Department of Physics

1.5 QUANTUM FREE ELECTRON THEORY

The failures of classical theories were removed by Sommerfeld in 1928. This theory uses the
quantum concepts and hence it is known as the quantum free electron theory.

He applied Schrodinger’s wave equation and De-Broglie’s concept of matter waves to obtain the
expression for electron energies. He treated the problem quantum mechanically using Fermi -
Dirac statistics rather than the classical Maxwell - Boltzmann statistics

Important Assumptions

 The potential of an electron is uniform or constant within the crystal

 The electrons posses wave nature.
 The allowed energy levels of an electron are quantized.
 The electrons are free to move within the crystal itself and they are restricted from leaving
the crystal due to potential barrier at its surfaces.

Merits of Quantum free electron theory

This theory treats the electron quantum mechanically, rather than classically. This theory
explains the electrically conductivity, thermal conductivity and specific heat capacity of metals,
photoelectric effect, Compton effect, etc.

Demerits of Quantum free electron theory

Even though it explains most of the physical properties of metals, it fails tot provides the
difference between metals, semiconductors and insulators.
It also fails to explain the positive value of Hall coefficient and some transport properties of
metals.

1.6 FERMI DISTRIBUTION FUNCTION

The classical and quantum free electron theories failed to explain many electrical and thermal
properties of the solids. However, these properties can be easily understood using Fermic –
Dirac statistics.
Fermi – Dirac statistics deals with the particles having half integral spin. The particles like
electrons are the examples of half integral spin and hence they are known as Fermi particles or
Fermions.

The expression which gives the distributions of electrons among the various energy levels, as a
function of temperature is known as Fermi distribution function.

Definition
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Fermi distribution is the probability function F(E) of an electron occupying a given

energy level at absolute temperature. It is given by
1
F (E)   E  E F  / kT
1 e
Where

F(E) is called Fermi distribution (FD) function or Fermi function

E – Energy of the level whose occupancy is being considered;

EF - Energy of the Fermi level; (Fermi energy)
 - Boltzmann’s constant;
T – Absolute temperature.
The probability value F(E) lies between 0 and 1. If F (E) = 1, the energy level is occupied by an
electron. If F (E) = 0, the energy level is vacant. If F (E) = 0.5 OR ½ then is a 50 % chance for
finding the electron in the energy level.

1.7 EFFECT OF TEMPERATURE ON FERMI FUNCTION

The dependence of Fermi distribution function on temperature and its effect on the occupancy of
energy level is shown in fig. 1.7 (a) and (b).

Case (i) Probability of occupation for E < EF at T = 0

1
F (E) 
1  e E E F  / kT

When T = 0 K and E < EF , We have

1
F (E) 
1  e  VE / 0 
1 1 1
F (E)    [e-=0]
1  e  1 0 1
 F(E) = 1

Thus at T = 0, there is 100% chance for the electrons to occupy the energy levels below the Fermi
level ie., below the Fermi energy level, all the levels are occupied with the electrons.

(ii) Probability of occupation for E > EF at T = 0

When T = 0 K and E > EF

1 1 1 1
F (E)   VE / 0 
   0
1 e 1 e 
1  

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 F(E) = 0

Thus there is 0% chance for the electrons to occupy energy level above Fermi energy level.
Ie, all energy levels above Fermi energy level are unoccupied.

From the Above two cases, at T= 0K the variation of F(E) for different energy values becomes a step
function, as shown in fig. 1.7 (a).

T3 > T2> T1>0K

F(E) F(E) T3 T2 T1
1 T=0K 1 T=0K

0.5

0 E EF O EF E
(a) (b)

Fig.1.7 Variation of Fermi distribution function with E at different temperatures

Case (iii) Probability of occupation at ordinary temperature

At ordinary temperature, the value of probability starts, reducing from 1 for values of E
slightly less than EF

With the increase of temperature, i.e., T > 0 K, Fermi function F(E) varies with E as shown in fig.
1.7(b).
At any temperature other than 0K and E = EF,
1
F (E) 
1  e0
1 1
F (E)    0.5 [ e 0  1]
11 2
Hence, there is 50% chance for the electron to occupy Fermi energy level. ie., the value of F
(E) becomes ½ at E = EF

The above result is used to define the Fermi energy level.

Further, for E > EF, the probability value falls off rapidly to zero (fig 1.7(b).

Case (IV) at high temperature

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When T >> EF or T , the electrons lose their quantum mechanical character and Fermi
distribution function reduces to classical Boltzmann distribution.

Uses of Fermi distribution function

 It gives the probability of an electron occupying a given energy level at a given

temperature.
 It is very useful in the calculation of number of free electrons per unit volume at a
given temperature.
 Further, it is very useful in the calculation of Fermi energy of a metal.

1.8 DENSITY OF ENERGY STATES

The ability of a metal to conduct electricity depends on the number of quantum states and also
the energy levels that are available for the electrons. Hence, it is essential to find the energy
states which are available for the occupation of the charge carriers.
Definition
Density of states is defined as the number of available electron states per unit volume in
an energy interval E and E + d E. It is denoted by Z(E) and its given by

Number of energy states in energy int erval EandE  dE in a metal piece( N ( E )dE )
Z ( E )dE 
Volume of the metal piece(V )

Calculation of Density of states in three dimensions (Derivation):

Let us consider a cubical sample with side ‘’. A sphere is constructed with the quantum
numbers nx, ny, nz as three coordinate axes in three-dimensional space as shown in fig. 1.8.
nz
E
E+dE

dn

nx

Fig. 1.8 Calculation of Density of states

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A radius vector n is drawn from the origin ‘O’ to a point nx ,ny and nz in space and all the points on
the surface of that sphere will have the same energy E. Thus, denotes the radius of the
sphere with energy E.

This sphere is further divided into many shells. Each shell represents a particular combination of
quantum numbers (nx ,ny and nz) and therefore, it represents a particular energy value with a
particular radius. In this space, unit volume represents one energy state.

Number of energy states within

4 3
a sphere of radius n = n ……(1)
3
(Volume of the sphere)

Since the quantum numbers nx ,ny and nz can have only positive integer values, we have to take
1
only one octant of the sphere, i.e., th of the spherical volume.
8
Therefore, the number of available energy states within one octant of the sphere of radius n
corresponding to energy E is
1 4 3 
n  …… (2)
8  3
=

Similarly, the number of number of available energy states within one octant of the radius n + dn
Corresponding to energy E + d E

1 4 3
 n  dn  …… (3)
8  3 
=

Now, the number of available energy states between the shell of radius n and n + dn (between the
energy values E and E + d E ) is found by subtracting equation (2) found equation (3). Thus we have

1  4  1  4  3
 n  dn   n   n
3 3
N(E) d E =
8 3  8 3 

1  4 
=
8 3 

  n  dn   n
3 3

  3
N(E) =  n  dn  3n dn  3ndn  n 
3 2 2 3

6

 a  b 3
 a 3  b 3  3a 2b  3ab 2 
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Since the dn is very small, the higher powers of dn are negligible. Therefore, the terms dn 2 and dn3
are neglected.


 N ( E )dE  3n 2 dn
6


N ( E )dE  n 2 dn ….. (4)
2
We know that the energy of an electron in a cubical metal piece of sides a is given by

n2h2
E= ……. (5)
8ma 2
2 8ma 2 E
Or n = …….. (6)
h2
1/ 2
2  8ma 2 E 
n = …….. (7)
Or

 h 
2

Differentiating equation (6), we get

2 8ma 2 dE
2n =
h2

8ma 2 dE
Or ndn  …….. (8)
2h 2
Equation (4) is rewritten as

N (E) dE = nndn  ……..(9)
2
Substituting equation (7) and (8) in equation (9), we have

  8ma 2 E   8ma 2 dE 
1/ 2

N (E) dE =    
2 h2   2h
2


1   8ma 2 E   8ma 2 dE 
1/ 2

 
2 2  h 2   h 2 
=

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  8ma 2 
1/ 2
 8ma 2 E 
  E  dE
1/ 2
=
4  h2   h 
2

  8ma 2 
1/ 2

 2  E dE
1/ 2
N(E) dE = …….(10)
4 h 
Pauli’s exclusion principle states that two electrons of opposite spins can occupy each state and
hence the number of energy states available for electron occupancy is given by

  8ma 2 
3/ 2

=2  2  E dE
1/ 2
N(E) dE
4 h 

  8ma 
3/ 2

 2  a E dE
3 1/ 2
=
2 h 
4
= 3 2m  a E dE
3/ 2 3 1/ 2
N(E) dE
h

8m  3/ 2
8m 8m  1/ 2

 
h  3 3/ 2
h3
=
4  2m4  2m  4  2m  2  (2m)1 / 2 8(2m) 3 / 2
1/ 2

   ]
h3 h3 h3
Density of states is given by the number of energy states per unit volume.

4
Z(E) dE = 3
2 m 3/ 2
a 3 E 1 / 2 dE .….(11)
h
This is the expression for the density of charge carriers in the energy interval E and E + d E. It is
used to calculate carrier concentration in metals and semiconductors.

1.12 CARRIER CONCENTRATION

Carrier concentration, i.e., the number of electrons per unit volume in a given energy interval is
calculated by summing the product of the density of states Z(E) and the occupancy probability F(E).

i.e., nc   Z E F E dE

Substituting the expression for Z(E) and F(E), we have

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4 1
nc   2 m 3/ 2
E 1/ 2
dE …….(12)
h3 1  e E E F kT

Fermi energy

It is the energy of a state at which the probability of electron occupation is ½ (half) at

any temperature above 0k. It is the maximum energy of field states at 0k.

Expression for carrier concentration in terms of Fermi energy.

For a metal at absolute zero, the upper most occupied level is E F and all the levels are
completely filled below EF and all the levels are filled below EF,

Therefore, F (E) = 1

for the energy levels E = 0 to E = E F

Now, the equation (12) reduces to

EF
4
nc   3
2m3 / 2 E 1 / 2 dE
0 h

4 E

nc  3 2m  E 1 / 2 dE
F
3/ 2

h 0

4
E
3/ 2  E 
3/ 2 F

nc  3 2m    0
h  3 / 2 
4
 3 2m 
3/ 2 1
E 3 / 2 E 0 F

h 3/ 2
4
 3 2m 
h
3/ 2 2

3
EF  0
3/ 2
 
8
i.e., nc  3
2mEF 3 / 2
3h
This equation is used to calculate carrier concentration in metals and semiconductors in terms
of Fermi energy.

Expression for energy

8
We know that nc  3
2mEF 3 / 2
3h
8
nc  3
( 2 m) 3 / 2 ( E F ) 3 / 2
3h
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 3nc   h 
3

  3/ 2 
 ( EF ) 3 / 2
 8   (2m) 
3/ 2

 3nc   h3  
  3/ 2 
 EF
 8   (2m)  
3/ 2

 3nc   h3  
or, EF    3/ 2 
 8   (2m)  
3/ 2 3/ 2

 3n   h  3

EF   c   3/ 2 
 8   (2m) 
3/ 2

 3nc   ( h ) 
3 2/3

   3/ 2 2 / 3 
 8  [(2m) ] 
3/ 2

 h 2  3nc 
(or) EF    
 2m  8 
This is the expression for Fermi energy of electrons in solids at absolute zero. Thus, Fermi
energy of a metal depends only on the density of electrons of that metal.

When the temperature increases, Fermi level or Fermi energy slightly decreases.

  2
 kT 
2

It can be shown that E F  EF o 1    
 12  EF

 
 o

Where
EFo is Fermi energy at 0k

T is absolute temperature

 is Boltzmann’s constant