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.

1
 The Free Electron Gas Model

Plot U(x) for a 1-D

crystal lattice:

Simple and
crude finite- U
square-well
model: U=0

Can we justify this model? How can one replace the entire lattice by a
constant (zero) potential?
 Free-Electron Model
 

classical description
p2 2 k 2
  
2m 2m
Quantum Mechanical Viewpoint
In a 3D slab of metal, e’s are free to move
but must remain on the inside
 

2 2
    0   E
2m
Solutions are of the form:
8
   xyz   sin k x x sin k y y sin k z z
L3

nz 
With energy: L
h2
 
8mL2
n 2
x n 2
y  n 2
z 
At T = 0, all states are filled
up to the Fermi energy

h2
 Fo 
8mL 2

2 2 2
nx  n y  n z 
max

A useful way to keep track of the states that are filled is:

nx2  n 2y  nz2  n 2 max

 h2
 Fo  n 2 max
8mL2
total number of states up to an energy efermi:

3
N  2 1  volume
of
  2 1 4 nmax
8 8 3
 sphere 

2/3 2/3
h 2
3N  2 N 
 Fo     3.646 x10 eV .m 
19

8m  V 
  V 

# states/volume ~ # free e’s / volume

Example: Numerical Values for Copper slab

N
= 8.96 gm/cm3 1/63.6 amu 6e23 = 8.5e22 #/cm3 = 8.5e28 #/m3
V

2/3 2/3
h 2
3N  N 
 Fo    19 2
 3.646 x10 eV .m    7.0eV
8m  V 
  V 

nmax = 4.3 e 7

so we can easily pretend that there’s a smooth distrib of nxnynz-states

 Density of States Tot KE 


 
0
f   g   d
How many combinations of are there
within an energy interval e to e + de ?
2/3
h 3N
2

 Fo   
8m   V 


Huge number of states, it can be treated in

continuous energy
3/ 2
 V   8mE 
N    2 
 3  h 
1/ 2
 V  3  8mE  8m
dN     2  dE
 3  2 h  h2
dN 8 V 3N 1/ 2
g(E)   3
2m 
3 1/ 2
E 1/ 2
 3/ 2
E
dE h 2 EFo
Electron follow Fermi-Dirac Distribution

1
f ( E )  E  E f / kT
e 1
At T ≠ 0 the electrons will be spread out among the allowed states

How many electrons are contained in a particular energy range?

n( E )  g ( E ) f ( E )
 number of ways to have   probability of 
   
 a particular energy   this energy occuring 

8 V 1
n( E )  3 2m 
3 1/ 2
E 1/ 2
( E  f ) / kT
h e 1
this assumes there are no other issues
 Electron Conductivity
• Electrical transport (relaxation time) in conductor

dv d vd ne2 N
m m  eE j   nevd  E n
dt  m V

Ohm Law j  E   relaxation time  collision time

e 2 l l l  electron mean free path
 n *   
m vr vF n  electron density
e2 l vF  Fermi velocity
 n *
m vF   conductivity
 Simple Kinetic Theory of Heat Conduction

1
qx  nEv x  x  v x τ  1 nEv x  x  v x τ Hot qx Cold

2 2 x

d (nEvx ) vxt x
qx  -vx
,
Taylor Expansion: dx
d (nE ) du dT
 -vx 2  -vx 2
dx dT dx

local thermodynamics equilibrium: u=u(T) C  du / dT

2 2 v2 dT
vx  v / 3 qx  -  C
3 dx
 Cv 2 Cv
k   thermal conductivity
3 3
 Assigments
• Proof that at T=0 the total energy of
electron 3
U NEFo
5

• 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
 Heat Capacity of the Quantum-Mechanical FEM
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:
1
f (E)   E    / kT
where  = chemical potential  EF for kT << EF
e 1
1

FERMI-DIRAC DISTRIBUTION
0.8

1000 K
0.6

0.4

0.2 100 K 300 K

0
-0.1 -0.05 0 0.05 0.1
E- (eV)
 Heat Capacity of Metals: Theory vs. Expt. at low T

Very low temperature

measurements reveal:

Results for simple Meta expt/ FEG =

expt FEG
l m*/m
metals (in units
Li 1.63 0.749 2.18 The discrepancy is
mJ/mol K) show
Na 1.38 1.094 1.26 “accounted for” by
that the FEG values
defining an effective
are in reasonable K 2.08 1.668 1.25
electron mass m* that is
agreement with Cu 0.695 0.505 1.38
due to the neglected
experiment, but are Ag 0.646 0.645 1.00 electron-ion interactions
always too high:
Au 0.729 0.642 1.14

Al 1.35 0.912 1.48

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

k  /2

2
a   /2  /2
k

2
a /2 /2
k
 Nearly-Free Electron Model
version 2 – SP324

This treatment assumes that when

a reflection occurs, it is 100%.
• Bloch Theorem
• Special Phase Conditions, k = +/- m p/a
• the Special Phase Condition k = +/- p/a
  
~~~~~~~~~~ (x) ~ u e i(kx-wt)
amplitude

In reality, lower energy waves are sensitive to the lattice:

(x) ~ u(x) e i(kx-wt)

Bloch’s
Amplitude varies with location
Theorem

u(x) = u(x+a) = u(x+2a) = ….

 (x) ~ u(x) e i(kx-wt)
u(x+a) = u(x)

(x+a) e -i(kx+ka-wt)  (x) e -i(kx-wt)

(x+a)  e ika (x)

Something special happens with the phase when

e ika = 1

ka = +/ m p m = 0 not a surprise

m = 1, 2, 3, …
 
k   ,  2 , ...
a a

What it is ?
 
Consider a set of waves with +/ k-pairs, e.g. k  
a

k = + p/a moves  k =  p/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

|+|2 ~ 4 cos2 kx ||2 ~ 4 sin2 kx

Kittel
 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
free electron KE functional form
2 k 2
 
2 m*

ER Ch 13 p461 starting w/ eqn (13-19b)

 Effective Mass m*
-- describing the balance between applied ext-E and lattice site reflections

2
1 1 

m*  2 k 2

m* a = S Fext

q Eext
 2) greater curvature, 1/m* > 1/m > 0,  m* < m 
net effect of ext-E and lattice interaction
provides additional acceleration of electrons

m = m*

greater |curvature| but negative,

At inflection pt
net effect of ext-E and lattice interaction
de-accelerates electrons

No distinction between m & m*,

1) m = m*, “free electron”, lattice structure does
not apply additional restrictions on motion.
 Another way to look at the discontinuities

2 k 2 apply perturbation from lattice

2 k 2
  
2m 2 m*
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 applied field
enhanced by change in reflection coefficients

change in motion
due to reflections
is more significant
than change in motion
due to applied field
Nearly-Free Electron Model
version 3
à 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:
 from  t eiKx
 from  e iKx  r e iKx the
the left
left

2 K 2
 
2m
Waves from the right behave like:
 from  t e iKx  from  e iKx  r eiKx
the
right the
right

2 K 2
 
2m
 sum  A left  B right

unknown weights
Bloch’s Theorem defines periodicity of the wavefunctions:

sum x  a   e ika sum  x 

 x  a   e ika sum
sum  x 
Related to
Lattice spacing
 Applying the matching conditions at x   a/2

sum  x  a   eika sum  x    x  a   eika sum

sum  x 

A + B A + B A + B
A + B

left right left right

left right
left right

And eliminating the unknown constants A & B leaves:

t 2  r 2 iKa 1 iKa
cos ka  e  e
2t 2t 2 K 2
 
2m
For convenience (or tradition) set:
i 2 2
tt e 1 t  r r   i r e i

cosKa   
 cos ka
t
 cosKa   
 cos ka
t
Related to
Energy Related to
possible
2 K 2 Lattice spacings
 
2m

allowed solution regions

allowed solution regions