Solution of the theoretical problem 3

3A. Average specific heat of each free electron at constant volume

(1). Each free electron has 3 degrees of freedom. According to the equipartition of

3
energy theorem, at temperature T its average energy E equals to 2 k BT ， therefore

the average specific heat cv equals to

dE 3
cV   kB
dT 2

(2). Let U be the total energy of the electron gas, then

S
U   Ef ( E )dS
0

where S is the total number of the electronic states, E the electron energy.

Substitution of (1) for dS in the above expression gives

∞
U  CV  E 3 / 2 f ( E )dE  CVI ,
0

where I represents the integral

∞
I = ∫ E 3 / 2 f ( E )dE .
0

Usually at room temperature k BT << E F . Therefore, with the simplified f ( E )

  1 E < E F − k BT

 E − ( E F + k BT )
f ( E ) = − E F − k BT < E < E F + k BT
 2 k BT
 0 E > EF + k BT

I can be simplified as

2 3/ 2 E  k BT 5/ 2
I EF (1  k BT / EF )5/ 2  F EF  (1  k BT / EF )5 / 2  (1  k BT / EF )5/ 2 
5 5k BT
1
 EF 7 / 2  (1  k BT / EF )7 / 2  (1  k BT / EF )7 / 2 
7 k BT
 2 3 2
 E f 5/ 2    k BT / E F  
 5 4 

Therefore

 2 3 2
U  CVEF 5/ 2    k BT / E F  
 5 4 

However the total electron number

EF0
2
N  CV E dE  CVEF0 3/ 2
1/ 2

0
3
3
CV  N  EF0 
3/ 2

0
where E F is the Fermi level at 0K, leading to

3  2 3 2
N  EF0 
3/ 2
U EF 5/ 2    k BT / EF  
2  5 4 

Taking E F  E F , and U  NE ，
0
 3 2 3 2
E≈ E F  + ( k BT / E F ) 
2 5 4 
∂E 9 k BT 3
cv = = kB << k B
∂T 4 EF 2

(3). Because at room temperature k BT =0.026eV while Fermi level of metals at room
temperature is generally of several eVs, it can be seen from the above expression that
according to the quantum theory the calculated average specific heat of each free
electron at constant volume is two orders of magnitude lower than that of the classical
theory. The reason is that with the temperature increase the energy of those electrons

whose energy is far below Fermi level (several times of k BT less than EF) does not
change obviously, only those minor electrons of energy near EF contribute to the
specific heat, resulting in a much less value of the average specific heat.