considering
kT
1
= | we write:

1
1
/
÷
= =
kT
i
i
i
i
e e g
n
f
c o
, BE occupation number.

Particles which follow BE statistics are called „Bosons‟. For example, Photons, Phonons,
Mesons etc.

Photon Statistics:

For photons total number is not conserved: =
¯
i
i
n const.
Hence, we put 0 = o in the BE distribution formula and the distribution becomes
1
1
÷
=
i
e
f
i
|c

For continuous distribution:
c c c
c
d
e
d f
kT
1
1
) (
/
÷
= , where we put v c h = for photons and we get

1
1
) (
/
÷
=
kT h
e
f
v
c

Application: Planck Radiation Formula.

Lecture-10

The Planck Radiation Formula:
Planck Considered that the electromagnetic waves emitted from a black body does have
energy which is quantized in units of v h , where v is the frequency of the wave and h is
Planck‟s constant.

The black body is assumed to be a cavity whose walls are constantly emitting and
absorbing radiation. It has been observed that each wave originates in an atomic
oscillator, the energy of which is written as v c nh
n
= , where = n 0, 1, 2, ….. ·.

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 25

The average energy of an oscillator is
1
/
÷
=
kT h
e
h
v
v
c , considering Photon statistics.

To derive a formula for the Spectral energy density it is assumed that the cavity has some
volume V and it contains a large number of indistinguishable photons of various
frequencies.
To count the photons we have to estimate the number of cells in the phase space
(constructed by positions and momentum of all photons).
If each cell has the infinitesimal volume
3
h then the number of cells in the phase space
where the momentum lies between p and dp p + is
3
) (
h
dp dp dxdydzdp
dp p g
z y x
í
= .
Here,

í í í
=V dxdydz = volume of the cavity
dp p dp dp dp
z y x
2
4t =
í í
= volume of the spherical cell of radius p and thickness
dp in the momentum space.

Therefore,

3
2
4
) (
h
dp Vp
dp p g
t
= .
Since the momentum of a photon is
c
h
p
v
= , we have
3
2 3
2
c
d h
dp p
v v
= .
v v
t
v v d
c
V
d g
2
3
4
) ( = .

Note:
Every substance emits electromagnetic radiation, the character of which
depends upon the nature and temperature of the substance.
An ideal solid body which absorbs all radiation incident upon it, regardless
of frequency is called a black body.

Model of a Black body:
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 26

This is the number of cells in the frequency between v and v v d + .
The spectral energy density v v d u ) ( is the energy per unit volume betweenv and v v d +

V
d g
d u
c v v
v v
· ·
=
) ( 2
) ( ,
where the factor 2 comes from the fact that each cell can be occupied by two photons of
two different directions of polarizations.

1
8
) (
/
2
3
÷
=
kT h
e
h
d
c
d u
v
v
v v
t
v v

¬
1
8
) (
/
3
3
÷
· =
kT h
e
d
c
h
d u
v
v v t
v v . This is Planck Radiation formula.

Wien’s Displacement Law:

In the Planck‟s radiation formula above we put
kT
hv
n = (dimensionless quantity).
We arrive at

1
1 8
) (
3
3
÷
· |
.
|

\
|
=
n
n
n t
v v
e
d
h
kT
h
kT
c
h
d u

=
|
|
.
|

\
|
÷1
8
3
4
3 3
4
n
n n t
e
d
T
h c
k

The plot of the above equation looks like

max
n
÷ n
4 4
3 3
8 T
u
k
h c
|
|
.
|

\
|
t

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 27

The maximum in the above curve occurs at 3
max
~ n which means we have
=
kT
h
max
v
Constant. This is Wien’s displacement law.

It quantitatively expresses the empirical fact that the peak in the black-body spectrum
shifts to progressively shorter wavelengths (higher frequencies) as the temperature is
increased.

Stefan-Boltzmann Law:

The total energy density within the cavity over all frequencies can be obtained as

í í
· ·
÷
= =
0
3
4
0
3 3
4
1
8
) (
n
n n t
v v
e
d
T
h c
k
d u u .
The definite integral is just some constant.
Hence we can write

4
) ( T T u o = ,

where o is a universal constant. This is Stefan-Boltzmann law which states that the total
energy density is proportional to the fourth power of the absolute temperature of the
cavity walls.

Raleigh-Jeans Formula:

For high enough temperature ( ÷ T large) one can approximate
kT
h
e
kT h
v
v
+ ~1
/
.
Therefore, Planck Radiation formula can be approximated as

( )
.
8
/
8
) (
3
2 3
3
c
kTd
kT h
d
c
h
d u
v tv
v
v v t
v v = · ~
This is Rayleigh-Jeans formula which was originally obtained by considering the
continuous distribution of energy due to Classical Physics.

According to Rayleigh-Jeans formula:

2
) ( v v · u which means 0 ) ( ÷ v u as 0 ÷ v and · ÷ ) (v u as · ÷ v .

But experimentally one finds that 0 ) ( ÷ v u as · ÷ v .
This is called Rayleigh-Jeans catastrophe or “ultraviolet catastrophe”.

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 28
Lecture-11

Fermi-Dirac (FD) Statistics:

Particles are identical, indistinguishable and are governed by Pauli‟s Exclusion principle.
No two particles can occupy same energy state. That is each cell can be occupied by
maximum one particle.

Assume that there are
i
g cells having the same energy
i
c and
i
n particles are to occupy
the
i
g cells. This means
i
n cells are filled and ) (
i i
n g ÷ cells are vacant.
(We assume
i i
n g > .)
Now total
i
g cells (some are filled and some are vacant) cane be arranged in !
i
g
different ways among themselves. But the !
i
n permutations of the filled cells and
)! (
i i
n g ÷ permutations of the vacant cells are irrelevant as the particles (and cells) are
indistinguishable.
Therefore, the numbers of distinct arrangements are
)! ( !
!
i i i
i
n g n
g
÷
.
The „thermodynamic probability‟ P of the entire distribution of particles is the product
.
)! ( !
!
I
÷
=
i i i i
i
n g n
g
P
Taking natural logarithm on both sides,
| |
¯
÷ ÷ ÷ =
i
i i i i
n g n g P )! ln ln( ! ln ! ln ln .
Using Stirling‟s formula:
| |
¯
÷ + ÷ ÷ ÷ + ÷ ÷ ~
i
i i i i i i i i i i i i
n g n g n g n n n g g g P ) ( ) ln( ) ( ln ln ln
For the distribution to represent maximum probability
max
P P = , small variation
i
n o in the
particle numbers must not alter P .

Hence,
| |
i
i
i i i
n n g n P o o
¯
÷ + ÷ = = ) ln( ln 0 ln
max
…………………………(1)
We also consider the conservation of particles and of energy (as before),
0 =
¯
i
i
n o …………………….(2)
0 =
¯
i
i i
n o c ………………..…(3).
We combine the above three equations by multiplying (2) by o ÷ , (3) by | ÷ and then
adding them up with (1):
| | 0 ) ln( ln = ÷ ÷ ÷ + ÷
¯ i
i
i i i i
n n g n o |c o ,
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 29
where o and | are Lagrange‟s undetermined multipliers.
Since the
i
n o ‟s are independent, the quantity in the brackets must vanish for each value
of i . Therefore,
0 ln = ÷ ÷
|
|
.
|

\
| ÷
i
i
i i
n
n g
|c o
¬
i
e e
n
n g
i
i i |c o
=
÷

¬ 1 + =
i
e e
n
g
i
i |c o
.

1 +
=
i
e e
g
n
i
i
|c o
, where
kT
1
= | .

This is Fermi-Dirac (FD) distribution law.

FD distribution in continuous form:
1
1
1
1
) (
/
+
=
+
=
kT
e e e e
f
c o |c o
c , ) (c f is called occupation index.

Fermi Energy:
To evaluate the constant o we examine the condition of „electron gas‟ at low
temperatures. For small T , the occupation index ) (c f is 1 at 0 = c and ) (c f =1 up to a
certain energy
F
c c ~ , called Fermi energy. For
F
c c > , ) (c f drops to zero rapidly.
To incorporate the above we set
kT
F
c
o ÷ = .
The occupation index is now
1
1
) (
) (
) (
/ ) (
+
= =
÷ kT
F
e g
n
f
c c
c
c
c .
At = T
o
0 K
1 ) ( = c f when
F
c c <
= 0 when
F
c c > .
As the temperature increases, the occupation index changes from 1 to 0 more and more
But at any T we have
2
1
) ( = c f when
F
c c = .
The occupation index for FD distribution at K T
o
0 = and at a higher temperature is
drawn below:
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 30

Lecture-12

Comparison among three distributions:

kT
i
i
i
i
e e
g
n
f
/ c o ÷ ÷
= = MB

1
1
/
÷
=
kT i
i
e e
f
c o
BE

1
1
/
+
=
kT i
i
e e
f
c o
FD

Occupation index
i
f signifies the average number of particles in each of the states of that
energy
i
c . This does not depend upon how the energy levels of a system of particles are
distributed. Hence, this provides a convenient way of comparing the essential features of
the three distribution laws.

For MB distribution:
The ratio of two occupation indices for two energy levels
i
c and
j
c does not depend
upon the parametero .
.
) (
) (
/
/ ) (
kT E
kT
j
i
e e
f
f
j i A
÷
= =
c c
c
c

This is the relative degree of occupancy for two energy states. This formula is
particularly useful for BE and FD distributions as we often ask this question for quantum
states. But we can arrive at the above formula there only when BE and FD distributions
behave like MB distribution under certain conditions.

BE distribution:
K T
o
0 =
K T
o
0 >
) (c f
÷ c
F
c
2
1
) ( = c f
1
0
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 31
When kT
i
>> c , the BE distribution approaches MB distribution.

1
1
/
÷
=
kT i
i
e e
f
c o
~
kT
i
e e
/
1
c o
=
kT
i
e e
/ c o ÷ ÷
.

FD distribution:

1
1
/ ) (
+
=
÷ ÷ kT
i
i F
e
f
c c
for
F i
c c s .
At low temperatures ( ) 0 ÷ T virtually all the energy states are filled with the occupation
index dropping rapidly towards zero near Fermi energy (
F
c ).

At high temperatures ( ÷ T large) the occupation index is sufficiently small at all
energies.

Then we can write
kT
F
e e f
/ ) (
) (
c c o
c
÷ ÷
~ , the FD distribution becomes similar to the MB.

Calculation of Fermi Energy:

1
1
) (
) (
) (
/ ) (
+
= =
÷ kT
F
e g
n
f
c c
c
c
c
Suppose a system (a metal sample for example) contains N free electrons.
) (c f
c
0 >> T
0 = T
0 = T
1
T
2
T
) (c f
c
2 1
0 T T < <
PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 32
For the calculation of Fermi energy (
F
c ) we consider that all energy states are filled up
starting from 0 = c up to
F
c c = . That means 1 ) ( = c f ,
F
c c s s 0 .
So,
í
·
=
0
) ( N d g c c .
To calculate c c d g ) ( we start evaluating dp p g ) ( .
3
) (
h
dp dp dxdydzdp
dp p g
z y x
í
= , integrated over the phase space.
We know

í
=V dxdydz (Volume of the system) and
dp p dp dp dp
z y x
2
4t =
í
(Volume of the momentum space contained in the
Spherical cell between p and dp p + )

3
2
. 4
2 ) (
h
V dp p
dp p g
t
× = =
3
2
. 8
h
V dp p t
.
The factor 2 comes from the fact that each electron has two possible spin states (+1/2
and 2 / 1 ÷ ).
As we know c m p 2
2
= , we get c c d m dp p
2 / 1 3 2
) 2 ( = .

= c c d g ) ( c c
t
d
h
Vm
2 / 1
3
2 / 3
2 8
.
Now,
= N c c
t
c
d
h
Vm
F
í
0
2 / 1
3
2 / 3
2 8
=
2 / 3
3
2 / 3
3
2 16
F
h
Vm
c
t
.
Hence,

3 / 2
2
3 / 2
2
8
3
2 8
3
2
|
.
|

\
|
= |
.
|

\
|
= p
t t
c
m
h
V
N
m
h
F
, where
V
N
= p is density of free electrons.

Example:

In copper atom the electron configuration is such that we can assume each atom is
contributing one free electron to the electron gas.
Therefore, the electron density can be written as

= p
Volume
atoms of Number ÷ ÷

=
mole mass
volume mass mole atoms
/
) / ( ) / ( ×

=
) (
) ( ) (
copper of mass Atomic
atoms copper of Density Number Avogadro
÷ ÷ ÷
÷ ÷ ÷ × ÷

PBC Lecture Notes in Physics Series– Statistical Physics by Dr. Abhijit Kar Gupta 33
=
3
3 23
10 5 . 63
10 94 . 8 10 023 . 6
÷
×
× × ×
= 8.5
28
10 × electrons/m
3

3 / 2
28
31
2 34
8
10 5 . 8 3
10 11 . 9 2
) 10 63 . 6 (
|
|
.
|

\
| × ×
×
× ×
×
=
÷
÷
t
c
F
= 1.13
18
10
÷
× Joule = 7.04 eV

Fermi Temperature, k T
F F
/ c = ~ 10
5
K
o
.

We have used:

34
10 63 . 6
÷
× = h Joule-sec
m = 9.11
31
10
÷
× kg, electron mass
k = 1.381
23
10
÷
× Joule/ K
o

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