Metals I: Free Electron Model

Physics 355
Free Electron Model
Schematic model of metallic
crystal, such as Na, Li, K, etc. + + + + +

The equilibrium positions of

the atomic cores are + + + + +
positioned on the crystal lattice
and surrounded by a sea of + + + + +
conduction electrons.

For Na, the conduction + + + + +

electrons are from the 3s
valence electrons of the free
atoms. The atomic cores + + + + +
contain 10 electrons in the
configuration: 1s22s2p6.
Free Electrons?

 How do we know there are free electrons?

 You apply an electric field across a metal

piece and you can measure a current – a
number of electrons passing through a unit
area in unit time.
 But not all metals have the same current for a
given electric potential. Why not?
Paul Drude
• resistivity ranges from 108 m (Ag) to
1020 m (polystyrene)
• Drude (circa 1900) was asking why? He
was working prior to the development of
quantum mechanics, so he began with a
classical model:
• positive ion cores within an electron
(1863-1906)
gas that follows Maxwell-Boltzmann
statistics
• following the kinetic theory of gases-
the electrons in the gas move in
straight lines and make collisions
only with the ion cores – no electron-
electron interactions.
Paul Drude
• He envisioned instantaneous collisions in
which electrons lose any energy gained
from the electric field.

• The mean free path was approximately

the inter-ionic core spacing.

(1863-1906) • Model successfully determined the form

of Ohm’s law in terms of free electrons
and a relation between electrical and
thermal conduction, but failed to explain
electron heat capacity and the magnetic
susceptibility of conduction electrons.
Ohm’s Law E

Experimental observation: V I
V  RI
L
 I
A
V
I  j
 L  Lj L
A
E  j
or j  E
Ohm’s Law: Free Electron Model
number
 e  ne
volume

Conventional current
j  nevd

The electric field accelerates each electron for an average

time  before it collides with an ion core.
Ohm’s Law: Free Electron Model
F  eE  ma
vd
m

eE ne 2
 vd  j  nevd  E
m m

Ohm’s Law: Free Electron Model
ne 
2
 If electrons behave like a gas…
m 8k BT
v 
m
The mean free time is related
to this average speed…
 a
  typical value
v v About 1014 s

Then,
1 ne 2 a m
 
 m 8k B T
Ohm’s Law: Free Electron Model
12

10
Predicted
behavior
8

B
Resistivity

6
High T: Resistivity
4 limited by lattice
2 thermal motion.
0

0 20 40 60 80 100 120 Low T: Resistivity

Temperature
limited by lattice
defects.

The mean free path is actually many

times the lattice spacing – due to the
wave properties of electrons.
Wiedemann-Franz Law (1853)
Electrical Thermal
2
ne 
Conductivities    12 n v k B
mv
8k BT
where v 
m

 4k B T
2

 e 2

Lorentz number (Incorrect!!)

Wiedemann-Franz Law (1853)

(Ludwig) Lorenz Number

(derived via quantum mechanical treatment)

2 2
 1  kB 8 W  
L   2.45  10
T 3e 2
K2
Free Electron Model: QM Treatment


• Assume N electrons (1 for each ion) in a
cubic solid with sides of length L –
particle in a box problem.
• These electrons are free to move about
without any influence of the ion cores,
except when a collision occurs.
• These electrons do not interact with one
another.
• What would the possible energies of
these electrons be?

• We’ll do the one-dimensional case first.

0 L
Free Electron Model: QM Treatment

At x = 0 and at L, the
wavefunction must be zero,
since the electron is confined to
the box.

One solution is:

Free Electron Model: QM Treatment
Free Electron Model: QM Treatment
Free Electron Model: QM Treatment
If an electron is added, it goes
into the next available energy
level, which is at the Fermi
energy. It has little temperature
dependence.

Fermi-Dirac Distribution
1
f ( )  (   ) / k T For lower energies,
e B 1 f goes to 1.
1
 (  ) / k T For higher energies,
e F B 1 f goes to 0.
Free Electron Model: QM Treatment
From thermodynamics,
the chemical potential,
and thus the Fermi
Energy, is related to
the Helmholz Free
Energy:
  F ( N  1)  F ( N ) T ,V
where
F  U  TS
Free Electron Model: QM Treatment

where nx, ny, and nz are integers

Free Electron Model: QM Treatment

and similarly for y and z, as well

i  k r 
k  e
2 4
k x  0,  , , ...
L L
2 4
k y  0,  , , ...
L L
2 4
k z  0,  , , ...
L L
Free Electron Model: QM Treatment

 2 k F2
F 
2m

p k
v 
m m
Free Electron Model: QM Treatment
• Each value of k exists within a volume
3
 2 
V  
 L 

• The number of states inside the sphere

of radius kF is
4  k3 1/ 3
N Vs F  3 N  2
  3  kF   
2 V  
2 3
L
 V 
 
2/3
 2 k F2  2  2 N 
F    3 
2m 2m  V 
• This successfully relates the Fermi energy to the electron density.
Free Electron Model: QM Treatment
1/ 3
   3 N 
2
vF  kF   
m m V 

F
TF 
kB
Free Electron Model: QM Treatment
2/3
 2 k F2  2  2 N 
F    3 
2m 2m  V 
3/ 2
V  2m 
 N  2  2 F 
3   

3/ 2
dN V  2m 
g ( )    2  1/ 2
d 2   
2
Free Electron Model: QM Treatment
3/ 2
V  2m 
N  2  2 F 
3   
 ln N  23 ln   constant
then The number of orbitals per unit
dN 3 N energy range at the Fermi energy
g     is approximately the total
d 2  number of conduction electrons
divided by the Fermi energy.
Free Electron Model: QM Treatment
This represents how many
energies are occupied as a
function of energy in the
3D
k-sphere.

As the temperature
increases above T = 0 K,
electrons from region 1
are excited into region 2.