LECTURE 07 SOLID STATE PHYSICS -II

FREE ELECTRON DESCRIPTION OF SPECIFIC HEAT

The amount of heat required to raise the temperature of 1 kg of the metal through 1 C is
called specific heat. The amount of heat required to raise the temperature of 1 mole of metal
through 1 C is called molar specific heat.
All conduction electrons are capable of observing the heat energy as per Maxwell
Boltzmann statistics which results in large value of specific heat according to classical free
electron theory.
According to quantum free electron theory, only those electrons that are occupying energy
levels close to EF, are capable of observing the heat energy to get excited to higher energy levels.
Hence only a small percentage of the conduction electrons are capable of receiving the thermal
energy input. Thus the specific heat value becomes very small for metal.
The average kinetic energy of a free electron according to classical statistics is given as
3
Eo = kBT
2
The total kinetic energy “E” of N free electrons of metal is
E = N Eo
3
E = N kB T
2
 E  3
  = 2 N kB
 T V
3
CV = N kB - - - - - - (1)
2

The measurement of optical reflection coefficient of metals indicates that number of

electrons per atom in metals is of the order of unit. The value of electronic specific heat for
one gram atom of metal is
3
CV = R = 3 cal/g K
2
On the other hand, specific heat associated with the lattice vibrations at high temperature is
about 3R or 6 cal/g K. Thus one might conclude that the specific heat of metals should be about
50% greater than specific heat of insulators. This is contradictory to the experimental
observations which indicate that the electronic contribution to the specific heat is very small. At
room temperature, the electronic contribution is not more than 0.01 of the value given in eq(1).
This contribution decreases linearly to zero as T approaches zero. It appears that all the electrons
might not contribute to the specific heat. Only a small fraction of the total number of electrons
might contribute. This view is supported by quantum theory.
The quantum mechanics suggests that only those electrons contribute to the specific heat
which lie within an energy range kBT below the Fermi level. This happens because when the
electron gas is heated up to a temperature T, these electrons acquire energy of the order of k BT
and jump to the empty higher energy state. The deep lying electrons cannot do so because the
unfilled energy states are not available to these electrons for excitation. These electrons do not
contribute to the specific heat.
k T
The number of electrons which contribute to the specific heat is of the order of N  B 
 EF 
T
or N   .
 TF 
Where TF is called Fermi temperature and defined by the equation as
E F = kB T F
The eq(1) using effective value of N is given as
2

3 T
CV  N kB  
2  TF 
This indicates that CV is proportional to T and approaches zero as T  0 . Using typical
values of T = 300 K and TF = 30000 K, the above equation gives the value of C V as
3
CV   0.01 N k B
2
The specific heat calculated from this equation agrees with the experimental observations.
Thus quantum mechanics modifies the thermal behaviour of free electrons in a simple manner.