Chapter 6

Free Electron Fermi Gas

(FEFG)
Phys 175A
Dr. Ray Kwok
SJSU
Classification of Solids
Many ways to classify solids
(a) lattice structure and
(b) crystal bonding
(c) measurable properties
One of the easiest and earliest properties
observed is the dc electrical conductivity
Electrical Properties
Some solids conduct current at all temperatures and,
generally, the resistivity of such solids increases when
temperature increases. We call them METALS
Other solids stop conducting at low temperatures and their
resistivity decreases with increasing temperature. We call
them INSULATORS
SEMI-CONDUCTORS are basically insulators with higher
conductivity (due to smaller band gap).
Another way to understand this is to examine the band
structure of the compound (next chapter).
The Free Electron Gas Model
(FEG)
U(x) for a 1-D
crystal lattice:
Simple and
crude finite-
square-well
model:
Can we justify this model?
How can one replace the entire lattice by a constant (zero) potential?
U
U = 0
Conduction Band
Atom 1
Atom 2
R
Discrete Electronic
Energy States
V(r) -1/r

Split Energy
Levels
Atom 1
Atom 2
R
0
-5
-25
-30
-35
0 5 10 3.67
-10
2p
3s
3p
E
n
e
r
g
y

(
e
V
)
Interatomic Distance ()
Free electron band
Na: 1s
2
2s
2
2p
6
3s
1
monovalent alkali
Justifications of the FEG Model
1. Metals have high electrical conductivity and no apparent activation
energy, so at least some of their electrons are free and not bound to atoms.
Measured V=IR.
4. Therefore model the behavior of the free
electrons with U = 0 inside the volume of the
metal and a finite potential step at the
surface. Each atom has n
0
free electrons,
where n
0
= chemical valence. Resistance
comes from electrons interacting with lattice
through occasional collisions:
2. Coulomb potential energy of positive ions U 1/r is screened by bound
electrons and is weaker at large distances from nucleus. Its further
screened by mobile electrons around to minimize U ~ 0.
3. Electrons would have lowest U (highest KE) near nuclei, so they
spend less time near nuclei and more time far from nuclei where U is
not changing rapidly. Pauli Exclusion Principle also forbid mobile
electrons to be right too close to the core.
Particle in a box (QM - wave)
1. Wave functions:
2. Energies:
Time-independent
Schrdinger Equation:
E U
m
= +
2
2
2
h
With U = 0:
E
m
=
2
2
2
h

2
2
2
h
mE
=

2 2
k =
) ( t r k i
Ae

=
v
v
Traveling waves (plane waves)
m
k
E
2
2 2
h
=
Parabolic energy bands
E
k
x
electronic dispersion
Particle in a 3D box
1-D Potential Well
3-D Cubic Potential Well (with sides length L)
2
2
2 2
n
n
n
mL 2
E
n
L
x
sin
L
2
) x (
h
=
|

\
|

=
( )
2
0
2
3
2
2
2
1
2
2 2
n n n
3 2 1
2 / 3
n n n
n E n n n
mL 2
E
n
L
z
sin n
L
y
sin n
L
x
sin
L
2
) x (
3 2 1
3 2 1
= + +

=
|

\
|

\
|

\
|

\
|
=
h
Degenerate states with n
1
, n
2
, n
3.
(n
i
> 0)
Here, n is the quantum number
n > 0
Example: 34 Electrons in a box
Quantum numbers (n
1,
n
2,
n
3
), E = n
2
E
o
The lowest energy for this system is 3E
0
, which corresponds
to n
1
= n
2
= n
3
= 1
Thus only 2 (two) electrons can have this energy:
one with spin and one with spin
Next energy level (6E
0
), for which one of ns is 2 (3
combinations)
Thus total of 6 (six) electrons can have this energy
Next energy level (9E
0
) can also accommodate 6 electrons
What are the combinations of ns for this energy level?
Next energy level (11E
0
) also accommodates 6 electrons
What are the ns?
Next energy level (12E
0
) is two-fold degenerate
34 Electrons in a box (cont.)
So far we have placed 22 electrons, so we need
to add 12 more electrons
What is the next energy level? 14E
0
What are n
1
, n
2
, and n
3
?
What is degeneracy?
This is the energy carried by each of the 12
electrons (what kind of energy is this?)
We placed all 34 electrons!!
0
1
2
3
4
5
6
7
8
9
1 0
1 1
1 2
1 3
1 4
1 5
1 6
1 7
1 8
( 3 , 2 , 2 )
( 3 , 2 , 1 )
( 3 , 1 , 1 )
( 2 , 2 , 2 )
( 2 , 2 , 1 )
( 2 , 1 , 1 )
( 1 , 1 , 1 )
E
n
e
r
g
y

(
i
n

u
n
i
t
s

o
f

E
0
)
Reading Energy Diagram
Energy is plotted in terms
of E
o
Values of ns are shown
on the right.
In this example E
F
= 14 E
o
Configuration shown is at
T = 0.
Probability to find
electrons with energy
greater than 14E
o
is 0,
and below 14 E
o
is 1
(at T = 0)
Density of States: FEG
so the volume in k-space per state is:
By using periodic boundary conditions for a cubic solid with edge L and
volume V = L
3
, we define the set of allowed wave vectors:
... , 3 , 2 , 1 n , n , n
L
n 2
k
L
n 2
k
L
n 2
k
z y x
z
z
y
y
x
x
=

=
3
L
2
|

\
|

and the density of states in k-space is:
( )
3 3
8
V
L / 2
1
) k ( N

=
Just as in the case of phonons!
such that:
) L r ( ) L r ( ) r ( ) L r (
z y x
+ = + = = +
r r r r
(No upper limit)
Fermi Surface
( )
(

\
|
=
|
|

\
|
=
3
3
3
4
8
2 _
_
#
2 #
F
k
V
N k volume
k volume
states
e

Since the FEG is isotropic, the surface of

constant E in k-space is a sphere. Thus for
a metal with N electrons we can calculate
the maximum k value (k
F
) and the maximum
energy (E
F
).
F
k
k
x
k
z
k
y
Fermi sphere
2 spin states per k
N = # of mobile electrons
( )
3 / 1
2
3 / 1
2
3 3 n
V
N
k
F
=
|

\
|
=
( )
3 / 2
2
2 2 2
3
2 2
n
m m
k
E
F
F

h h
= =
Fermi wave vector
Fermi energy
( )
3
1
2
3
e F
k =
Fermi Parameters
Fermi Energy, E
F
: Work Function
Energy
Fermi Energy
Fermi Velocity:
( )
( )
3
1
2
3
2
2
2 2 2
3
3
2 2
e
F
F
e
F
F
m m
k
v
m m
k
E


h h
h h
= =
= =
Element Electron
Density,

e
[10
28
m
-3
]
Fermi
Energy
E
F
[eV]
Fermi
Temperature
T
F
[10
4
K]
Fermi
Wavelength

F
[]
Fermi
Velocity
v
F
[10
6
m/s]
Work
Function

[eV]
Na 2.65 3.24 3.77 6.85 1.07 2.35
Cu 8.47 7.00 8.16 4.65 1.57 4.44
Ag 5.86 5.49 6.38 5.22 1.39 4.3
Au 5.90 5.53 6.42 5.22 1.40 4.3
Fe 17.0 11.1 13.0 2.67 1.98 4.31
Al 18.1 11.7 13.6 3.59 2.03 4.25
Sn 14.8 10.2 11.8 3.83 1.9 4.38
Vacuum
Level
Band Edge
Fermi Temp.
B
F
F
k
E
T =
Fermi wavevector
Density of States N(E)
k d k N dE E N dN
3
) ( 2 ) ( = =
2 / 1
2 2 2 2
2
2
2
3
2
2
/ /
4
8
2
4
) ( 2 ) (
|

\
|
= =
|

\
|
= =
h h h
mE mV
m k
k V
dk dE
k V
dE
dk k
k N E N

2 / 1
2
2
|

\
|
=
h
mE
k
( )
2 / 1
3
3 2
2 ) ( E m
V
E N
h
=
The differential number of
electron states in a range of
energy dE or wavevector dk is:
m
k
E
2
2 2
h
=
Free electron gas
N(E)
E
E
F
density of state
# of e per E
( )
2 / 1
3
3 2 2
2 / 1
2 2
2 / 3
2 2
3
3
2
2 2
2
) (
2
3 3
4
8
2
E m
V m mE V
dE
dN
E N
mE V
k
V
N
h h h
h

=
|

\
|
|

\
|
= =
|

\
|
=
(

\
|
=
Or
Fermi-Dirac Distribution
The probability distribution function, f(E), which describes
the probability that a state with energy E is occupied for
electrons is the Fermi-Dirac Distribution Function

>
=
F
F
E E for , 1
E E for , 0
) E ( f
at T = 0
Fermi-Dirac Distribution T > 0
1 e
1
) E ( f
T k / ) E (
B
+
=

0
1
E
F
Electron Energy, E
O
c
c
u
p
a
t
i
o
n

P
r
o
b
a
b
i
l
i
t
y
,

f
Work Function,
Increasing T
T = 0 K
k T
B
Vacuum
Energy
is the Chemical Potential
which is equal to E
F
at T=0.
Often, and E
F
are mixed up.
1/2
T
Heat Capacity of the FEG
So the electronic contribution to the
molar heat capacity would be expected
to be
) (
2
3
kT N E
el
=
or expressed per
mole (n):
RT kT N kT
n
N
n
E
A
el
2
3
2
3
2
3
= = =
R
n
E
dT
d
C
el
el 2
3
=
|

\
|
=
This is temperature independent!!! Only half of the 3R we found for
the lattice heat capacity at high T. But experiments show that the
total C for metals is only slightly higher than for insulators, which
conflicts with the classical theory!
19
th
century puzzle: each monatomic gas molecule in sample at
temperature T has energy, so if the N free electrons in a metal make up
a classical gas they should behave similarly.
kT
2
3
Heat Capacity of the FEFG
So at temperature T
the total energy is:
( )
( )
( )

= =
0
2
kT / E
kT / E E
F
2
el
el
dE
1 e
e ) E E )( E ( N E
kT
1
dT
dE
C
F
( )

= =
0
kT / E
0
el
dE
1 e
) E ( N E
dE ) E ( N ) E ( f E E
And the electronic
heat capacity is:
T ) E ( N k C
F
2
3 el
2

= C
el
T
FEG + Pauli + Fermi-Dirac (QM)
This integral is complicated because is also a function of T.
Treatment of this approximation is given in advance texts.
The result is:
Understand linear T dependence
T E N k
dT
dE
C
F
el
el
) ( 3
2
=
# electrons that can
absorb extra
thermal energy N(E)
E
E
F
N(E)f(E)
2kT ( )
) (
) ( ) ( 2
F
F F
E N kT
E f E N kT

total thermal energy

of electrons at T
( )
) ( ) (
) ( ) (
2 2
2
3
0
2
3
0
F
F
E N T k E T E
E N kT kT E T E
+
+
FEG heat
capacity at T
T T E N k C
F el

= = ) (
2
3
2
Remarkably
close to the
exact result!
Only electrons near the Fermi surface
can gain energy !!
Total C
But the linear dependence is impossible to measure directly, since the
heat capacity of a metal has two contributions. Now for a metal at low
temperatures we can write the total heat capacity:
3
) ( T T C C T C
lattice el
+ = + =
Heat Capacity of Metals (expt)
Metal
expt

FEG

expt
/
FEG
=
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 FEG values are in
reasonable agreement with
experiment, but are always
higher:
The discrepancy is
accounted for by defining
an effective electron mass
m* that is due to the
neglected electron-ion
interactions.
i.e. phonons drag electrons
& make them move slower.
Ohms Law
E E J
J
E
A
L
A
L
R
A
L
J
E
A J
L E
i
V
R

1
1
1
= =
= =

= =
=

= =
Examples of Resistivity ()
Ag (Silver): 1.5910
-8
m
Cu (Copper): 1.6810
-8
m
Graphite (C): (3 to 60)10
-5
m
Diamond (C): ~10
14
m
Glass: ~10
10
- 10
14
m
Pure Germanium: ~ 0.5 m
Pure Silicon: ~ 2300 m
At Room Temp
Microscopic Model
) ( ) ( T v E v v
RMS d avg
r r r
+ =
m/s 10
) 10 )( 10 )( 10 6 . 1 (
6 . 1
) m (10 mm 1 and A 6 . 1
C 10 6 1 ; m 10 cm 10 ~
4
6 - 29 19
2 6 - 2
19 3 29 3 23

= =
= =
= =
= =
enA
i
v
A i
. e n
n e
J
v nv e J
d
d d
T k v m
RT at
m
T k
v v
B e
e
B
RMS
2
3
2
1

s
m
10
3
2
6 2
=
= =
v
RMS
>>v
d
v
avg
v
RMS
(speed)
depends on T only, not E
!??
0.1 mm/s? Takes forever to turn on the light??
Drude Model - conductivity
The FEG model was developed by Paul Drude
(1900) in order to describe the electrical and
thermal conductivity of metals. This work greatly
influenced the course of solid-state physics and it
introduces basic concepts we still use today.
F = qE = mv/t mv
d
/
v
d
= qE/m
J = nqv
d
= E
= nq
2
/m
Temperature dependence of is just that of
l is the relaxation time = /v
avg
l is the mean free path
Conductivity in Reciprocal Space
The Fermi sphere contains all occupied
electron states in the FEG. In the
absence of an electric field, there are
the same number of electrons moving
in the x, y, and z directions, so the
net current is zero.
But when a field E is applied along the
x-direction, the Fermi sphere is shifted
by an amount related to the net change
in momentum of the FEG:

x x x x
eE mv p k = = = h
h

x
x x x
eE
mv p k = = =
F
k
k
x
k
z
k
y
Fermi surface
The shift in Fermi sphere creates a net current
flow since more electrons move in the x direction
than the +x direction. But the excess current
carriers are only those very near the Fermi
surface. So the current carriers have velocity v
F
.
k
x
k
y
E
Analysis of Mean Free Path
Since the velocity of current-carrying electrons is essentially independent
of T, we need to examine the behavior of the mean-free-path.
The probability of a collision in a distance x is:
x
e
-
v
F
collision cross-section = <r
2
>
cross-sectional area of slab = A
atomic density = n
a
slab of area sectional cross
collision for area sectional cross total
P

=
2
2
r x n
A
r x A n
P
a
a

=
2
a
r n
1

= l
Now in a distance x = , P = 1 is
true, so we can solve for :
l
Electrons collide with atoms dominatesCoulomb.
(T)
Now if we assume that the collision cross-section is due to vibrations of
atoms about their equilibrium positions, then we can write:
T
1

2 2 2
y x r + =
kT Cy Cx
2
1
2
2
1
2
2
1
= =
And the thermal average potential energies can be written as:
Therefore
T r
2

and
T r
1 1
2

> <
l
Finally T
l = nq
2
/m nq
2
/mv
F
or
At low T, is limited by size or impurities, so becomes constant l
Example : (T) of K
The Hall Effect
This phenomenon, discovered in 1879 by American physics
graduate student (!) Edwin Hall, is important because it allows us
to measure the free-electron concentration n for metals (and
semiconductors!) and compare to predictions of the FEG model.
It also confirmed the electron-hole description of charge carriers.
Hall probe
I
F
B
= q v x B
Hall Coef.
A hypothetical charge carrier of
charge q experiences a Lorentz
force in the lateral direction:
I
t
w
qvB F
B
=
As more and more carriers are deflected, the
accumulation of charge produces a Hall field E
H
that imparts a force opposite to the Lorentz force:
H E
qE F =
Equilibrium is reached when these two opposing
forces are equal in magnitude, which allows us to
determine the drift speed:
H
qE qvB =
B
E
v
H
=
From this we can write the current density:
B
nqE
nqv J
H
= =
And it is customary to define the Hall coefficient in terms of
the measured quantities: (E
H
is transverse to J)
nq JB
E
R
H
H
1
= =
n is # of charge carriers per unit volume
Hall Effect Results!
In the lab we actually measure the Hall voltage V
H
and the current I, which
gives us a more useful way to write R
H
:
If we calculate R
H
from our measurements
and assume |q| = e (which Hall did not
know!) we can find n. Also, the sign of V
H
and thus R
H
tells us the sign of q! (carriers)
( ) nq IB
t V
B wt I
w V
JB
E
R
H H H
H
1
/
/
= = = =
w E V
H H
=
Jwt JA I = =
R
H
(10
-11
m
3
/As)
Meta
l
n
0
solid liquid FEG value
Na 1 -25 -25.5 -25.5
Cu 1 -5.5 -8.25 -8.25
Ag 1 -9.0 -12.0 -12.0
Au 1 -7.2 -11.8 -11.8
Be 2 +24.4 -2.6 -2.53
Zn 2 +3.3 -5 -5.1
Al 3 -3.5 -3.9 -3.9
The discrepancies between the FEG
predictions and expt. nearly vanish when
liquid metals are compared. This reveals
clearly that the source of these
discrepancies lies in the electron-lattice
interaction. But the results for Be and Zn
are puzzling. How can we have q > 0 ???
Look at the diagram for +/- charges again.
*
*
Thermal Conductivity of Metals
In metals at all but the lowest temperatures, the electronic
contribution to far outweighs the contribution of the lattice.
So we can write:
l v C
3
1
el el
=
Also, the electrons that can absorb extra thermal energy and
therefore contribute to the heat capacity have energies very
near E
F
, so they essentially all have velocity v
F
. This gives:
The electron mean-free path can be
rewritten in terms of the collision time:
= v l
=
2
el
v C
3
1
From our earlier discussion the electronic heat capacity is:
T ) E ( N k C
F
2
3 el
2

=
=
2
F el
v C
3
1
It is easy to show that
N(E
F
) can be expressed:
F
F
E 2
N 3
) E ( N =
or per unit volume
F
F
F
E
n
V
E N
E N
2
3 ) (
) ( =

Which gives the heat capacity per unit volume:

F
el
el
E
T
n k
V
C
C
2
2
2

Wiedemann-Franz Law
Now long before Drudes time, Gustav Wiedemann and
Rudolf Franz published a paper in 1853 claiming that the ratio
of thermal and electrical conductivities of all metals has nearly
the same value at a given T:
Now the thermal conductivity
per unit volume is:
or T
m
n k
3
2 2

=

2 2
2
2
3
1
F
F
v
E
T
n k =

2
2
2
1
2
2
2
3
1
F
F
v
mv
T
n k =
constant =

Gustav Wiedemann
Not long after (1872) Ludwig Lorenz (not
Lorentz!) realized that this ratio scaled
linearly with temperature, and thus a
Lorenz number L can be defined:
L
T

very nearly constant for all

metals (at room T and above)
~ 1/T, so ~ independent of temperature!!
Lorenz Number
We can readily compare the prediction of the
FEG model to the results of experiment:
This is remarkableit is
independent of n, m, and even !!
T
m
ne
T
m
n k
T
L
FEG

2
2 2
3
= =
L = /T 10
-8
(J/CK)
2
Metal 0 C 100 C
Cu 2.23 2.33
Ag 2.31 2.37
Au 2.35 2.40
Zn 2.31 2.33
Cd 2.42 2.43
Mo 2.61 2.79
Pb 2.47 2.56
2
2 2
3e
k
=
( )
2
8
10 45 . 2
CK
J
FEG
L

=
Agreement with experiment is
quite good, although the value of L
is about a factor of 10 less at
temperatures near 10 KCan you
speculate about the reason?
An Historical Footnote
Drude of course used classical values for the electron velocity v and heat
capacity C
el
. By a tremendous coincidence, the error in each term was about two
orders of magnitude in the opposite direction! So the classical Drude model
gives the prediction:
[ C ~ 3/2 Nk, a factor T/T
F
missing,
mv
2
= 3/2 kT instead of E
F
, v
2
= (2kT/m) (T
F
/T), the factor T
F
/T is missing
= 1/3 Cv
2
becomes right order!! ]
But in Drudes original paper, he inserted an erroneous factor of two, due to a
mistake in the calculation of the electrical conductivity. So he originally
reported:
( )
2
8
10 12 . 1
CK
J
Drude
L

=
( )
2
8
10 24 . 2
CK
J
L

= !!!
So although Drudes predicted electronic heat capacity was far too high, this
prediction of L made the FEG model seem even more impressive than it really
was, and led to general acceptance of the model.