CHAPTER 5
FREE ELECTRON
THEORY
Free Electron Theory
Many solids conduct electricity.
There are electrons that are not bound to atoms but are able to move through the
whole crystal.
Conducting solids fall into two main classes; metals and semiconductors.
and increases by the addition of small
amounts of impurity. The resistivity normally decreases monotonically with
decreasing temperature.
and can be reduced by the addition of
small amounts of impurity.
Semiconductors tend to become insulators at low T.
6 8
( ) ;10 10
metals
RT m µ
÷ ÷
÷ O÷
( ) ( )
pure semiconductor metal
RT RT µ µ
÷
Why mobile electrons appear in some
solids and others?
When the interactions between electrons are considered this
becomes a very difficult question to answer.
The common physical properties of metals;
• Great physical strength
• High density
• Good electrical and thermal conductivity, etc.
This chapter will calculate these common properties of metals
using the assumption that conduction electrons exist and consist
of all valence electrons from all the metals; thus metallic Na, Mg
and Al will be assumed to have 1, 2 and 3 mobile electrons per
atom respectively.
A simple theory of ‘ free electron model’ which works
remarkably well will be described to explain these properties of
metals.
Why mobile electrons appear in some
solids and not others?
According to free electron model (FEM), the
valance electrons are responsible for the
conduction of electricity, and for this reason
these electrons are termed conduction electrons.
Na
11
￫ 1s
2
2s
2
2p
6
3s
1
This valance electron, which occupies the third atomic shell,
is the electron which is responsible chemical properties of
Na.
Valance electron (loosely bound)
Core electrons
When we bring Na atoms together to form a Na
metal,
Na has a BCC structure and the distance between
nearest neighbours is 3.7 A˚
The radius of the third shell in Na is 1.9 A˚
Solid state of Na atoms overlap slightly. From this
observation it follows that a valance electron is no
longer attached to a particular ion, but belongs to
both neighbouring ions at the same time.
Na metal
The removal of the valance electrons leaves
a positively charged ion.
The charge density associated the positive
ion cores is spread uniformly throughout the
metal so that the electrons move in a
constant electrostatic potential. All the
details of the crystal structure is lost when
this assunption is made.
+
+
+
+
+ +
A valance electron really belongs to the whole
crystal, since it can move readily from one ion to
its neighbour, and then the neighbour’s
neighbour, and so on.
This mobile electron becomes a conduction
electron in a solid.
According to FEM this potential is taken as zero
and the repulsive force between conduction
electrons are also ignored.
Therefore, these conduction electrons can be
considered as moving independently in a square
well of finite depth and the edges of well
corresponds to the edges of the sample.
Consider a metal with a shape of cube with edge
length of L,
Ψ and E can be found by solving Schrödinger equation
0
L/2
V
L/2
2
2
2
E
m
¢ ¢ ÷ V =
0 V =
Since,
( , , ) ( , , ) x L y L z L x y z ¢ ¢ + + + =
• By means of periodic boundary conditions Ψ’s are running waves.
The solutions of Schrödinger equations are plane waves,
where V is the volume of the cube, V=L
3
So the wave vector must satisfy
where p, q, r taking any integer values; +ve, ve or zero.
( )
1 1
( , , )
x y z
i k x k y k z
i k r
x y z e e
V V
¢
+ +
= =
Normalization constant
Na pì =
2
, where k
t
ì
 
=

\ .
2
Na p
k
t
=
2 2
k p p
Na L
t t
= =
2
x
k p
L
t
=
2
y
k q
L
t
=
2
z
k r
L
t
=
;
;
The wave function Ψ(x,y,z) corresponds to an
energy of
the momentum of
Energy is completely kinetic
2 2
2
k
E
m
=
2
2 2 2
( )
2
x y z
E k k k
m
= + +
( , , )
x y z
p k k k =
2 2
2
1
2 2
k
mv
m
=
2 2 2 2
m v k =
p k =
We know that the number of allowed k values
inside a spherical shell of kspace of radius k of
2
2
( ) ,
2
Vk
g k dk dk
t
=
where g(k) is the
density of states per
unit magnitude of k.
The number of allowed states
per unit energy range?
Each k state represents two possible electron
states, one for spin up, the other is spin down.
( ) 2 ( ) g E dE g k dk =
( ) 2 ( )
dk
g E g k
dE
=
2 2
2
k
E
m
=
2
dE k
dk m
=
2
2mE
k =
( ) g E = 2 ( ) g k
dk
dE
2
2
2
V
t
kk
2
2mE
2
m
k
3/ 2 1/ 2
2 3
(2 )
2
( )
V
m E g E
t
=
Ground state of the free electron gas
Electrons are fermions (s=±1/2) and obey
Pauli exclusion principle; each state can
accommodate only one electron.
The lowestenergy state of N free
electrons is therefore obtained by filling
the N states of lowest energy.
Thus all states are filled up to an energy E
F
,
known as Fermi energy, obtained by
integrating density of states between 0 and E
F,
should equal N. Hence
Remember
Solve for E
F
(Fermi energy);
2/ 3
2 2
3
2
F
N
E
m V
t  
=

\ .
3/ 2 1/ 2
2 3
(2 )
2
( )
V
m E g E
t
=
3/ 2 1/ 2 3/ 2
2 3 2 3
0 0
( ) (2 ) (2 )
2 3
F F
E E
F
V V
N g E dE m E dE mE
t t
= = =
} }
The occupied states are inside the Fermi sphere in kspace
shown below; radius is Fermi wave number k
F
.
2 2
2
F
F
e
k
E
m
=
k
z
k
y
k
x
Fermi surface
E=E
F
k
F
2/ 3
2 2
3
2
F
N
E
m V
t
 
=

\ .
From these two equation k
F
can be found as,
1/ 3
2
3
F
N
k
V
t  
=

\ .
The surface of the Fermi sphere represent the
boundary between occupied and unoccupied k
states at absolute zero for the free electron gas.
Typical values may be obtained by using
monovalent potassium metal as an example; for
potassium the atomic density and hence the
valance electron density N/V is 1.402x10
28
m
3
so
that
Fermi (degeneracy) Temperature T
F
by
19
3.40 10 2.12
F
E J eV
÷
= × =
1
0.746
F
k A
÷
= °
F B F
E k T =
4
2.46 10
F
F
B
E
T K
k
= = ×
It is only at a temperature of this order that the
particles in a classical gas can attain (gain)
kinetic energies as high as E
F
.
Only at temperatures above T
F
will the free
electron gas behave like a classical gas.
Fermi momentum
These are the momentum and the velocity values
of the electrons at the states on the Fermi
surface of the Fermi sphere.
So, Fermi Sphere plays important role on the
behaviour of metals.
F F
P k =
F e F
P m V =
6 1
0.86 10
F
F
e
P
V ms
m
÷
= = ×
2/ 3
2 2
3
2.12
2
F
N
E eV
m V
t  
= =

\ .
1/ 3
2
1
3
0.746
F
N
k A
V
t
÷
 
= = °

\ .
6 1
0.86 10
F
F
e
P
V ms
m
÷
= = ×
4
2.46 10
F
F
B
E
T K
k
= = ×
Typical values of monovalent potassium metal;
The free electron gas at finite temperature
At a temperature T the probability of occupation
of an electron state of energy E is given by the
Fermi distribution function
Fermi distribution function determines the
probability of finding an electron at the energy
E.
( ) /
1
1
F B
FD
E E k T
f
e
÷
=
+
E
F
E<E
F
E>E
F
0.5
f
FD
(E,T)
E
( ) /
1
1
F B
FD
E E k T
f
e
÷
=
+
Fermi Function at T=0
and at a finite temperature
f
FD
=? At 0°K
i. E<E
F
ii. E>E
F
( ) /
1
1
1
F B
FD
E E k T
f
e
÷
= =
+
( ) /
1
0
1
F B
FD
E E k T
f
e
÷
= =
+
FermiDirac distribution function at
various temperatures,
T>0
T=0
n(E,T)
E
g(E)
E
F
n(E,T) number of free
electrons per unit energy
range is just the area
under n(E,T) graph.
( , ) ( ) ( , )
FD
n E T g E f E T =
Number of electrons per unit energy range
according to the free electron model?
The shaded area shows the change in distribution
between absolute zero and a finite temperature.
FermiDirac distribution function is a
symmetric function; at finite
temperatures, the same number of levels
below E
F
is emptied and same number of
levels above E
F
are filled by electrons.
T>0
T=0
n(E,T)
E
g(E)
E
F
Heat capacity of the free electron gas
From the diagram of n(E,T) the change in the
distribution of electrons can be resembled into
triangles of height 1/2g(E
F
) and a base of 2k
B
T so
1/2g(E
F
)k
B
T electrons increased their energy by
k
B
T.
T>0
T=0
n(E,T)
E
g(E)
E
F
The difference in thermal
energy from the value at
T=0°K
2
1
( ) (0) ( )( )
2
F B
E T E g E k T ÷
Differentiating with respect to T gives the
heat capacity at constant volume,
2
( )
v F B
E
C g E k T
T
c
= =
c
2
( )
3
3 3
( )
2 2
F F
F
F B F
N E g E
N N
g E
E k T
=
= =
2 2
3
( )
2
v F B B
B F
N
C g E k T k T
k T
= =
3
2
v B
F
T
C Nk
T
 
=

\ .
Heat capacity of
Free electron gas
Transport Properties of Conduction Electrons
FermiDirac distribution function describes the
behaviour of electrons only at equilibrium.
If there is an applied field (E or B) or a
temperature gradient the transport coefficient of
thermal and electrical conductivities must be
considered.
Transport coefficients
σ,Electrical
conductivity
K,Thermal
conductivity
Total heat capacity at low temperatures
where γ and β are constants and they can
be found drawing C
v
/T as a function of T
2
3
C T T ¸  = +
Electronic
Heat capacity
Lattice Heat
Capacity
Equation of motion of an electron with an applied
electric and magnetic field.
This is just Newton’s law for particles of mass m
e
and charge (e).
The use of the classical equation of motion of a
particle to describe the behaviour of electrons in
plane wave states, which extend throughout the
crystal. A particlelike entity can be obtained by
superposing the plane wave states to form a
wavepacket.
e
dv
m eE ev B
dt
= ÷ ÷ ×
The velocity of the wavepacket is the group
velocity of the waves. Thus
So one can use equation of mdv/dt
1
e e
d dE k p
v
m m
dk dk
e
= = = =
2 2
2
e
k
E
m
p k
e = =
=
e
dv v
m eE ev B
dt t
 
+ = ÷ ÷ ×

\ .
t = mean free time between collisions. An electron
loses all its energy in time t
(*)
In the absence of a magnetic field, the applied E
results a constant acceleration but this will not
cause a continuous increase in current. Since
electrons suffer collisions with
phonons
electrons
The additional term cause the velocity v to
decay exponentially with a time constant when
the applied E is removed.
e
v
m
t
 

\ .
t
The Electrical Conductivty
In the presence of DC field only, eq.(*) has the
steady state solution
Mobility determines how fast the charge carriers
move with an E.
e
e
v E
m
t
= ÷
a constant of
proportionality
(mobility)
e
e
e
m
t
µ =
Mobility for
electron
Electrical current density, J
Where n is the electron density and v is drift
velocity. Hence
( ) J n e v = ÷
N
n
V
=
2
e
ne
J E
m
t
=
J E o =
2
e
ne
m
t
o =
e
e
v E
m
t
= ÷
Electrical conductivity
Ohm’s law
1
µ
o
=
L
R
A
µ
=
Electrical Resistivity and Resistance
Collisions
In a perfect crystal; the collisions of electrons are
with thermally excited lattice vibrations
(scattering of an electron by a phonon).
This electronphonon scattering gives a
temperature dependent collision time
which tends to infinity as T 0.
In real metal, the electrons also collide with
impurity atoms, vacancies and other
imperfections, this result in a finite scattering
time even at T=0.
( )
ph
T t
0
t
The total scattering rate for a slightly imperfect
crystal at finite temperature;
So the total resistivity ρ,
This is known as Mattheisen’s rule and illustrated in
following figure for sodium specimen of different
purity.
0
1 1 1
( )
ph
T t t t
= +
Due to phonon
Due to imperfections
0
2 2 2
0
( )
( )
e e e
I
ph
m m m
T
ne ne T ne
µ µ µ
t t t
= = + = +
Ideal resistivity
Residual resistivity
Residual resistance ratio
Residual resistance ratio = room temp. resistivity/ residual resistivity
and it can be as high as for highly purified single crystals.
6
10
Temperature
pure
impure
Collision time
t
o
10 1
5.3 10 ( )
pureNa
residual
x m o
÷
= O÷
7 1
( ) 2.0 10 ( )
sodium
RT x m o
÷
= O÷
28 3
2.7 10 n x m
÷
=
e
m m =
14
2
2.6 10
m
x s
ne
o
t
÷
=
11
7.0 10 x s
÷
6
1.1 10 /
F
v x m s =
( ) 29 l RT nm =
( 0) 77 l T m µ = =
can be found by taking
at RT
at T=0
F
l v t = Taking ; and
These mean free paths are much longer than the interatomic
distances, confirming that the free electrons do not collide with the
atoms themselves.
Thermal conductivity, K
metals non metals
K K
÷
1
3
V F
K C v l =
V
C
Due to the heat tranport by the conduction electrons
Electrons coming from a hotter region of the metal carry
more thermal energy than those from a cooler region, resulting in a
net flow of heat. The thermal conductivity
l
F
v
B
k T
F
c
F
l v t =
2
1
2
F e F
m v c =
where is the specific heat per unit volume
is the mean free path; and Fermi energy
is the mean speed of electrons responsible for thermal conductivity
since only electron states within about of change their
occupation as the temperature varies.
2 2 2
2
1 1 2
( )
3 3 2 3
B
V F B F
F e e
N T nk T
K C v k
V T m m
t t t
t c t = = =
2
2
v B
F
T
C Nk
T
t  
=

\ .
where
WiedemannFranz law
2
e
ne
m
t
o =
2 2
3
B
e
nk T
K
m
t t
=
2
2
8 2
2.45 10
3
K k
x W K
T e
t
o
÷ ÷
 
= = O

\ .
B
The ratio of the electrical and thermal conductivities is independent of the
electron gas parameters;
8 2
2.23 10
K
L x W K
T o
÷ ÷
= = O
Lorentz
number
For copper at 0 C