STATISTICAL

MECHANICS
•statistical distributions – general considerations
•Maxwell-Boltzmann
•Bose-Einstein
•Fermi-Dirac
•Maxwell-Boltzmann statistics
•Maxwell-Boltzmann distribution
•energies in an ideal gas
•equipartition of energy
•quantum statistics
•fermions and bosons
•Bose-Einstein and Fermi-Dirac distribution
•comparison of the three statistical distributions
•applications
•Planck radiation law
•specific heats of solids
•free electrons in a metal
general considerations
central question: how does the behavior of a many-particle system
depend on the properties of the single particles?
but: too many single particles to describe them one by one

therefore: look at probabilities for particle properties

example: a room filled with air

•number of particles >> 1023
•mainly two kinds of particles (N2 and O2)

impossible to know all coordinates and kinetic energies

but: STAT MECH allows to calculate the probability of each
particle
to e.g. have a certain amount of kinetic energy at a time t
statistical distributions
most easy setting:
•system of N particles in thermal equilibrium at temperature T
question:
•how is the total energy E distributed over the particles?
or:
•how many particles have the energy 12 etc.

particles interact “weakly” with one another and the container walls
thermal equilibrium but no correlation

more than one particle may have a certain energy 

i Microstates and Macrostates
The evolution of a system can be represented by a trajectory
2
1 in the multidimensional (configuration, phase) space of micro-
parameters. Each point in this space represents a microstate.
During its evolution, the system will only pass through accessible microstates
– the ones that do not violate the conservation laws: e.g., for an isolated
system, the total internal energy must be conserved.
Microstate: the state of a system specified by describing the quantum state
of each molecule in the system. For a classical particle – 6 parameters (xi, yi,
zi, pxi, pyi, pzi), for a macro system – 6N parameters.
The statistical approach: to connect the macroscopic observables
(averages) to the probability for a certain microstate to appear along the
system’s trajectory in configuration space, P( 1,  2,..., N).
Macrostate: the state of a macro system specified by its macroscopic
parameters. Two systems with the same values of macroscopic parameters
are thermodynamically indistinguishable. A macrostate tells us nothing about a
state of an individual particle.
For a given set of constraints (conservation laws), a system can be in many
macrostates.
 The Phase Space vs. the Space of Macroparameters
some macrostate
P numerous microstates
in a multi-dimensional
T
configuration (phase)
space that correspond
V the same macrostate

the surface i
defined by an
equation of i
states 2
1
2
1
i etc., etc., etc. ...
i

2
2 1
1
 Probability of a Macrostate, Multiplicity
Probability of a particular microstate of a microcanonical ensemble
1

# of all accessiblemicrostates

The probability of a certain macrostate is determined by how many

microstates correspond to this macrostate – the multiplicity of a given
macrostate  .

Probability of a particular macrostate 

 # of microstates that correspondto a given macrostate

# of all accessiblemicrostates

This approach will help us to understand why some of the macrostates are
more probable than the other, and, eventually, by considering the interacting
systems, we will understand irreversibility of processes in macroscopic
systems.
statistical distributions

most easy case:

•thermal equilibrium
•constant energy (E=const.)
•constant number of particles (N=const., for “classical” particles)

n()=g( )f()

probability of occupancy
number of particles of each state with energy 
with energy  (distribution function) or average
Number of particles in each state of
number of states Energy 
with energy 
(statistical weight)
statistical distributions
classical system:
d , etc. g()d 

Maxwell Bose Fermi

Boltzmann Einstein Dirac

•identical particles
•identical particles •identical particles
•integral spin
•“far” apart •odd half-integral spin
(bosons)
(no overlap of Y) (fermions)
•close together
•close together
(overlapping Y)
(overlapping Y)
distinguishable
indistinguishable
indistinguishable
statistical distributions

Maxwell Bose Fermi

Boltzmann Einstein Dirac

e.g. molecules in a gas e.g. photons e.g. electrons

Maxwell-Boltzmann distribution
Maxwell-Boltzmann distribution function:

fMB()=A e-/kT

k=1.381 x 10-23 J/K=8.617 x 10-5 eV/K (Boltzmann constant)

n ( )  g ( ) f ( )  A g ( ) e  / kT

N()d is the number of particles whose energy lie between

 And  +d 
6 units of energy, 3 particles to give it to

321 411
312 141
213 114
231 3 ways
123
132 more likely
6 ways
energies in an ideal gas
ideal gas:
•PV=RT
•N is large
•translational motion, quantization is irrelevant

n ( ) d   ( g ( ) d  ) f ( )  A g ( ) e  / kT d 

(number of molecules between  and  + d)

2 N / kT
n () d  e d
( kT ) 3/ 2

(energy distribution)
   
 
n   Ag e KT 
For continuousdistribution of molecular energy
  
 
n d  Ag  e  KT 
d
g  d  number of availablestates having
energy to   d
p  2mE
In momentum space, the number of states
gp dp  volume of sphericalcell from radius
p to p  dp
gp dp  Bp2dp
Corresponding to every value of momentum is a value of
energy.

We need to find how many momentum states are in this

spherical shell.
 md
p  2m ,
2
2 pdp  2md , dp  ,
2m
md
g  p dp  Bp dp  B2m 
2
 g  d
2m
Since each momentum magnitude p corresponds to energy 
3 1 3
g  d  2 Bm 2 2 d  2 Bm 2  d
3 
n d  A 2 Bm 2 e KT d


n d  C  e KT d
 C  2 ABm 3
Total number of molecules is N
2
   

N  n d  C
0 
0
e KT d

2N
 KT  2  C 
C 3


2 KT  2
3

1 

 ax
xe dx 
2a a
0

SO, n d 

2N
e

KT
d
KT  3
2

THIS IS MOLECULAR ENERGY DISTRIBUTION

totalinternalenergy of N gas moleculeat T
  
 2N  3  

E  n d 
0 KT 
3 
2 0
 2 e KT  d

2N

3
KT  KT
2

KT  3 

4 3 3
2 x 2 e  axdx 
3 4a 2 a
 NKT 0
2
E
SO AVERAGEMOLECULARENERGY, 
N
3
 KT
2
Most probable energy

dn 
0
d
 Molecular speed distribution
n d 
2N
e
 
KT d
KT 3 2
1 2
  mv , d  mvdv
2
  mv 2 
2N  
nv dv 
m
ve  mvdv
2 KT

KT  3
2 2
  mv 2 
2m 3 2
N 2  2 KT 
 dv
 v e
KT  3
2
3 2   mv 2 
 m  2  2 KT 
 dv
 4N   v e
 KT 
Molecular speed distribution
 1. Mean velocity:
 

v
 0
vnv dv

 0
vnv dv

8KT
 1.59
KT
 m
 nv dv
N m
0
1. Root mean square velocity:

3KT
vrms  v 2

m
1. Most probable velocity:

dnv  2 KT
v p when  0, vp 
dv m
Here’s a plot of
the distribution:

Notice how “no” molecules have E=0, few molecules have high
energy (a few kT or greater), and there is no maximum of
molecular energy.
k has units of [energy]/[temperature] so kT has units of energy.
 Here’s how the distribution changes with temperature (each
vertical grid line corresponds to 1 kT).

Notice how the

distribution for higher
temperature is skewed
towards higher
energies (makes
sense!) but all three
curves have the same
total area (also makes
sense).

Notice how the probability of a particle having energy greater

than 3kT (in this example) increases as T increases.
Continuing with the physics, the total energy of the system is
 
2πN
E=  ε n  ε  dε =  ε 3/2
e -ε/kT
dε .
 kT 
3/2
0 0

Evaluation of the integral gives

3NkT
E= .
2
This is the total energy for the N molecules, so the average

3 energy per molecule is

ε = kT ,
2
 Example 9.4 Find the rms speed of oxygen molecules at
0 ºC.

Would anybody (who hasn’t done the calculation yet) care to

guess the rms speed before we do the calculation?
 1.66×10-27 kg 
mass of O2 =  2 16 u   = 5.31×10 kg
-26

 u 
You need to know that an oxygen molecule is O . The atomic
2
mass of O is 16 u (1 u = 1 atomic mass unit = 1.66x10-27 kg).

3kT
v rms =
m
 3 1.38×10 J/K    0+273 K 
-23

v rms =
5.31×10 -26
kg

vrms = 461 m/s

fermions and bosons
distinguishable particles (non overlapping wavefunctions)

indistinguishable particles (overlapping wavefunctions)

bosons:
•integral spin (0,1,2,…)
•symmetric wave function
(exchange of two bosons does not change the system)
•all bosons can be in the same quantum state
•Photons, Phonons
•Wave function of system of boson is not affected any
exchange of any pair of particle

1
f BE ()  / kT
Ae 1
 FERMIONS
odd half integral spin (1/2,3/2,5/2,…)
• antisymmetric wave function
– (exchange of two fermions changes symmetry of the
system)
• only one fermion can be in a quantum state
– (exclusion principle, Pauli principle)
• probability for two particles in one state: 0!

1
f FD ()  / kT
Ae 1
1 F / kT
f FD ()  ( F ) / kT
, Ae
e 1
Bose-Einstein / Fermi-Dirac distribution
bosons:
one boson of a system in a certain state increases the probability
of finding another boson in this state!
fermions:
one fermion of a system in a certain state prevents all other
fermions from being in that state!

1 1
f BE ()     / kT
Ae / kT 1 e e 1

1 1
f FD ()    / kT
Ae/ kT 1 e e 1
1
f FD ()  , A  e F / kT
e (F ) / kT  1

• A describes the system and may be a function of T

• >>kT fBE and fFD converge into fMB
• F is the Fermi energy
 Consider the F-D distribution at T = 0 K

AT T=0 K

1
(1)    F f FD  1
0 e  1
1
(2)    F f FD  
0
e 1
∞

From this we conclude that all energy states above F are

Empty (fFD) and all energy states below F are occupied
(fFD = 1). So F gives the energy of the highest filled state at
T = 0.
comparison of the distributions
Maxwell Bose Fermi
Boltzmann Einstein Dirac

identical indistinguishable indistinguishable,

distinguishable no Pauli principle Pauli principle

classical particles bosons fermions

any spin spin 0,1,2 … spin 1/2,3/2,5/2 …

Y don’t overlap Y overlap Y overlap
Y symmetric Y antisymmetric

e.g. gas molecules e.g. cavity photons (laser) e.g. free electrons in metals
liquid He at low T electrons in white dwarfs

unlimited number of unlimited number of never more than 1

particles per state particles per state, particle per state,
more than in MB less than in MB
aproaches MB for high T aproaches MB for high T
 KT = 0.1 F
T=0
1
fFD 0.5
fFD

0  F F

KT = 1.0 F
0.75

fFD 0.5

F
free electrons in a metal

T=0

T>>0

EF
free electrons in a metal

8 2 V m 3/ 2
g () d  3
d 
h
(number of electron states)

F
N

0
g  d
free electrons in a metal
2/3
h  3N 
2
N
F      : electron density
2 m  8 V  V
Fermi energy

8 2 V m 3/ 2 1
n () d  (F )/ kT
d 
h 3
e 1
(electron energy distribution)
 Total internal energy

3
E0  N F
5

AVERAGE ELECTRON ENERGY

3
0   F
5
comparison of the distributions
Maxwell Bose Fermi
Boltzmann Einstein Dirac

identical indistinguishable indistinguishable,

distinguishable no Pauli principle Pauli principle

classical particles bosons fermions

any spin spin 0,1,2 … spin 1/2,3/2,5/2 …

Y don’t overlap Y overlap Y overlap
Y symmetric Y antisymmetric

e.g. gas molecules e.g. cavity photons (laser) e.g. free electrons in metals
liquid He at low T electrons in white dwarfs

unlimited number of unlimited number of never more than 1

particles per state particles per state, particle per state,
more than in MB less than in MB
aproaches MB for high T aproaches MB for high T
Distribution functions:
Maxwell-Boltzmann distribution function:

1   / kT
f M B ( )  e e
Bose-Einstein distribution function:

1
f B E ()  1 / kT
e e 1
Fermi-Dirac distribution function:

1
f FD ()  1 / kT
e e 1
Comparison of the distributions

2
1
f BE () 
e 1e/ kT  1
f M B ( )  e 1 e  / kT
1
f FD () 
f()

1 e 1e/ kT  1

0
0 1 2 3 4 5
(kT)
 ASSIGNMENT
1. Define microstate, macrostate and ensemble.

1. Make a comparison between MB, BE FD statistics (mention

distribution function).

2. Derive Planck’s law of radiation from BE statistics.

3. 2. Calculate the Fermi energy at 0K of metallic silver

containing one free electron per atom. The density and
atomic weight of silver is 10.5 g/cm3 and 108 respectively.

4. 3. Distribute two particles in three different states

according to i) MB, ii) BE and iii) FD statistics.

5. 4. A system has non-degenerate single particle state 0,1,2,3

energy units. Three particles are to be distributed in these
states so that the total energy of the system is 3 units.
Find the number of microstates if the particles obey i) MB,
ii) BE and iii) FD statistics.
 ASSIGNMENT
5. Consider a two particle system each of which can exist in
states E1, E2 and E3 units. What are the possible states if the
particles are i) bosons and ii) fermions.

6. Three distinguishable particles each of which can be in one of

the E, 2E, 3E and 4E units having total energy 6E. Find all
possible number of distributions of all particle in the energy
states. Find the number of microstates in each case.

7. The Fermi energy of silver is 5.51 eV. (a) what is the average
energy of the free electrons in Silver at 0 K. (b) What is the
speed of the electron corresponding to the above average
energy?

8. Plot Fermi distribution at T=0K and T≠0K. From this plot

define Femi energy.