1

Free Electron Model for Metals

Metals are very good at conducting both heat and electricity.
Metals were described as behaving like a set of nuclei forming a
lattice with a sea of electrons shared between all nuclei/lattice
(moving freely between them):
This is referred to as the free electron model for metals.
This model explains many of the properties of metals:
Electrical Conductivity: The mobile electrons carry current.
Thermal Conductivity: The mobile electrons can also carry heat.
Malleability and Ductility: Deforming the metal still leaves each
cation surrounded by a sea of electrons, so little energy is
required to either stretch or flatten the metal.
Opacity and Reflectance (Shininess): The electrons will have a
wide range of energies, so can absorb and re-emit many different
wavelengths of light.
The Free Electron Gas Model
Plot 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
Free-Electron Model

m
k
m
p
2 2
2 2 2

= = c
classical description

+ = + + + V E
m
0
2
2
2

( ) z k y k x k
L
xyz
z y x
sin sin sin
8
3
= + = +
In a 3D slab of metal, es are free to move
but must remain on the inside
Solutions are of the form:
L
n
z
t
( )
2 2 2
2
2
8
z y x
n n n
mL
h
+ + = c
With energy:
Quantum Mechanical Viewpoint
At T = 0, all states are filled
up to the Fermi energy
( )
max
2 2 2
2
2
8
z y x Fo
n n n
mL
h
+ + = c
A useful way to keep track of the states that are filled is:
max
2 2 2 2
n n n n
z y x
+ +
Electron follow Fermi-Dirac Distribution
( )
1
1
) (
/
+
=
kT
f
E E
e
E f
total number of states up to an energy c
fermi
:
3
3
max
4
8
1
8
1
2 2
n
sphere
of
volume t
=
|
.
|

\
|
= N
3 / 2
2 19
3 / 2
2
. 10 646 . 3
3
8
|
|
.
|

\
|
=
|
|
.
|

\
|
=

V
N
m eV x
V
N
m
h
Fo
t
c
max
2
2
2
8
n
mL
h
Fo
= c
# states/volume ~ # free es / volume
Example: Numerical Values for Copper slab
V
N
= 8.96 gm/cm
3
1/63.6 amu 6e23 = 8.5e22 #/cm
3
= 8.5e28 #/m
3
n
max
= 4.3 e 7
so we can easily pretend that theres a smooth distrib of n
x
n
y
n
z
-states
eV
V
N
m eV x
V
N
m
h
Fo
0 . 7 . 10 646 . 3
3
8
3 / 2
2 19
3 / 2
2
=
|
|
.
|

\
|
=
|
|
.
|

\
|
=

t
c
Density of States
How many combinations of are there
within an energy interval c to c + dc ?
3 / 2
2
3
8
|
|
.
|

\
|
=
V
N
m
h
Fo
t
c
2 / 3
2
8
3
|
.
|

\
|
|
.
|

\
|
=
h
mE V
N
t
dE
h
m
h
mE V
dN
2
2 / 1
2
8 8
2
3
3
|
.
|

\
|
|
.
|

\
|
=
t
( )
2 / 1
2 / 3
2 / 1
2 / 1
3
3
2
3
2
8
) ( E
E
N
E m
h
V
dE
dN
E g
Fo
= = =
t
( ) ( ) c c c c d g f KE Tot
}

=
0
Huge number of states, it can be treated in
continuous energy
At T 0 the electrons will be spread out among the allowed states
How many electrons are contained in a particular energy range?
|
|
.
|

\
|
|
|
.
|

\
|
occuring energy this
of y probabilit
energy particular a
have to ways of number
( )
1
1
2
8
) (
/ ) (
2 / 1 2 / 1 3
3
+
=
kT
f
E
e
E m
h
V
E n
c
t
) ( ) ( ) ( E f E g E n =
this assumes there are no other issues
Electrical transport (relaxation time) in conductor




eE
v
m
dt
dv
m
d d
= +
t
j nev
ne
m
d
= =
2
t
E
Electron Conductivity
F
F r
v
l
m
e
n
v
l
v
l
m
e
n
E j Law Ohm
*
2
*
2
=
= = =
=
o
t
t
o
o
V
N
n =
ty conductivi
velocity Fermi v
density electron n
path free mean electron l
time collision time relaxation
F
=
=
=
=
= =
o
t
Simple Kinetic Theory of Heat Conduction
ty conductivi thermal
Cv
= =
3

q
x

x
Hot
Cold
x
v
x
t
( ) ( )
v x x v x x x
x x
nEv
2
1
nEv
2
1
q
+
=
2
( )
-
( )
-
x
x x
x
d nEv
q v
dx
d nE
v
dx
t
t
=
=
2
-
x
du dT
v
dT dx
t =
/ = C du dT
,
2 2
/ 3
x
v v =
2
-
3
=
x
v dT
q C
dx
t
2
3
=
Cv
k
t
Taylor Expansion:
local thermodynamics equilibrium: u=u(T)
Assigments
Proof that at T=0 the total energy of
electron

Calculate specific heat capacity using FEM
What fraction of free electron in Cu have a
kinetic energy between 3.95 eV and 4.05 eV
at room temperature
Fo
NE U
5
3
=
Heat Capacity of the Quantum-Mechanical FEM
( )
1
1
) (
/

=
kT E
e
E f

where = chemical potential ~ E
F
for kT << E
F
Quantum mechanics showed that the occupation of electron states is governed
by the Pauli exclusion principle, and that the probability of occupation of a
state with energy E at temperature T is:
0
0.2
0.4
0.6
0.8
1
-0.1 -0.05 0 0.05 0.1
F
E
R
M
I
-
D
I
R
A
C

D
I
S
T
R
I
B
U
T
I
O
N
E- (eV)
1000 K
300 K
100 K
Heat Capacity of Metals: Theory vs. Expt. at low T
Very low temperature
measurements reveal:
Meta
l

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 too high:
The discrepancy is
accounted for by
defining an effective
electron mass m* that is
due to the neglected
electron-ion interactions
Problems with Free Electron Model

* * * * * * * * * * * * * * * * * * * * * * * * * * * *
1) Bragg reflection
2) .
3) .
Other Problems with the Free Electron Model
graphite is conductor, diamond is insulator
variation in colors of x-A elements
temperature dependance of resistivity
resistivity can depend on orientation of crystal & current I direction
frequency dependance of conductivity
variations in Hall effect parameters
resistance of wires effected by applied B-fields
.
.
.

Nearly-Free Electron Model
version 1 SP221

2 /
2
2 /
k
a
t
= =
2 / t = k
2 /
2
2 /
k
a
t
= =
Nearly-Free Electron Model
version 2 SP324
Bloch Theorem
Special Phase Conditions, k = +/- m t/a
the Special Phase Condition k = +/- t/a

This treatment assumes that when
a reflection occurs, it is 100%.
+(x) ~ u e
i(kx-et)
+(x) ~ u(x) e
i(kx-et)

~~~~~~~~~~
amplitude
In reality, lower energy waves are sensitive to the lattice:
Amplitude varies with location
u(x) = u(x+a) = u(x+2a) = .
Blochs
Theorem
u(x+a) = u(x)
+(x+a) e
-i(kx+ka-et)
= +(x) e
-i(kx-et)
+(x) ~ u(x) e
i(kx-et)
+(x+a) = e
ika
+(x)
Something special happens with the phase when
e
ika
= 1
ka = +/ m t m = 0 not a surprise
m = 1, 2, 3,
... , 2 ,
a a
k
t t
=
What it is ?
a
k
t
= Consider a set of waves with +/ k-pairs, e.g.
k = + t/a moves k = t/a moves

This defines a pair of waves moving right & left
Two trivial ways to superpose these waves are:
+
+
~ e
ikx
+ e
ikx
+

~ e
ikx
e
ikx
+
+
~ 2 cos kx +

~ 2i sin kx
+
+
~ 2 cos kx +

~ 2i sin kx
Kittel
,+
+
|
2
~ 4 cos
2
kx ,+

|
2
~ 4 sin
2
kx
Free-electron Nearly Free-electron
Kittel
Discontinuities occur because the lattice is impacting the movement of electrons.
Effective Mass m*
A method to force the free electron
model to work in the situations where
there are complications
ER Ch 13 p461 starting w/ eqn (13-19b)
* 2
2 2
m
k
= c
free electron KE functional form
Effective Mass m*
-- describing the balance between applied ext-E and lattice site reflections
2
2
2
1
*
1
k m c
c
=
c

m* a = E F
ext
q E
ext
No distinction between m & m*,
m = m*, free electron, lattice structure does
not apply additional restrictions on motion.
m = m*
greater curvature, 1/m* > 1/m > 0, m* < m
net effect of ext-E and lattice interaction
provides additional acceleration of electrons
greater |curvature| but negative,
net effect of ext-E and lattice interaction
de-accelerates electrons

At inflection pt
1)
2)
*
2 2 2 2
2 2 m
k
m
k
lattice from on perturbati apply

= c
Another way to look at the discontinuities
Shift up implies effective mass has decreased, m* < m,
allowing electrons to increase their speed and join
faster electrons in the band.
The enhanced e-lattice interaction speeds up the electron.
Shift down implies effective mass has increased, m* > m,
prohibiting electrons from increasing their speed and making
them become similar to other electrons in the band.
The enhanced e-lattice interaction slows down the electron
From earlier:
Even when above barrier,
reflection and transmission coefficients can
increase and decrease depending upon the energy.
change in motion
due to reflections
is more significant
than change in motion
due to applied field
change in motion
due to applied field
enhanced by change in reflection coefficients
Nearly-Free Electron Model
version 3
la Ashcroft & Mermin, Solid State Physics
This treatment recognizes
that the reflections of electron
waves off lattice sites can
be more complicated.
A reminder:
Waves from the left behave like:
iKx iKx
left
the
from
e r e

+ = +
iKx
left
the
from
e t = +
m
K
2
2 2

= c
Waves from the right behave like:
iKx iKx
right
the
from
e r e + = +

iKx
right
the
from
e t

= +
m
K
2
2 2

= c
right left sum
B A + + + = +
Blochs Theorem defines periodicity of the wavefunctions:
( ) ( ) x e a x
sum
ika
sum
+ = + +
( ) ( ) x e a x
sum
ika
sum
+
'
= + +
'
unknown weights
Related to
Lattice spacing
( ) ( ) x e a x
sum
ika
sum
+ = + +
( ) ( ) x e a x
sum
ika
sum
+
'
= + +
'
Applying the matching conditions at x a/2
A+ + B+
left
right
A+ + B+
left
right
A+ + B+
left
right
A+ + B+
left
right
iKa iKa
e
t
e
t
r t
ka

+

=
2
1
2
cos
2 2
m
K
2
2 2

= c
And eliminating the unknown constants A & B leaves:
For convenience (or tradition) set:
2 2
1 r t + =
o i
e t t =
o i
e r i r =
( )
ka
t
Ka
cos
cos
=
+o
( )
ka
t
Ka
cos
cos
=
+o
Related to
possible
Lattice spacings
Related to
Energy
m
K
2
2 2

= c
allowed solution regions
a
l
l
o
w
e
d

s
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t
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o
n

r
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