Energy States and Energy Levels

The principles of quantum mechanics:

the energy of a particle (not acted on by conservative force field)
cannot change in a continuous manner
Schrodinger’s equation for a particle moves freely in 1 D is analogous
to the wave equation describing the propagation of a transverse
wave in a stretched string, fixed at both ends.
1
j = 2L nj=1,2,3,.....
nj
h
p=

h
pj =nj
2L
If a particle is free to move in any direction (x, y, z axes) within a cubical
box of side length L then:
h h h
px = nx py = ny pz = nz
2L 2L 2L

p 2j = p x2 + p 2y + p z2 = (
n x2 + n 2y + n z2 ) h2
4 L2

p 2j = n 2j
h2
4L 2
(n 2
x + n 2y + n z2 = n 2j )
p 2j
h2
j = =n 2
j
2m 8 m L2

p 2j
h2 − 3
2
j = =n V 2
j
2m 8m
2
3 h2 − 3
The lowest energy level j =1 (nx = ny = nz =1) then n12 =3 and 1 = V
8m
There is only one state (one set of quantum numbers) having this
energy. This lowest energy is therefore nondegenerate and g1 =1.
In the next level (j=2), the states are:
nx ny nz 2
6 h2 − 3
2 1 1 2 = V The degeneracy g2 = 3
1 2 1 8m
1 1 2

(n 2
x )
+ n y2 + nz2 = n 2j = 66 The degeneracy gj = ? (12)

A schematic representation of a set of energy levels, their degeneracies gj

and their occupation numbers Nj.

Nj = N
j

 j N j = U
j
 Macrostates and Microstates

An assembly (or simply as a system) consists of

a number N of identical entities (particles).
An ensemble consists of a number N of identical systems.
The macroscopic properties of a system can be determined
if the distribution of the particles among its energy states is known.
Thus, the problem is to determine the possible distributions of
particles among energy levels and energy states.
Particles: distinguishable or indistinguishable

Macrostate of an assembly is specified by the number of

particles Nj in each energy level.
Macrostate of the above assembly is specified by a set
occupation numbers N1=5, N2=4, N3=3, and N4=2.
Microstate of an assembly is specified by the number of particles
in each energy state. (for indistinguishable particles).

Microstate of an assembly is specified by the number of particles

and which particles in each energy state. (for distinguishable
particles).

Many different microstates may have the same macrostate.

 Interaction between particles
in an isolated system

In an isolated system:
the energy U (=E) and the total number of particles N are constant.

Interaction between particles in an isolated system might be:

• collision between gas molecules or with the walls of the container,
• energy interchange between the oscillating molecules of a crystal.

Interaction between particles in an isolated system will change:

• the numbers of particles occupying energy states.
• the microstate of the assembly, but every possible microstate
must satisfy the conditions of constant N and U
 The Fundamental Postulate
of Statistical Physics (1)

All possible microstates of an isolated assembly are equally probable

1. Consider an isolated system. Observe the system in a time interval t that is

long enough so that each possible microstate occurs a large number of times.
microstate 1: N1 times with total interval time t1
microstate 2: N2 times with total interval time t2
............................................................................
microstate : N times with total interval time t.

the postulate asserts that

t1 = t2 = ....... = t => t
 The Fundamental Postulate
of Statistical Physics (2)

All possible microstates of an isolated assembly are equally probable

2. Consider an ensemble (N replicas of a given system). At any instant:

microstate 1: N1 replicas
microstate 2: N2 replicas
........................................
microstate : N replicas

the postulate claims that

 N1 =  N2 = ....... =  N => N
 Thermodynamic Probability

The thermodynamic probablity Wk of macrostate k is the number of

microstates that correspond to macrostate k.

The total number of possible microstates of a system is 

 =  Wk
k
N j = the average number of particles in each of the permitted energy levels j
Njk = the occupation number of level j in macrostate k.
N jg = the group average value of the occupation number of level j
N tj = the time average value of the occupation number of level j
1
N j = N = N =  N jkWk
g t

 k
j j
 The Bose-Einstein Statistics (1)

The basic assumptions:

• the particles are considered indistinguishable
• there is no restriction on the number of particles that can occupy any energy state

The possible distributions of 3 indistinguishable particles (Nj =3) among

3 energy states (gj =3) in level j.

xxx x xx

(N + g j − 1)!
xx x xxx
5!
j
= = 10
N j ! (g j − 1)!
xx x xx x
3!2!
x xx x xx

x x x xxx
 The Bose-Einstein Statistics (2)

The total number of possible distributions over all levels:

WBE = Wk = 
(N j + g j − 1)!
j N j ! (g j − 1)!
 The Fermi-Dirac Statistics (1)

The basic assumptions:

• the particles of an assembly are considered indistinguishable
• particles obey the Pauli exclusion principle
(no more than one particle in each permitted energy state)

The possible distributions of 3 indistinguishable particles (Nj =3) among

5 energy states (gj =5) in level j.
x x x x x x

x x x x x x
g j! 5!
= = 10
x x x x x x N j ! (g j − N j )! 3!2!
x x x x x x

x x x x x x
 The Fermi-Dirac Statistics (2)

The total number of possible distributions over all levels:

g j!
WFD = Wk = 
j N j ! (g j − N j )!
 The Maxwell-Boltzmann Statistics (1)

The basic assumptions:

• the particles of an assembly are considered distinguishable
• there is no restriction on the number of particles that can occupy
the same energy state
(classical statistics with distinguishable identical particles)
 The Maxwell-Boltzmann Statistics (2)

The possible macrostates for the distribution of 4 distinguishable particles

(N =4: a,b,c,d) between 2 nondegenerate energy levels (g1 = g2 =1).
Macrostate I II III IV V
N2 0 1 2 3 4
N1 4 3 2 1 0

How many microstates for each macrostate?

I (N1 = 4 & N2 = 0) II (N1 = 3 & N2 = 1) V(N1 = 0 & N2 = 4)

N2 N2 d c b a N2 abcd

N1 abcd N1 abc abd acd bcd N1

 The Maxwell-Boltzmann Statistics (3)

III(N1 = 2 & N2 = 2) IV (N1 = 1 & N2 = 3)

N2 cd bd bc ad ac ab N2 bcd acd abd abc

N1 ab ac ad bc bd cd N1 a b c d
d

Macrostate (k) I II III IV V

N!
Wk 1 4 6 4 1 N 1! N 2 !

N!
N 1! N 2 ! N 3 !. . . . . .N n !
 The Maxwell-Boltzmann Statistics (4)

In level j: gj =2 and Nj =3 (a,b,c)

abc ab c ac b bc a

a bc b ac c ab abc

The total number of possible distributions over all levels:

N!
WMB = Wk = g1N1 g 2N 2 g 3N3 ..... g nN n
N 1! N 2! N 3!......N n !
Nj
g
WMB = Wk = N! N! j
j

j
 Thermodynamic Probability

The thermodynamic probablity Wk of macrostate k is the

number of microstates that correspond to macrostate k.

WBE = Wk = 
(N j + g j − 1)!
 =  Wk
j N j ! (g j − 1)! k

g j!
WFD = Wk = 
j N j ! (g j − N j )!
Nj
gj
WMB = Wk = N! N! j j
Nj
g
WSK =  j

j N j!
 The Statistical Interpretation of Entropy

N1 , V1 , U1 N 2 , V2 , U 2
S1 , 1 S2 ,  2

Entropy is an extensive property. The total entropy (S) of two

independent systems (S1, S2) is the sum of the entropies S1 and S2.

S = S1 + S2

The number  of possible microstates of the two systems is the product

of the thermodynamic probabilities of the two systems ( 1, 2).

 = 1 2
S is some unknown function of .
S = J()

J(1) + J( 2) = J(1 2)

Take the partial derivative of both sides of this equation with respect to 1.
dJ (1 ) dJ (1 2 )
+ 0 = 2
d1 d (1 2 )
Take the partial derivative of both sides of this equation with respect to 2.
dJ ( 2 ) dJ (1 2 )
0+ = 1
d 2 d (1 2 )
It follows from these equations that:
1 dJ ( 2 ) 1 dJ (1 ) dJ (1 2 )
= =
1 d 2  2 d1 d (1 2 )
 dJ ( 2 ) dJ (1 )
2 = 1
d 2 d1

Since 1 and 2 are independent, the equation can be satisfied only if

each side equals the same constant kB. For any arbitrary system,

dJ ()
 = kB
d
d
dJ () = kB


J () = kB ln 
and hence
S = kB ln 
S = kB ln   kB ln W