PHY 3201 FIZIK KEADAAN PEPEJAL

Heat Capacity of the

Electron Gas
The heat capacity, C is the amount of heat dQ, which is
needs to be transferred to a substance on order to raise
its temperature by a certain temperature interval.
V
V
T
U
C
|
.
|

\
|
c
c
=
The specific heat capacity is the heat capacity per unit
mass
m
C
c =
Heat Capacity, C
The heat capacity at constant volume is defined as
PHY 3201 FIZIK KEADAAN PEPEJAL
Source: Chris Wiebe
PHY 3201 FIZIK KEADAAN PEPEJAL
Source: Chris Wiebe
PHY 3201 FIZIK KEADAAN PEPEJAL
Electronic Heat
Capacity
The increase AUU(T)-U(0) in the total energy of a
system of N electrons when heated from 0 to T is
} }
= A

F
D d f D d U
c
c cc c c cc
0 0
) ( ) ( ) (
where f(c,T) is the Fermi distribution function and D(c) is
the density of states.
( ) | | 1
1
+
=
T k
T f
B
/ exp
) , (
c
c
The Fermi-Dirac Distribution Function is given as
The function f(c, T) gives the probability that the energy
level c, is occupied by an electron at Temperature T
At 0 K, the upper limit is c
F

and the FD function is 1
PHY 3201 FIZIK KEADAAN PEPEJAL
We multiply the identity
} }
= =

F
D d f D d N
c
c c c c c
0 0
) ( ) ( ) (
By
F
to obtain
} } }
= +

F
F
F
D d f D d
F F
c
c
c
c cc c c cc
0 0
) ( ) ( ) ( ) (
0 ) ( ) ( ) ( ) ( ) (
0 0
= +
} } }

F
F
F
D d f D d f D d
F F F
c
c
c
c cc c c cc c c cc
PHY 3201 FIZIK KEADAAN PEPEJAL
} }
= A

F
D d f D d U
c
c cc c c cc
0 0
) ( ) ( ) (
} }
+ = A

F
F
D f d f D d U
F F
c
c
c c c c c c c c c c
0
) ( )] ( 1 )[ ( ) ( ) ( ) (
} } }
+ = A

F
F
F
D d f D d f D d U
c
c
c
c cc c c cc c c cc
0 0
) ( ) ( ) ( ) ( ) (
+ = A
} } }

F
F
F
D d f D d f D d U
c
c
c
c cc c c cc c c cc
0 0
) ( ) ( ) ( ) ( ) (
) ) ( ) ( ) ( ) ( ) ( (
0 0
} } }
+

F
F
F
D d f D d f D d
F F F
c
c
c
c cc c c cc c c cc
PHY 3201 FIZIK KEADAAN PEPEJAL
} }
+ = A

F
F
D f d f D d U
F F
c
c
c c c c c c c c c c
0
) ( )] ( 1 )[ ( ) ( ) ( ) (
The energy needed to take electrons from c
F to

the orbital of energy c > c
F

Energy needed to bring the electrons
to c
F
from orbital below c
F

dT
D f d f D d d
dT
dU
C
F
F
F F
el
|
|
.
|

\
|
+
= =
} }

c
c
c c c c c c c c c c
0
) ( )] ( 1 )[ ( ) ( ) ( ) (
PHY 3201 FIZIK KEADAAN PEPEJAL
} }
= =

F
F
D
dT
df
d
dT
df
D d
dT
dU
C
F F el
c
c
c
c
c c c
c
c c c c
0
) (
) (
) (
) (
) ( ) (
}

=
0
) (
) , (
) ( c
c
c c c D
dT
T df
d C
F el
Since the electrons at c
F
are of importance, we make
D(c) = D(c
F
)
}

~
0
) , (
) ( ) (
dT
T df
d D C
F F el
c
c c c c
PHY 3201 FIZIK KEADAAN PEPEJAL
If we ignore the variation of the chemical potential with
temperature and assume that = c
F
, which is good
approximation at room temperature and below. Then
| |
2 2
1 +

=
T k
T k
T k dT
T df
B F
B F
B
F
/ ) exp(
/ ) exp( ) , (
c c
c c c c c
( )
| |
} }

+
=
(
(

=
T k
x
x
B
B
F
T k
T k
B
F
F el
B F
B
F
B
F
dx
e
e
T k
T k x
D d
e
e
T k
D C
/
) (
) (
) (
) (
) (
c
c c
c c
c c
c c
c
2 2
3
2
0
2 2
1
1
Therefore,
PHY 3201 FIZIK KEADAAN PEPEJAL
Taking into account that c
F
>>k
B
T, we can put the low
integration limit to minus infinity and obtain
| |
T k D dx
e
e x
T k D C
B F
x
x
B F el
2
2
2
2
2
3
1
) ( ) ( c
t
c =
+
=
}

Using the density of states for a free electron gas
F
F
N
D
c
c
2
3
= ) (
we finally obtain
F
B el
T
T
Nk C
2
2
t
=
where we defined the Fermi
temperature T
F
= E
F
/k
B

PHY 3201 FIZIK KEADAAN PEPEJAL
The total heat capacity, taking into account the electron
and the lattice contribution, equals to:
3
AT T C + =
For temperatures below both the Debye temperature u
and Fermi Temperature, T
F

PHY 3201 FIZIK KEADAAN PEPEJAL
Metal
expt

FEG

expt
/

FEFG
=
m*/m

Li 1.63 0.749 2.18
Na 1.38 1.094 1.26
K 2.08 1.668 1.25
Cu 0.695 0.505 1.38
Ag 0.646 0.645 1.00
Au 0.729 0.642 1.14
Al 1.35 0.912 1.48
Results for simple metals (in units mJ/mol K)
show that the FEFG values are in reasonable
agreement with experiment, but are always
too high:
The departure from unity involves three
separate effects:
2. Interaction of conduction electrons with
phonons (phonons can distort the
lattice that the electrons see .electron-
phonon scattering is common in most
materials)
3. Interaction of the conduction electrons
with themselves (these are negative
charges, which should repel one
another!)
1. Interaction of conduction electrons with
the periodic potential of the lattice