Lecture 5

Nearly Free Electron Model

5.1 Nearly Free Electron Model
5.1.1 Brilloiun Zone
5.1.2 Energy Gaps
5.2 Translational Symmetry – Bloch’s Theorem
5.3 Kronig-Penney Model
5.4 Examples
References:
1. Marder, Chapters 7-8
2. Kittel, Chapter 7
3. Ashcroft and Mermin, Chapter 9
4. Kaxiras, Chapter 3
Lecture 5 5. Ibach, Chapter 7 1

Sommerfeld’s theory does not explain all…

Metal’s conduction electrons form highly degenerate Fermi gas

Free electron model: works only for metals

- heat capacity, thermal and electrical conductivity, magnetic susceptibility, etc

Drawbacks:
predicted electron mean path is too long
increases with temperature
positive values for the Hall coefficient, magnetotransport

difference between a good conductor (10-10 Ohm-cm) and a good insulator

(10-22 Ohm-cm) – 1032 !!!

Lecture 5 2

Electron Occupancy of Allowed Energy Bands

Adapted from Kittel

• No electrons can move in an electric field (energy band is completely filled or
empty) – insulator ;
• One or more bands are partly filled – conductor

Basic Assumptions: - crystal structure is periodic

- periodicity leads to formation of energy bands (allowed energy levels)
- energy bands are separated by energy Lecturegaps
5 or band gaps (region in energy3
for which no wavelike electron orbital exist)

1
 5.1 Nearly Free Electron Model
In free electron model: all energy values from 0 to infinity are allowed

ε kr =
h2 r2 h2 2
2m
k =
2m
(
k x + k y2 + k z2 )
r r r
Wavefunctions are in the form: ψ (r ) = exp(ik ⋅ r ),
r
k
r 2π 4π
where the components of the wavevector k are: k x = 0;± ;± ;...
L L
Nearly free electron model: weak perturbation of electrons by periodic
potential of ions

Lecture 5 4

Nearly Free Electrons

Consider the effects due to a periodic crystal structure

1 nπ
Under condition k = ± G=± , the
2 a
electron wave will undergo Bragg
reflection

Energy gaps develop at these k due to

these reflections

At k = n π/a the wavefunctions are not

the traveling wave of free electrons

The region between - π/a and π/a :

first Brillouin zone of this 1D lattice

Lecture 5 5

5.1.1 Brilloiun Zone in 1D: extended, reduced

and repeated
Repeated

Extended

Reduced

BZLecture 5
boundaries 6

2
 Reduction to the first Brillouin zone

This general demand of periodicity implies that the possible electron states are
not restricted to a single parabola in k-space, but can be found on any
parabola shifted by any G-vector:
r r r h2 r r 2
ε (k ) = ε ( k + G ) = k +G
2m

r 2π
For 1D case: G → G =
a

Lecture 5 7

Brilloiun Zone in 3D
Brilloiun Zone in 3D: Wigner-Seitz cell of the reciprocal lattice
r r r r
Recall: reciprocal lattice vector G = 2π n1b1 + 2π n2b2 + 2π n3b3 ,
r r r r r r
r r r r a2 × a3 r a3 × a1 r a ×a
where b1 , b2 , b3 are basic vectors such that b1 = r r r ; b2 = r r r ; b3 = r 1 r 2 r ;
a1 ⋅ a2 × a3 a1 ⋅ a2 × a3 a1 ⋅ a2 × a3

Some properties of reciprocal lattice:

The direct lattice is the reciprocal of its own reciprocal lattice
The unit cell of the reciprocal lattice need not be a paralellopiped, e.g.,
Wigner-Seitz cell

first Brilloin Zone (BZ)

Lecture 5 8
of the fcc lattice

5.1.2 Origin of the Energy Gap

Crystal Potential - U
The probability density of the particle is
ψ*ψ = | ψ|2

For pure traveling wave:

ρ = exp(−ikx) exp(ikx) = 1

For plane waves the charge

density is not constant:
for the wave ψ (+ ) :
πx
ρ (+) =| ψ (+) |2 ∝ cos2
a
for the wave ψ (−) :
πx
ρ (−) =| ψ (−) |2 ∝ sin 2
a
Lecture 5 9

3
 Magnitude of the Energy Gap

The potential energy due to the crystal can be approximated as:

2πx
U ( x) = U cos
a
This potential has the periodicity of the lattice, U(x) = U (x + a)

The wavefunctions at the Brillouin zone boundary k = π/a (normalized over unit
length of line, a) are
πx πx
2 cos and 2 sin
a a

The difference between the two standing wave states is

The gap is equal to the Fourier component of the crystal potential

Lecture 5 10

5.2 Translational Symmetry – Bloch’s Theorem

Bloch’s theorem: the wave functions of the electrons in a crystal must be of a

special form (the Bloch form)
r r r r
ψ kr (r ) = exp(ik ⋅ r )u k (r )
r r r
uk (r ) = u k (r + T )

uk(r) – the periodicity of the lattice (depends on the wave vector!)

Note: the Bloch function can be decomposed into a sum of traveling waves
In 1D: Consider a crystal of length L = N a (N primitive u. c. of length a on a ring)
The periodic boundary condition demans that

Addition of the translational symmetry gives :

i 2πsx
Therefore ψ ( x) = u k ( x) exp( ) Lecture 5 11
Na Kittel, pp.179-180

Bloch’s Theorem

For non-interacting electrons moving in a periodic potential, U (r)

r r r
U (r + R) = U (r )

Bloch wave functions are periodic functions u (r) modulated by a plane wave of
a longer period
Periodic function u (r)

Lecture 5 12

4
 Translation Operators
r
r Pˆ R
−i
Let TˆRr translate wave function by R : Tˆ Rr = e h

Theorem: if one has a collection of Hermitian operators that commute with one
another, they can be diagonalized simultaneously

Any eigenvector of the Hamiltonian can be taken as an eigenfunction of all the

translational operators as well:
Use theorem: r
Pˆ R
−i
Tˆ Rr| ψ = e h | ψ = C Rr | ψ
r r r
ψ (r + R) = C Rrψ (r )

Lecture 5 13

Translation Operators

Operating with eigenfunction of momentum:

rr r r
eikR k ψ = C Rr k ψ
rr r r
⇒ either C Rr = e
ik R
or k ψ =0 k: Bloch wave vector
r
hk : Crystal momentum
n: Band index
For a given value of Bloch wavevector, there is still the possibility of many
energy eigenvalues (can be labeled by the band index n)
The eigenfunctions made possible by periodicity is: Hˆ ψ nkr = E nkr ψ nkr
rr

r rr TˆRr ψ nkr = e ik R ψ nkr

r r
ψ nkr (r + R ) = e ikRψ nkr (r ) or
rr
r r
u nkr ( r ) = e −ikrψ nkr (r )
Lecture 5 14

Allowed values of k

r r r
If crystal is periodic
r with
r
(macroscopic) dimensionsr M 1a1 , M 2 a2 , M 3 a3 then
requiring exp[ik ⋅ r ] to be periodic constrains k to
r 3 m r r r r r
k = ∑ l bl ,0 ≤ ml ≤ M l , where b1...b3 are such that bl ⋅ al ' = 2πδ ll '
l =1 M l

Periodic boundary condition place a condition on how small k can be

rr
Demanding that C Rr = e ikR be unique places conditions on how big k can be

Number of points in crystal equals number of unique Bloch wave vectors

Lecture 5 15

5
 Energy Bands and Group Velocities

Velocity of electrons in the nth band with wave number k is:

r 1
vnkr = ∇ kr Enkr
h
∂ω
Note: this is similar to the solution of wave equations for a group velocity: v =
∂k
r r r r ikr 'rr −iE r t / h rr r
Wave packet: W (r , k , t ) = ∫ w(k '− k ) ⋅ e k'
ψ kr 'e − ik 'r dk ' ≈
rr
ik 'r − iEkr 't / h
r r rr
ik ' r − iEkr 't / h
≈e ∫ w(k ' ' )dk ' ∝ e

Lecture 5 16

5.3 Kronig-Penney Model

h 2 d 2ψ
The wave equation is − + U ( x )ψ = εψ
2m dx 2
In the region 0<x<a (U = 0), the eigenfunction is a linear combination
2 2
of plane
waves traveling to the right and to the left with energy ε = h K
2m

ψ = AeiKx + Be−iKx
In the region –b < x < 0 within the barrier the solution is

ψ = CeQx + De − Qx ,
h 2Q 2
where U 0 − ε =
2m

Lecture 5 17

Kronig-Penney Model

Solution must be in the Bloch form:

ψ (a < x < a + b) = ψ ( −b < x < 0)eik ( a +b )
The constants A, B, C, D are chosen so that wavefunction and its derivative are
continuous at x = 0 and x = a

At x = 0 A+B =C+D
i K (A-B) = Q (C - D)

At x = a AeiKa + Be − iKa = (Ce −Qb + DeQb )e ik ( a +b )

iK ( AeiKa − Be −iKa ) = Q (Ce −Qb − DeQb )e ik ( a+b )

Solution: [(Q 2 − K 2 ) 2QK ] sinh Qb sin Ka + cosh Qb cos Ka = cos k (a + b)

In the limit Q >> K and Qb << 1
P
sin Ka + cos Ka = cos ka
Ka Lecture 5 18

6
Functions and Energy for the K-P potential

Lecture 5 19

First Brillouin Zone for fcc lattice

Lecture 5 20

First Brillouin Zone for bcc lattice

4π
a
Lecture 5 21

7
 First Brillouin Zone for hcp lattice

Lecture 5 22

Example: Nearly Free Electron in 1D

Electrons of mass m are confined to one dimension. A weak periodic potential

is applied:
2πx 4πx
V ( x) = Vo + V1 cos + V2 cos
a a
(a) Under what conditions will the nearly free-electron approximation work?
(b) Sketch the three lowest energy bands in the first Brillouin zone. Number the
energy bands (starting from one at the lowest band)
(c) Calculate (to first order) the energy gap at k = π /a (between the first and
second band) and k = 0 (between the second and third band)

Lecture 5 23

Lecture 5 24

8
 Nth Brillioun zone: geometrical view
Nth Brillioun zone: geometrical view

Procedure:
• perpendicular bisectors are drawn
between the origin and all nearby
reciprocal lattice points ⇒ zone
boundaries
• the 1st , 2nd, and 3 rd BZ are shaded
in different color (same volume)

• electron response to the external electric field same as for free electron
till it approaches a zone boundary plane
• an electron once in the nth BZ remains in the nth BZ

Lecture 5 25

Example in two dimensions

Suppose 2D lattice has two conduction el. per lattice sites

The # of k-states in BZ = the # of lattice points

For a weak potential, shape of the energy surface ~

sphere

Lecture 5 26

Example in two dimensions

• Fermi surface • portion of the Fermi

completely surface in 2nd BZ is
enclosing the 1st BZ mapped back into
the 1st zone
• shape of surface is
modified near the
zone boundary

• portion of the Fermi Harrison

surface in 3rd BZ is construction:
made continuous by nth BZ mapped
translation through into 1st BZ
reciprocal lattice
vectors

Lecture 5 27

9
Nearly Free Electron Fermi Surface Gallery

http://www.phys.ufl.edu/fermisurface/periodic_table.html
Lecture 5 28

10