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 1
Magnesium metal

2
 From Molecular Orbitals to Band Theory
H2

Bond order = ½ ( # of bonding electrons - # of anti-

bonding electrons )
Electron configuration of H2 : (σ1s)2
B.O. of H2 = ½ (2 - 0) = 1
3
M.O. from Linear Combinations of Atomic Orbitals (LCAO)
Ψ ( x ) = ∑ cn χ n ( x )
n

χn(x) : atomic orbital of atom n

Cn : coefficient

For H2 molecule,
Ψbonding = c1ϕ1s(1) + c2ϕ1s(2) = 1/√2(1+S) [ϕ1s(1) + ϕ1s(2) ]
~ 1/√2 [ϕ1s(1) + ϕ1s(2) ]

Ψantibonding = c1ϕ1s(1) - c2ϕ1s(2) = 1/√2(1-S) [ϕ1s(1) - ϕ1s(2) ]

~ 1/√2 [ϕ1s(1) - ϕ1s(2) ]

where, S = ∫ϕ1s(1)* ϕ1s(2) > 0 Overlap integral

4
Constructive Interference for bonding orbital

+ +

The electron density is given by

ρ(x) = Ψ*(x) Ψ(x) =|Ψ(x)|2

5
Destructive Interference for antibonding orbital

6
Energies of the States
* ˆ

Ek =
∫ k Hψ k
ψ
∫ kψ k
ψ *

α +β
Ebonding = ≈α +β if S~0 (neglecting overlap)
1+ S
α −β
Eantibonding = ≈α −β
1− S

α = ∫ψ 1*s (1) Hˆ ψ 1s (1) < 0

Coulomb integral -β
α
β = ∫ψ (1) Hˆ ψ 1s (2) < 0
*
1s +β
Exchange integral
7
(He)2 molecule is not present!

8
Species Electron B.O. Bond Bond
configuration energy length (pm)
(kJ/mol)
H2 (σ1s)2 1 435 74

H2+ (σ1s)1 ½ 269 106

H2- (σ1s)2(σ1s*)1 ½ 238 108

He2 (σ1s)2(σ1s*)2 0 - -

9
10
 2nd Period Homo-nuclear Diatomic
Molecules

Electron configuration of Li2 : KK(σ1s)2

B.O. of Li2 = ½ (2 - 0) = 1

11
Hetero-nuclear Diatomic Molecule

Lewis Structure

12
Chemical bond from molecules to solids
1 D array of atoms

orbitals

empty

filled

13
The 2s Band in Lithium Metal

Anti-bonding
Conduction band
e- e-
Valence band
Bonding

14
Band Overlap in Magnesium

Conduction band

Valence band

15
Band Structure of Insulators
and Semiconductors

16
 n = number of states
Density of state
= dn/dE

(a) (b)

Density of states in (a) metal, (b) semimetal

(e.g. graphite).

17
Conductivity of Graphite
insulator

e- -conductor

18
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.
1
Population, P = ( E − µ ) / kT where, µ = chemical potential
e +1
When E= µ, P= 1/2 19
 (a) population (b)

Fermi distribution and the band gap at T> 0 for

(a) Intrinsic semiconductor, (b) Insulator
20
Extrinsic semiconductor: (a) n-type, e.g. P doped Si
(b) p-type, e.g. Ga doped Si.
21
p-type n-type

p-n junction
22
23
 LUMO

LUMO

HOMO

HOMO

24
One-dimensional chain with n π-orbitals, jth level
Ej = α + 2βcosjπ/(n+1) , j =1, 2, 3 …. 25
Linear Conjugated Double Bonds

Anti-
E bonding

Bonding

π-M.O.
26
Cyclic ring

empty

filled

Cyclic system with n ≥ 4 atoms, jth level

Ej = α + 2βcos2jπ/n , j = 0, 1, 2, 3 …. 27
The π-Molecular Orbitals of Benzene

28
29
30
31
Elementary Band Theory

32
If Ψ(x) is the wave function along the chain

Periodic boundary condition:

The wavefunction repeats after N lattice spacings
Or, Ψ(x+ Na) = Ψ(x) (1)

The electron density is given by

ρ(x) = Ψ*(x) Ψ(x) (2)

The periodicity of electron density ⇒ ρ(x +a) = ρ(x) (3)

33
ρ(x +a) = ρ(x) (3)
This can be achieved only if Ψ(x+ a) = µ Ψ(x) (4)
µ is a complex number µ* µ = 1 (5)
Through n number of lattice space Ψ(x+ na) = µn Ψ(x) (6)
Through N number of lattice space Ψ(x+ Na) = µN Ψ(x) (7)

Since Ψ(x+ Na) = Ψ(x), µN = 1 (8)

⇒ µ = exp(2πip/ N) = cos(2πp/ N) + i sin(2πp/ N) (9)
Where, i = √-1, and p is an integer or quantum number

Define another quantum number k (Wave number or Wave vector)

k = 2πp/(N a) (10)
⇒ µ = exp(ika) (11)
considering wave function repeats after N lattice spacings (N a) ~ λ
Although p = 0, ±1, ±2, …. , If N is very large in a real solid
⇒ k is like a continuous variable 34
Since Ψ(x+ a) = µ Ψ(x) (4)
Ψ(x+ a) = µ Ψ(x) = exp(ika) Ψ(x) (12)

Free electron wave like Ψ(x)= exp(ikx) = cos(kx) + i sin(kx) (13)

can satisfy above requirement

A more general form of wave function

Bloch function Ψ(x) = exp(ikx) µ(x) (14)
and, µ(x+a) = µ(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.

35
 Free e- real

wavelength imaginary
λ= ∞

Ψ(x) =µ(x)= ϕ1s

Real part λ= 2π/k

of
restricted e-
Ψ(x) = exp(ikx) ϕ1s
λ= 2a

36
 λ= 2a

node Anti-bonding between

all nearby atoms
E
node
λ= ∞

Wave vector (Wave number) k = 2π/λ

1. Determining the wavelength of a crystal orbital
2. In a free electron theory,
k α momentum of e- ↔ conductivity
3. -π/a ≤ k ≤ +π/ a often called the First Brillouin Zone 37
Crystal Orbitals from Linear Combinations of Atomic Orbitals
(LCAO)
∑
Ψ ( x ) = cn χ n ( x )
n
(15)

χn(x) : atomic orbital of atom n

Cn : coefficient Cn = exp(ikx) = exp(ikna) (16)
Ψ ( x) = ∑ exp(ikna ) χ n ( x) Bloch sums of atomic orbitals
n
(17)
From eq (10), k = 2πp/(N a) for quantum number p of repeating
unit N
Consider a value k’, corresponding to a number of p + N
k’ = 2π(p + N)/(N a) = k + 2π/a
Cn’ = exp{i(k + 2π/a )na}= exp(ikna)∙exp(i2πn) = Cn
⇒ A range of 2π/a contains N allowed values of k
However, Since k can be negative, usually let -π/a ≤ k ≤ +π/ a
⇒ First Brillouin Zone 38
1-D Periodic
a

X0 X1 X2 X3 X4 X5 X6

Bloch function Ψk = Σn e-ikna Xn

where Xn atomic wavefunction

k value
Index of translation between 0 – π/a
or, 0 – 0.5 a* (a* = 2π/a)
Reciprocal lattice
39
σ-bond Xn = ϕ1s orbital
k=0 Ψ(0) = Σn e0 Xn = Σn Xn
= X0 + X1 + X2 + X3 + X4 + X5 + X6 + …

X0 X1 X2 X3 X4 X5 X6 λ=∞
k = π/a Ψ (π/a) = Σn e-inπ Xn = Σn (-1)n Xn
= 0.5 a* = X0 - X1 + X2 - X3 + X4 - X5 + X6 - …

X0 X1 X2 X3 X4 X5 X6 λ = 2a

k = π/2a Ψ (π/2a) = Σn e-inπ/2 Xn = Σn (-1)n/2 Xn

= 0.25 a* = X0 + iX1 - X2 - iX3 + X4 + iX5 - X6 + …

X0 X1 X2 X3 X4 X5 X6 λ = 4a
40
node
Energies of the States
∫ k Ĥψ k
ψ *

Ek =
∫ kψ k
ψ *

Express Ψk and Ψk* as Bloch sums

N
⎧ N
⎫
∫ψ Η ψ k = ∑
ˆ ⎨∑ exp[i (n − m)k ]∫ xm Η xn ⎬
* * ˆ
k
n =1 ⎩ m =1 ⎭
N
⎧N ⎫
∫ψ kψ k = ∑ ⎨∑ exp[i (n − m)k ]∫ xm xn ⎬
* *

n =1 ⎩ m =1 ⎭

Ek = α + 2βcos(ka)
α = ∫ χ n*Ĥχ n
β = ∫ χ m* Ηˆ χ n If m and n are neighbors
41
Ek = α + 2βcos(ka) and β < 0

Energy as a function of k for s-band

42
Xn = ϕ2p orbital
Ψ(0) = Σn e0 Xn = X0 + X1 + X2 + X3 + X4 + X5 + X6 + …

node
Ψ (π/a) = Σn e-inπ Xn = X0 - X1 + X2 - X3 + X4 - X5 + X6 - …

43
σ-bond

1st Brillouin zone

44
DOS(E)dE
= # of levels between E and E + dE

45
46
s-band as a function of a

k = 2π/ λ
k = 0 → 0.5a*
λ= ∞ → 2a

47
 a k λ
ϕ 0p z k=0
2a

ϕ0p.5a z
*
π/a ∞
0.5 a*

ϕ0p.25a
z
*
0.25 a*
π/2a 4a

ϕ ap z
*

6 1/6 a*
π/3a 6a
d
ϕ0 z2
bonding ∞
d
ϕ0.5a z2 antibonding 2a
*

ϕ0
f
z3 antibonding 2a

f
ϕ0.5a z3
*
bonding ∞
48
σ bond

49
 π- bond
Ej = α + 2βcos jπ/(n+1)
j = 1, 2, 3, ……, n
n
ψ j = ∑ C jr Φ r
r =1

Φ r π orbital of r center

C jr = ⎡ 2 ⎤ sin rjπ
⎢⎣ (n + 1)⎥⎦ (n + 1)

The evolution of the π-orbital picture for conjugated linear

polyenes.
50
The evolution of the π energy levels of an infinite one-
dimensional chain (-CH-)n.

51
Binary Chain

Bloch function
N
Ψb (k ) = ∑ exp(ikna )[ak χ ( A) n + bk χ ( B ) n ]
n =1

N
Ψa (k ) = ∑ exp(ikna )[bk χ ( A) n − ak χ ( B ) n ]
n =1

Where, χ(A)n and χ(B)n are atomic orbitals at position n

52
 χ(A) = s- orbital, χ(B) = σ p- orbital
X n = ak χ ( A) n + bk χ ( B ) n
Ψ(0) = Σn e0 Xn = X0 + X1 + X2 + X3 + X4 + X5 + X6 + …

No effective overlap between orbitals ⇒ non-bonding

Ψ (π/a) = Σn e-inπ Xn = X0 - X1 + X2 - X3 + X4 - X5 + X6 - …

Effective overlap between orbitals ⇒ bonding 53

E
Non-bonding

B band

54
 χ(A) = s- orbital, χ(B) = σ p- orbital
X n = bk χ ( A) n − ak χ ( B ) n

Ψ(0) = Σn e0 Xn = X0 + X1 + X2 + X3 + X4 + X5 + X6 + …

No effective overlap between orbitals ⇒ non-bonding

Ψ (π/a) = Σn e-inπ Xn = X0 - X1 + X2 - X3 + X4 - X5 + X6 - …

Antibonding between neighbor orbitals 55

antibonding

α2
non-bonding

non-bonding α1

bonding

56
57
Nearly-free electron model

Ψ = exp(ikx)
= cos(kx) + isin(kx)

E = ½ mv2 + V
= 2p2/m + V

de Broglie’s formula
Momentum p = h/λ
where h: Planck constant

λ= 2π/k
p = hk/2π ⇒ p α k

58
 1st Brillouin zone

Energy gap is produced due to

periodic potential

59
60
61
Schematic showing the method of generating the
band structure of the solid.

62
chain

63
 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.
64
65