10.

Introduction to statistical mechanics

For a system consisting of large number of particles moving freely (gas system), there are two
ways to describe its behaviour.
(1) Consider individual particle motion. This is not possible for large number of particles.
(2) Consider the energy distribution of the particles.
If there are N number of particles in the system, where
n1 particles each with energy E1
n2 particles each with energy E2
and so on.
so that,

N = ni and E = ni Ei (total energy)

i

Here

E = ni Ei
i

is the kinetic energy only if there is no interaction between the particles;

E = ni Ei + potential energy
i

if there is interaction between particles

potential energy = V12 + V13 +....... + V23 + V24 ....
If this system of multi particles is left closed and isolated for a sufficiently long time,
an equilibrium state will be achieved, and the values for n1 , n2 , ........ will not be changed again
The distribution of the values of ni will be expressed by a certain distribution function following
certain suitable distribution law. Three type of distribution laws are commonly used:
Maxwell-Boltzmann
Bose-Einstein
Fermi-Dirac
Studies on these distribution functions and how they vary with time is called
Statistical Mechanics

In statistical mechanics, the behaviour of the particles in a system is described by using

distribution function
f(r, v, t) which represents the number of particles at position r at time t having velocity between
vx dan vx + dvx , vy dan vy + dvy , vz dan vz + dvz
r:(x, y,z)

is referred to as spatial space

v : ( vx , vy , vz ) is referred to as velocity space

(r,v)

is referred to as phase space

The number of particles at position r at time t : n(r,t) =

f (r,v,t)dv

For any property of the system Q(r, v , t), its average value is :
1
< Q >=
f (r,v,t)Q(r,v,t)dv , N : total number of particles
N

Example : For a gas at equilibrium, the overall distribution function is

f (v ) function of v
Average velocity of particles:

rms velocity

v2 =

1
N

Average kinetic energy

v=

1
N

v 2 f (v)dv
1
E = mv 2
2

vf (v)dv

For this course, we introduce three types of distribution functions,

Maxwell-Boltzmann distribution
This is often referred to as the classical distribution function
(where the kinetic energy of the electrons are assumed to be continuous)
It is suitable for system with high temperature (room temperature and above)
All particles are identical and distinguishable
The particles are considered to be distributed at energy state E1, E2 ......
Every energy state has intrinsic probability of g
(statistical weight)

Fermi-Dirac distribution
For quantum system each energy level is splitted into sub-levels
the energy state is definied by three quantum numbers : principle, orbit dan spin
The number of splitted levels is expressed by degeneracy gi for energy level Ei
Each energy state is filled up by one particle (Exclusive Pauli Principle)

Bose-Einstein Distribution
Similar to F-D distribution, but the Exclusive principle is not obeyed
The general form of the three types of distribution function for energy level i can be written as
ni =

gi
exp( + E i ) +

For M-B distribution:

exp( ) =

N
Z

1
kT

=0

E
N = ni and Z = g i exp i
kT
i
i

where

Z = electronic partition function

For F-D distribution:

For B-E distribution:

F
kT

kT

1
kT

=1

1
kT

= -1

M-B

B-E

F-D

Consider ideal gas using M-B distribution,

Z = exp(
0

E
) g ( E )dE
kT
1

here

g ( E )dE =

4V ( 2m 3 ) 2
h
Z=

Therefore,

1
E2

4V ( 2m )
3

h3

Z=

1
2

from quantum physics

1
E2

1
E
exp
(kT )3
dE =
2
kT
3

1
E 2 dE

V ( 2mkT ) 2
h3

E
exp
dE
kT

Number of particles with energy E and E + dE :

dn =

Replace Z :

1
2

1
N
N 4V ( 2m )
E
E
2
exp
(
)
exp
=
g
E
dE
E

dE
3
Z
kT
Z
kT

1
dn
2N
E
2
=
E
exp

dE (kT )3 / 2
kT

This can also be expressed in terms of v :

Take

dn dn dE
dn
=
= mv
dv dE dv
dE
dn
m
= 4N

dv
kT
2

3/2

mv 2
= f (v )
v exp

2kT
2

Most probable value of v [peak of the function f (v)] is given by

2kT
m

vm =

1
2
mv m
= kT
2

which is when

By using f (v), we can obtain

Average velocity

v2
1
4 3
v = vf (v )dv =
v exp 2 dv

3
v
N
vm 0
m

which is

v=

vm =

8 kT
m

and the root mean square (rms) velocity

4
v
1

exp
v rms = v 2 f (v )dv =
v
3
v2
N

m
v m 0
1
2

dv

1
2

Which is,

v rms =

dn
dv

3
vm =
2

3kT
m

We can also express Maxwell-Boltzmann distribution as

or

the number of particles having velocity between v and v+dv per unit volume in the velocity space,
particle density in the velocity space
m
=
N
v =

2kT
4v 2 dv
dn

3/ 2

mv 2

exp

2kT

v is referred to asMaxwell-Boltzmann velocity distribution function

v has a maximum at v = 0