1

Band Theory
This is a quantum-mechanical treatment of bonding
in solids, especially metals and semiconductors.
The spacing between energy levels is so minute in
metals that the levels essentially merge into a band.
When the band is occupied by valence electrons, it is
called a valence band.
A partially filled or low lying empty band of energy
levels, which is required for electrical conductivity, is
a conduction band.
Band theory provides a good explanation of metallic
luster and metallic colors.
<Ref> 1. The Electronic Structure and Chemistry of Solids by P.A. Cox
2. Chemical Bonding in Solids by J.K. Burdett
2
Magnesium metal
3
From Molecular Orbitals to Band Theory
H
2
Bond order = ( # of bonding electrons - # of anti-
bonding electrons )
Electron configuration of H
2
: (
1s
)
2
B.O. of H
2
= (2 - 0) = 1
4
M.O. from Linear Combinations of Atomic Orbitals (LCAO)

=
n
n n
x c x ) ( ) (

n
(x) : atomic orbital of atom n
C
n
: coefficient
For H
2
molecule,

bonding
= c
1

1s(1)
+c
2

1s(2)
= 1/2(1+S) [
1s(1)
+
1s(2)
]
~ 1/2 [
1s(1)
+
1s(2)
]

antibonding
= c
1

1s(1)
- c
2

1s(2)
= 1/2(1-S) [
1s(1)
-
1s(2)
]
~ 1/2 [
1s(1)
-
1s(2)
]
where, S =
1s(1)
*

1s(2)
> 0 Overlap integral
5
+ +
Constructive Interference for bonding orbital
The electron density is given by
(x) = *(x) (x) =|(x)|
2
6
+
-
Destructive Interference for antibonding orbital
7
Energies of the States

=
k k
k k
k
H
E


*
*

+
+
+
=
S
E
bonding
1
if S~0 (neglecting overlap)

=
S
E
g antibondin
1

+
-

< = 0 ) 1 (

) 1 (
1
*
1 s s
H
Coulomb integral

< = 0 ) 2 (

) 1 (
1
*
1 s s
H
Exchange integral
8
(He)
2
molecule is not present!
9
Species Electron
configuration
B.O. Bond
energy
(kJ/mol)
Bond
length (pm)
H
2
(
1s
)
2
1 435 74
H
2
+
(
1s
)
1
269 106
H
2
-
(
1s
)
2
(
1s
*)
1
238 108
He
2
(
1s
)
2
(
1s
*)
2
0 - -
10
11
2nd Period Homo-nuclear Diatomic
Molecules
Electron configuration of Li
2
: KK(
1s
)
2
B.O. of Li
2
= (2 - 0) = 1
12
Hetero-nuclear Diatomic Molecule
Lewis Structure
13
Chemical bond from molecules to solids
1 D array of atoms
orbitals
empty
filled
14
The 2s Band in Lithium Metal
Bonding
Anti-bonding
e- e-
Valence band
Conduction band
15
Band Overlap in Magnesium
Valence band
Conduction band
16
Band Structure of Insulators
and Semiconductors
17
Density of state
= dn/dE
n = number of states
(a) (b)
Density of states in (a) metal, (b) semimetal
(e.g. graphite).
18
Conductivity of Graphite
insulator
e
-
-conductor
19
Fermi level- the highest occupied orbital at T= 0
(a) (b)
Fermi distribution (a) at T= 0, and (b) at T> 0.
The population decays exponentially at energies well above
the Fermi level.
Population,
1
1
/ ) (
+
=
kT E
e
P

where, = chemical potential
When E= , P= 1/2
20
(a)
population
(b)
Fermi distribution and the band gap at T> 0 for
(a) Intrinsic semiconductor, (b) Insulator
21
Extrinsic semiconductor: (a) n-type, e.g. P doped Si
(b) p-type, e.g. Ga doped Si.
22
p-n junction
n-type p-type
23
24
HOMO
LUMO
HOMO
LUMO
25
One-dimensional chain with n -orbitals, jth level
Ej = + 2cosj/(n+1) , j =1, 2, 3 .
26
Bonding
Anti-
bonding
Linear Conjugated Double Bonds
E
-M.O.
27
empty
filled
Cyclic system with n 4 atoms, jth level
Ej = + 2cos2j/n , j = 0, 1, 2, 3 .
Cyclic ring
28
E
The -Molecular Orbitals of Benzene
29
30
31
32
Elementary Band Theory
33
If (x) is the wave function along the chain
Periodic boundary condition:
The wavefunction repeats after N lattice spacings
Or, (x+ Na) = (x) (1)
The electron density is given by
(x) = *(x) (x) (2)
The periodicity of electron density (x +a) = (x) (3)
34
(x +a) = (x) (3)
This can be achieved only if (x+ a) = (x) (4)
is a complex number * = 1 (5)
Through n number of lattice space (x+ na) =
n
(x) (6)
Through N number of lattice space (x+ Na) =
N
(x) (7)
Since (x+ Na) = (x),
N
= 1 (8)
= exp(2ip/ N) = cos(2p/ N) + i sin(2p/ N) (9)
Where, i = -1, and p is an integer or quantum number
Define another quantum number k (Wave number or Wave vector)
k = 2p/(N a) (10)
= exp(ika) (11)
considering wave function repeats after N lattice spacings (N a) ~
Although p = 0, 1, 2, . , If N is very large in a real solid
k is like a continuous variable
35
Since (x+ a) = (x) (4)
(x+ a) = (x) = exp(ika) (x) (12)
Free electron wave like (x)= exp(ikx) = cos(kx) + i sin(kx) (13)
can satisfy above requirement
A more general form of wave function
Bloch function (x) = exp(ikx) (x) (14)
and, (x+a) = (x) a periodic function, unaltered by
moving from one atom to another
e.g. atomic orbitals
The periodic arrangement of atoms forces the wave functions of
e
-
to satisfy the Bloch function equation.
36
real
imaginary
=
= 2/k
= 2a
wavelength
(x) =(x)=
1s
(x) = exp(ikx)
1s
Free e
-
Real part
of
restricted e
-
37
=
= 2a
Wave vector (Wave number) k = 2/
1. Determining the wavelength of a crystal orbital
2. In a free electron theory,
k momentum of e
-
conductivity
3. -/a k +/ a often called the First Brillouin Zone
Anti-bonding between
all nearby atoms
node
node
E
38
Crystal Orbitals from Linear Combinations of Atomic Orbitals
(LCAO)

=
n
n n
x c x ) ( ) (

n
(x) : atomic orbital of atom n
C
n
: coefficient C
n
= exp(ikx) = exp(ikna)

=
n
n
x ikna x ) ( ) exp( ) (
Bloch sums of atomic orbitals
(15)
(16)
(17)
From eq (10), k = 2p/(N a) for quantum number p of repeating
unit N
Consider a value k, corresponding to a number of p + N
k = 2(p + N)/(N a) = k + 2/a
C
n
= exp{i(k + 2/a )na}= exp(ikna)exp(i2n) = C
n
A range of 2/a contains N allowed values of k
However, Since k can be negative, usually let -/a k +/ a
First Brillouin Zone
39
1-D Periodic
X
0
X
1
X
2
X
3
X
4
X
5
X
6
a
Bloch function

k
=
n
e
-ikna
X
n
where X
n
atomic wavefunction
k value
Index of translation between 0 /a
or, 0 0.5 a* (a* = 2/a)
Reciprocal lattice
40
-bond
X
n
=
1s
orbital
(0) =
n
e
0
X
n
=
n
X
n
= X
0
+ X
1
+ X
2
+ X
3
+ X
4
+ X
5
+ X
6
+
k = 0
=
X
0
X
1
X
2
X
3
X
4
X
5
X
6
k = /a
= 0.5 a*
(/a) =
n
e
-in
X
n
=
n
(-1)
n
X
n
= X
0
- X
1
+ X
2
- X
3
+ X
4
- X
5
+ X
6
-
X
0
X
1
X
2
X
3
X
4
X
5
X
6
= 2a
k = /2a
= 0.25 a*
(/2a) =
n
e
-in/2
X
n
=
n
(-1)
n/2
X
n
= X
0
+ iX
1
- X
2
- iX
3
+ X
4
+ iX
5
- X
6
+
X
0
X
1
X
2
X
3
X
4
X
5
X
6
= 4a
node
41
Energies of the States

=
k k
k k
k
E


*
*
H

Express
k
and
k
* as Bloch sums
[ ]

= =

=
N
n
n m
N
m
k k
x x k m n i
1
*
1
*

) ( exp

[ ]

= =

=
N
n
n m
N
m
k k
x x k m n i
1
*
1
*
) ( exp
E
k
= + 2cos(ka)

=
n n
H

=
n m

*
If m and n are neighbors
42
E
k
= + 2cos(ka) and < 0
E
Energy as a function of k for s-band
43
X
n
=
2p
orbital
(0) =
n
e
0
X
n
= X
0
+ X
1
+ X
2
+ X
3
+ X
4
+ X
5
+ X
6
+
(/a) =
n
e
-in
X
n
= X
0
- X
1
+ X
2
- X
3
+ X
4
- X
5
+ X
6
-
node
44
-bond
1st Brillouin zone
45
DOS(E)dE
= # of levels between E and E + dE
46
47
s-band as a function of a
k = 2/
k = 0 0.5a*
= 2a
48
k = 0
z
p
0

z
p
a
*
5 . 0

z
p
a
*
25 . 0

z
p
a
6
*

2
0
z
d

2
*
5 . 0
z
d
a

3
0
z
f

3
*
5 . 0
z
f
a

0.5 a*
0.25 a*
1/6 a*
bonding
antibonding
bonding
antibonding
a
/a
/2a
/3a

2a

4a
6a

2a
2a
k
49
bond
50
- bond
E
j
= + 2cos j/(n+1)
j = 1, 2, 3, , n
( ) ( ) 1
sin
1
2
center r of orbital
1
+

+
=

=
n
rj
n
C
C
jr
r
n
r
r jr j

The evolution of the -orbital picture for conjugated linear

polyenes.
51
The evolution of the energy levels of an infinite one-
dimensional chain (-CH-)
n.
52
Binary Chain
Bloch function
[ ]

=
+ =
N
n
n k n k b
B b A a ikna k
1
) ( ) ( ) exp( ) (
[ ]

=
=
N
n
n k n k a
B a A b ikna k
1
) ( ) ( ) exp( ) (
Where, (A)
n
and (B)
n
are atomic orbitals at position n
53
(A) = s- orbital, (B) = p- orbital
n k n k n
B b A a X ) ( ) ( + =
(0) =
n
e
0
X
n
= X
0
+ X
1
+ X
2
+ X
3
+ X
4
+ X
5
+ X
6
+
No effective overlap between orbitals non-bonding
Effective overlap between orbitals bonding
(/a) =
n
e
-in
X
n
= X
0
- X
1
+ X
2
- X
3
+ X
4
- X
5
+ X
6
-
54
B band
E
Non-bonding
55
(A) = s- orbital, (B) = p- orbital
n k n k n
B a A b X ) ( ) ( =
(0) =
n
e
0
X
n
= X
0
+ X
1
+ X
2
+ X
3
+ X
4
+ X
5
+ X
6
+
(/a) =
n
e
-in
X
n
= X
0
- X
1
+ X
2
- X
3
+ X
4
- X
5
+ X
6
-
Antibonding between neighbor orbitals
No effective overlap between orbitals non-bonding
56
bonding
antibonding

2
non-bonding
non-bonding
57
58
Nearly-free electron model
= exp(ikx)
= cos(kx) + isin(kx)
E = mv
2
+ V
= 2p
2
/m + V
de Broglies formula
Momentum p = h/
where h: Planck constant
= 2/k
p = hk/2 p k
59
1st Brillouin zone
Energy gap is produced due to
periodic potential
60
61
62
Schematic showing the method of generating the
band structure of the solid.
63
chain
64
Effect of Distortion
A comparison of the change in the energy levels and energy bands
associated with (a) the Jahn-Teller distortion of cyclobutadiene
and (b) the Peierls distortion of polyacetylene.
65