Band Theory

• This is a quantum-mechanical treatment of bonding in

solids, especially metals.
• 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
∫ k Ηψ k
ψ *

Ek =
∫ kψ k
ψ *

Ebonding = (α + β)/(1+S) ~ (α + β) if S~0 (neglecting overlap)

E antibonding = (α - β)/(1-S) ~ (α - β)

α = ∫ϕ1s(1) *H ϕ1s(1) < 0

β = ∫ϕ1s(1) *H ϕ1s(2) < 0
-β
α
+β

7
No (He)2 molecule present!

8
9
 2nd Period Homo-nuclear Diatomic
Molecules

Electron configuration of Li2 : KK(σ1s)2

B.O. of Li2 = ½ (2 - 0) = 1

10
Hetero-nuclear Diatomic Molecule

Lewis Structure

11
Chemical bond from molecules to solids
1 D array of atoms

orbitals

empty

filled

12
The 2s Band in Lithium Metal

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

13
Band Overlap in Magnesium

Conduction band

Valence band

14
Cyclic ring

empty

filled

Cyclic system with n = 4 atoms, jth level

Ej = α + 2βcos2jπ/n , j = 0, 1, 2, 3 … .
15
16
17
18
The π-Molecular Orbitals of Benzene

_
node
+ _
E +
node

π-M.O. of
+
benzene 19
 3 nodes

2 nodes
E

Cyclic system with n π-orbitals, jth level

Ej = α + 2βcos2jπ/n , j = 0, 1, 2, 3 … .
20
21
22
 Linear Conjugated Double Bonds

Anti-
E bonding

Bonding

One-dimensional chain with n π-orbitals, jth levelπ-M.O.

Ej = α + 2βcosjπ/(n+1) , j =1, 2, 3 … . 23
24
Elementary Band Theory

25
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)

26
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 27
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.

28
 real
Free e-

wavelength imaginary
? = 8

Ψ(x) =µ(x)= ϕ1s

Real part ? = 2p /k
of
restricted e-
Ψ(x) = exp(ikx) ϕ1s
? = 2a

29
 ? = 2a

node Anti-bonding between

all nearby atoms
E
node
? = 8

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 30
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
31
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)
32
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
33
node
Energies of the States
∫ k Ηψ k
ψ *

Ek =
∫ kψ k
ψ *

Express Ψk and Ψk* as Bloch sums

N
 N

∫ψ k Ηψ k = ∑ ∑ exp[i (n − m) k ]∫ xm Η xn 
* *

n =1  m =1 
N
 N

∫ k k ∑
ψ *
ψ = ∑ exp [i ( n − m ) k ]∫ x *
m n
x
n =1  m =1 

Ek = α + 2βcos(ka)
α = ∫ χ n*Ηχ n
β = ∫ χ m* Ηχ n If m and n are neighbors
34
Ek = α + 2βcos(ka) and β < 0

Energy as a function of k for s-band

35
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 - …

36
σ-bond

1st Brillouin zone

37
DOS(E)dE
= # of levels between E and E + dE

38
39
k = 0 → 0.5a*
? = ∞→ 2a

40
 a λ
ϕ 0p z k=0
2a

ϕ0p.5z a* π/a ∞
0.5 a*

ϕ0p.25
z
a* 0.25 a*
π/2a 4a

ϕ ap*z
6 1/6 a*
π/3a 6a
d2
ϕ 0
z
bonding ∞
d
ϕ0.z52a* antibonding 2a
f3
ϕ 0
z antibonding 2a

f
ϕ0.z53a* bonding ∞
41
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 (n + 1) sin rjπ (n + 1)

 

The evolution of the π-orbital picture for conjugated linear

polyenes.
42
The evolution of the π energy levels of an infinite one-
dimensional chain (-CH-)n.

43
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

44
 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 45

E

B band

46
 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 47

antibonding

α2

α1

bonding

48
49
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 αk

50
 1st Brillouin zone

Energy gap is produced due to

periodic potential

51
52
Schematic showing the method of generating the
band structure of the solid.

53
 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.
54
chain

55
56
σ bond

57