Statistical Mechanics

Black Body Radiation

All objects radiate electromagnetic energy continuously
regardless of their temperatures.
Though which frequencies will predominate, depends on the
temperature.
At room temperature most of the radiation is in infrared part
of the spectrum and hence is invisible.
The ability of a body to radiate is closely related to its ability
to absorb radiation.
A body at a constant temperature is in thermal equilibrium
with its surroundings and must absorb energy from them at
the same rate as it emits energy.
A perfectly black body is the one which absorbs completely
all the radiation, of whatever wavelength, incident on it.
Since it neither transmits any radiation, it appears black
whatever the color of the incident radiation may be.
There is no surface available in practice which will absorb all
the radiation falling on it. BUT a metallic cavity can work as
perfect black body.

The cavity walls are constantly emitting and absorbing
radiation, and this radiation is known as black body
radiation.
(i) The total energy emitted per second
per unit area (radiancy E or area under
curve) increases rapidly with increasing
temperature.
(ii) At a particular temperature, the
spectral radiancy is maximum at a
particular frequency.
Characteristics of Black Body Radiation
(iii) The frequency (or wavelength,
m
)
for maximum spectral radiancy
decreases in direct proportion to the
increase in temperature. This is called
Wiens displacement law
= T
m

constant (2.898 x 10
-3
m.K)

Every solid, liquid or gas is an assembly of
enormous number of microscopic particles.

Similarly, radiation is an assembly of photons.

It is impossible to study the movement of
individual particle/ photon.

However the MACROSCOPIC properties of
such assemblies can be explained in terms
of the statistical distributions.

Statistical Mechanics
Statistical Distribution
This expresses the most probable way in which a certain
total amount of energy E is distributed among the N
members of a system of particles in thermal equilibrium at
absolute temperature, T.
Thus Statistical Mechanics reflects overall behavior of
system of many particles.
Suppose n() is the no. of particles having energy,
then
) ( ) ( ) ( c c c f g n =
where g() = no. of states of energy or statistical weight
corresponding to energy (or simply density of states)
f() = distribution function
= average no. of particles in each state of energy
= probability of occupancy of each state of energy
Usually, we are interested, how the fixed amount of energy is distributed
among the various identical particles of an assembly. There are 3
kinds of identical particles-
1. Identical particles that are sufficiently far apart to be distinguishable.
Example: molecules of a gas.
Negligible overlapping of
Maxwell-Boltzmann Statistics is used.

2. Indistinguishable identical particles of 0 or integral spin.
Example: Bosons (Photons, Phonons, alpha particles) (dont obey the
Pauli exclusion principle)
Overlapping of
Bose-Einstein Statistics is used.

3. Indistinguishable identical particles with odd-half integral spin
(1/2, 3/2, 5/2 ..).
Example: Fermions (Electrons, Protons, Neutrons) (obey the exclusion
principle)
Fermi-Dirac Statistics is used.

Every kind of Statistics, is characterized by its
DISTRIBUTION FUNCTION.
Which means- number of particles inside a
state of energy
DISTRIBUTION FUNCTION for MB Statistics-

DISTRIBUTION FUNCTION for BE Statistics-


DISTRIBUTION FUNCTION for FD Statistics-

kT
Ae f
B M
c
c

= ) (
. .
1
1
) (
. .

=
kT
e e
f
E B
c
o
c
1
1
) (
. .
+
=
kT
e e
f
D F
c
o
c
Maxwell-Boltzmann Statistics
According to this law number of identical and distinguishable
particles in a system at temperature, T having energy is
n() = (No. of states of energy ).(average no. of particles in a
state of energy )
kT
Ae g n
c
c c

= ). ( ) (
Here A is a constant and
This law cannot explain the behavior of photons (Black body
radiation) or of electrons in metals (specific heat, conductivity)
kT
Ae f
B M
c
c

= ) (
. .
(i)
Equation (i) represents the Maxwell-Boltzmann Distribution Law
Applications of M.B. Statistics
(i) Molecular energies in ideal gas
No. of molecules having energies between and + d is given by
)} ( }{ ) ( { ) ( c c c c c f d g d n =
No. of states in momentum space having momentum between p and
p + dp is proportional to the volume element i.e.
The momentum of a molecule having energy is given by
( ) ( )
kT
n d Ag e d
c
c c c c

=
(i)
c m p 2 =
c
c
m
md
dp
2
=
z y x
dp dp dp
} } }
o
dp p g ) (
Each momentum corresponds to a single
3 3
3
4
) (
3
4
p dp p t t +
dp p
2
4t
o
dp p
2
4t
o
o
dp Bp dp p g
2
) ( =
dp Bp d g
2
) ( = c c
B is a constant
c
c
c c c
m
md
m B d g
2
. 2 . ) ( =
No. of molecules with energy between and + d
Put in (i)
c c c c d B m d g
2 / 3
2 ) ( =
3/ 2
( ) 2
kT
n d m BA e d
c
c c c c

=
(ii)
( )
kT
n d C e d
c
c c c c

=
Total No. of molecules is N
} }

= =
0 0
) ( c c c c
c
d e C d n N
kT
Put value of C in equation (ii)
above equation gives the number of molecules with energies
between and + d in an ideal gas that contains N
molecules and whose absolute temperature is T. It is called
molecular energy distribution equation.
2
3
) (
2
kT
N
C
t
t
=
}

=
0
2
1
2
1
a a
dx e x
ax
t
Using identity
c c
t
t
c c
c
d e
kT
N
d n
kT

=
2
3
) (
2
) (
Total energy of the system
Average Molecular Energy
}

=
0
) ( c c c d n E
}

=
0
2
3
2
3
) (
2
c c
t
t c
d e
kT
N
E
kT
(

= kT kT
kT
N
E t
t
t
2
) (
4
3
) (
2
2
3
}

=
0
2
4
3
2
3
a a
dx e x
ax
t
Using
Average energy per molecule
NkT E
2
3
=
N
E
= =

c
This is the average molecular energy and is independent of
the molecular mass
kT
2
3
=

c
At Room Temperature its value is 0.04 eV.
Equipartition of Energy: Equipartition Theorem
Average Kinetic Energy associated with each degree of freedom
of a molecule is
Put this in molecular energy distribution equation
c . .E K
kT
2
1
Distribution of molecular speed
2
2
1
mv =
mvdv d = c
(In statistics, the number of values in a study that are
free to vary are known as degree of freedom.)


It is called molecular speed distribution formula.

It is the square root of the average squared molecular speed
dv e v
kT
m
N dv v n
kT
mv
2
2
2
3
2
2
4 ) (

|
.
|

\
|
=
t
t

=
2
v v
rms
kT v m
2
3
2
1
2
= =

c
m
kT
v
rms
3
=
RMS Speed
Using
Average Speed
}

=
0
) (
1
dv v vn
N
v
dv e v
kT
m
kT
mv
2
2
2
3
0
3
2
4

}

|
.
|

\
|
=
t
t
}

=
0
2
3
2
1
2
a
dx e x
ax
|
|
.
|

\
|
|
.
|

\
|
=

2
2 2
2
4
.
2
4
2
3
m
T k
kT
m
v
t
t
m
kT
t
8
=
Most Probable Speed
m
kT
v
p
2
=
kT
mv
e v
kT
m
N v n
2
2
2
3
2
2
4 ) (

|
.
|

\
|
=
t
t
| | 0
2
4
) (
2
2
2
3
2
=
|
.
|

\
|
=

kT
mv
e v
dv
d
kT
m
N
dv
v dn
t
t
0
2
4
2
3
=
|
.
|

\
|
kT
m
N
t
t
| | 0
2
2
2
=

kT
mv
e v
dv
d
(i) Speed distribution is not symmetrical
M.B. Speed Distribution Curve
n(v)
v
most probable
= v
p

v
v
rms
v

rms p
v v v < <

(ii)
m
kT
m
kT
m
kT 3 8 2
< <
t
Variation in molecular speed with T and molecular mass
This curve suggests that most probable speed T
Also the most probable speed 1/m
Quantum Statistics
1. 0 or integral spin
(Indistinguishable identical particles)
Bosons
Fermions
1. Odd half integral spin
2. Do not obey exclusion
principle
2. Obey exclusion principle
3. Symmetric wave function 3. Anti-symmetric wave function
4. Any number of bosons
can exist in the same
quantum state of the
system
4. Only one fermion
can exist in a particular
quantum state of the
system
Consider a system of two particles, 1 and 2, one of which is in
state a and the other in state b.
) 2 ( ) 1 ( '
b a
=
When particles are distinguishable then
) 1 ( ) 2 ( "
b a
=
When particles are indistinguishable then
| | ) 1 ( ) 2 ( ) 2 ( ) 1 (
2
1
b a b a B
+ =
For Bosons,
symmetric
For Fermions,
| | ) 1 ( ) 2 ( ) 2 ( ) 1 (
2
1
b a b a F
=
anti-symmetric

F
becomes zero when a is replaced with b i.e.
Thus two Fermions cant exist in same state (Obey Exclusion
Principle)
| | 0 ) 1 ( ) 2 ( ) 2 ( ) 1 (
2
1
= =
a a a a F

Bose-Einstein Statistics
Any number of particles can exist in one quantum state.
Distribution function can be given by
1
1
) (
. .

=
kT
e e
f
E B
c
o
c
where may be a function of temperature, T.
For Photon gas
1 0 = =
o
o e
-1 in denominator indicates multiple occupancy of an energy state
by Bosons
Bose-Einstein Condensation
If the temperature of any gas is reduced, the wave packets grow
larger as the atoms lose momentum according to uncertainty
principle.
When the gas becomes very cold, the dimensions of the wave
packets exceeds the average atomic spacing resulting into
overlapping of the wave packets. If the atoms are bosons,
eventually, all the atoms fall into the lowest possible energy state
resulting into a single wave packet. This is called Bose-Einstein
condensation.
The atoms in such a Bose-Einstein condensate are barely
moving, are indistinguishable, and form one entity a
superatom.
Bose Einstein Statistics
1. 0 or integral spin
(Indistinguishable identical particles- BOSONS)
2. Do not obey exclusion principle
3. Symmetric wave function
( Means if we have two particles, THERE WILL BE NO CHANGE IN THE
WAVEFUNCTION IF WE EXCHANGE THE LOCATION FOR BOTH THE PARTICLES)
4. Any number of bosons can exist in the same
quantum state of the system.
5. Distribution function
1
1
) (
. .

=
kT
e e
f
E B
c
o
c
Plancks Radiation Law
Planck assumed that the atoms of the walls of cavity radiator (black
body) behave as oscillators with energy
nhv
n
= c .... 3 , 2 , 1 , 0 = n
The average energy of an oscillator is
N
c
c =

N is total no. of Oscillators

1
=

kT
hv
e
hv
c
(i)
Thus the energy density (u
v
) of radiation in the frequency range v to v
+ dv is

= c
t
3
2
8
c
dv v
dv u
v
( )
2
3
8 v dv
G dv
c
t
v =
represents the density of standing waves in a cavity
here
|
.
|

\
|

=
1
8
3
2
kT
hv
e
hv
c
dv v
dv u
v
t
1
8
3
3

=
kT
hv
e
dv
c
hv
dv u
v
t
In terms of wavelength
1
8
5

=
kT
hc
e
d hc
d u

This is Plancks Radiation formula in terms of frequency.

This is Plancks Radiation formula in terms of wavelength.
When is large then
1
8
5

=
kT
hc
e
d hc
d u

Case I : (Rayleigh-Jeans Law)

This is Rayleigh-Jeans
Law for longer s.
kT
hc
e
kT
hc

+ ~1

d
kT
hc
hc
d u
|
.
|

\
|
+
=
1 1
8
5

d
kT
d u
4
8
=
When is very small then
1
8
5

=
kT
hc
e
d hc
d u

Case II : (Weins Law)

This is Weins Law for small s.
1 >>
kT
hc
e

d e
hc
d u
kT
hc
=
5
8

d e
A
d u
kT
B
5
=
This is another form of
Weins Law..
Here A and B are constants.
Application of the BE Statistics for
understanding the specific heat of solids

Specific heat is the heat required to raise
the temperature of one gram of a
substance by one degree centigrade.
Earlier we had Dulong-Petits law for the
theoretical prediction of the specific heat of
solids.
This law is not in the good agreement with
experiments for lighter elements.
Specific Heat of Solids: The answer comes
from Statistical Mechanics
Each atom in the solid should have total energy = 3kT (3
degrees of freedom).
A- Classical Approach-
R
T
E
C
V
v
3 =
|
.
|

\
|
c
c
=
In case of solids total average energy per atom per degree
of freedom is kT.
For one mole of solid, total energy, E = 3N
o
kT (classically)
E = 3RT
Here N
o
is the Avogadro number.
Specific heat at constant volume is
~ 6 kcal/kmol.K
This is Dulong & Petits Law.
This means that atomic specific heat (at constant volume) for
all solids is approx 6 kcal/kmol.K and is independent of T.
Dulong and Petits Law fails for light elements such as B,
Be and C.
Also it is not applicable at low temperatures for all solids.
According to it the motion of the atoms in a solid is oscillatory.
B- Einsteins Approach of Specific Heat of Solids
The average energy per oscillator atom) is
1
=

kT
hv
e
hv
c
The total energy for one mole of solid in three degrees of freedom.
1
3

=
kT
hv
e
hv
N E
o
The molar specific heat of solid is
V
v
T
E
C
|
.
|

\
|
c
c
=
This is Einsteins specific heat formula.
2
2
) 1 (
3

|
.
|

\
|
=
kT
hv
kT
hv
e
e
kT
hv
hv N C
o v
Case I:
2
2
) 1 (
3

|
.
|

\
|
=
kT
hv
kT
hv
e
e
kT
hv
k N
o
2
2
) 1 (
3

|
.
|

\
|
=
kT
hv
kT
hv
e
e
kT
hv
R C
v
At high T, kT >> hv then
kT
hv
e
kT
hv
+ ~1
2
2
1 1
1
3
|
.
|

\
|
+
|
.
|

\
|
+
|
.
|

\
|
~
kT
hv
kT
hv
kT
hv
R C
v
|
.
|

\
|
+ ~
kT
hv
R C
v
1 3
R C
v
3 ~ ) ( hv kT >>
This is in agreement with Dulong & Petits Law at high T.
This implies that as
Case II:
kT
hv
e
kT
hv
R C
v

|
.
|

\
|
~
2
3
At low T, hv >> kT then
1 >>
kT
hv
e
i.e. is in agreement with experimental results at low T.
0 , 0
v
C T
Fermi-Dirac Statistics
Obey Paulis exclusion Principle
Distribution function can be given by
1
1
) (
. .
+
=
kT
e e
f
D F
c
o
c
f () can never exceed 1, whatever be the value of , and T. So
only one particle can exist in one quantum state. (Paulis
Principle)
is given by
kT
F
c
o =
F
c
where is the Fermi Energy and represents the
energy of highest occupied energy state at absolute
zero temperature.
Thus at T = 0, For <
F
all energy states from = 0 to
F

are occupied as
1 ) (
. .
= c
D F
f
Thus at T = 0, all energy states for which >
F
are vacant.
0 ) (
. .
= c
D F
f
Case II:
T > 0
Some of the filled states just below
F
becomes vacant while
some just above
F
become occupied.
2
1
1
1
) (
0
. .
=
+
=
e
f
D F
c
Case III:
At =
F
Probability of finding a fermion (i.e. electron in metal) having
energy equal to fermi energy (
F
) is at any temperature.
For all T

0.5
(eV)

0
1

F
1
) (
. .
c
D F
f
0 K
10000 K
1000 K
Typically, one metal atom gives one electron.
Free electrons in a metal
One mole atoms gives one mole of free electrons, (N
o
)

RT kT N E
o e
2
3
2
3
= =
Then total specific heat in metals at high T should be
( ) R
T
E
C
V
e
e
v
2
3
=
|
.
|

\
|
c
c
=
If each free electron can behave like molecules of an ideal gas.
Then

Average K.E. for 1 mole of electron gas,

Molar specific heat of electron gas,

R R R C
v
2
9
2
3
3 = + =
But experimentally at high T
It means free electrons are not contributing in the specific
heat.
The no. of electrons having energy is


By definition highest state of energy to be filled by a free electron
at T = 0 is obtained at =
F

0
( )
F
N n d
c
c c =
}
R C
v
3 ~
where
3
2
3
8 2
( )
Vm
n d d
h
t
c c c c =
Here V is the volume of the metal
where N/V is the density of free electrons.
}
=
F
d
h
Vm
N
c
c c
t
0
3
2
3
2 8
No. of electrons in the electron gas having energy between
and + d is
2
3
2
3
3
3
2 16
F
h
Vm
c
t
=
2
3
8
3
2
2
|
.
|

\
|
=
V
N
m
h
F
t
c
(i)
Electron energy distribution
c c c c c d f g d n ) ( ) ( ) ( =
This is electron energy distribution formula, according to
which distribution of electrons can be found at different
temperatures.
c
c c t
c c
c c
d
e h
Vm
d n
kT
F
1
2 8
) (
/ ) ( 3
2
3
2
3
+
=

using (i)
c
c c
c c
c c
d
e
N
d n
kT
F
1 2
3
) (
/ ) (
2
3
+
|
.
|

\
|
=

Total energy at 0K is
Average electron energy at 0K
}
=
F
d n E
o
c
c c c
0
) (
Then average electron energy
0
/ ) (
= =

e e
kT
F
c c
Since at 0K all electrons have energy less than or equal to
F
c c c
c
d
N
E
F
F o
}

=
0
2
3
2
3
2
3
F
N
c
5
3
=
F
o
o
N
E
c c
5
3
= =
|
.
|

\
|

at 0K.