Periodic Systems

• Molecules to Materials
𝜑𝑖 = 𝑐𝑖𝑟 χ𝑟
• LCAO-MO approach for periodic structures with 𝑟
Translational symmetry - Tight Binding Method
• Bloch Functions – Solutions to Schrodinger equation ψ𝑟 = 𝑒𝑖𝑘𝑟 𝑢(𝑟)
in a periodic potential
Plane wave Periodic function
at position r
k is the wave vector or crystal
momentum vector
a

r= 0 1 2 3 4 5
𝑁−1
• For a N-atom linear chain ψ𝑘 = 𝑒𝑖𝑘𝑟𝑎 χ𝑟 Bloch sums
𝑟=0
• Applying cyclic boundary conditions; Nth atom is same as the 0th atom
2𝜋
ckN = ck0 ; eikNa = 1 ; kNa = j 2π ; k=j k is quantized!
𝑁𝑎
𝑁−1

ψ𝑘 = 𝑒𝑖𝑘𝑟𝑎 χ𝑟
𝑟=0
• No. of Bloch Sums (MOs) should be equal to the number of atomic basis
functions

• For a given atomic orbital k functions are possible

• Overall nk values possible

• Adding 2π/a to k does not change the coefficient value; hence k values can be
restricted to a width of 2π/a
I Brillouin Zone; E(k) = E(-k)
• Standard choice k = -π/a to k = π/a
 ∗
Ψ𝑘 𝐻 Ψ𝑘
𝐸𝑘 = ∗
Ψ𝑘 Ψ𝑘
∗ 𝑁 𝑁 𝑖𝑘𝑎(𝑛 − 𝑚) ∗
Ψ𝑘 𝐻 Ψ𝑘 = 𝑛=1 𝑚=1 𝑒 χ𝑚 𝐻 χ𝑛
∗ 𝑁 𝑁 𝑖𝑘𝑎(𝑛 − 𝑚)
Ψ𝑘 Ψ𝑘 = 𝑛=1 𝑚=1 𝑒 χ𝑚 χ𝑛
∗ ∗
χ𝑚 𝐻 χ𝑛 = 𝛼; 𝑓𝑜𝑟 𝑚 = 𝑛 χ𝑚 𝐻 χ𝑛 = 𝛽 ; 𝑓𝑜𝑟 𝑚 = 𝑛 ± 1

∗ ∗
χ𝑚 χ𝑛 = 1 ; 𝑓𝑜𝑟 𝑚 = 𝑛 χ𝑚 χ𝑛 = 0 ; 𝑓𝑜𝑟 𝑚 ≠ 𝑛
∗
Ψ𝑘 𝐻 Ψ𝑘 = 𝑁𝛼 + 𝑁 𝛽 (𝑒𝑖𝑘𝑎 + 𝑒 − 𝑖𝑘𝑎)
= 𝑁{𝛼 + 𝛽 cos 𝑘𝑎 + 𝑖 sin 𝑘𝑎 + cos 𝑘𝑎 − 𝑖 𝑠𝑖𝑛 𝑘𝑎 }
= 𝑁 [𝛼 + 2𝛽 cos 𝑘𝑎 ]
∗
Ψ𝑘 Ψ𝑘 = 𝑁 𝐸𝑘 = 𝛼 + 2𝛽 cos 𝑘𝑎
 k as also a node counter for chemists! 𝑁−1

𝑁−1
ψ𝑘 = 𝑒𝑖𝑘𝑟𝑎 χ𝑟
𝑟=0
• At k = 0; 𝑒𝑖𝑘𝑟𝑎 =1 ψ𝑘 = χ𝑟 = χ0 + χ1 + χ2 + χ3 + … … . .
𝑟=0

𝑁−1
𝜋 𝑖𝑘𝑟𝑎
• At k = ;𝑒 = 𝑒𝑖𝜋𝑟 ψ𝑘 = 𝑒𝑖𝜋𝑟 χ𝑟 = χ0 − χ1 + χ2 − χ3 + … … . .
𝑎
= −1 𝑟 𝑟=0

Graphs of E(k) versus k are called

bands
Band runs up
 Nature of bands - pz orbitals

• At k = 0

χ0 + χ1 + χ2 + χ3 + χ4+ ..

𝜋
• At k =
𝑎

χ0 − χ1 + χ2 − χ3 + χ4 − ..

Band runs down

 Dispersion of bands - Bandwidth

• The energy difference between the

highest (most antibonding) and
lowest (most bonding) level in a
band is called the band width or
dispersion.

Fermi Energy • Not only a factor of distance, but

also of the nature of overlap or
interactions

• The energy of the highest occupied

level is called the Fermi energy
 Density of States - DOS

DOS is the number of states in an infinitesimal interval dE between E and E +

dE on the energy scale
Flat bands – high DOS
 Projected Density of States - pDOS

• Contribution from component atoms or atomic orbitals or fragment orbitals (crystal

orbitals) to the overall DOS
• Important tool for more complex structures
• Integration of these DOS curves up to the Fermi level results in an occupation
number for the orbital in question or in a charge of an atom (Mulliken Partition
scheme)
Crystal Orbital Overlap Population - COOP

• In the case of a periodic structure one considers an energy interval dE at an energy E and
weighs the DOS(E) with the average contribution of the levels in that interval to the
desired overlap population.
• The result is an overlap population-weighted density of states, which is called COOP
(crystal orbital overlap population).
• Integration of a COOP curve up to the Fermi level results in a total overlap population,
which indicates the bond strength
Cn chains

2.2 Å
Degenerate band

• σ bands have larger

dispersion than π
• Depends on overlap
(interactions) between
unit cells
In general, s and z Bloch functions are of the same symmetry, although there is no such
mixing at the zone boundaries, Γ and Z, where additional mirror planes perpendicular to
the z axis render the s and z band symmetry distinct. But in the interior of the Brillouin
zone, s and z orbitals can mix.
-

+/-

+ +/-
Avoided Crossing
1.4
1.3
 Pierl’s Distortion

• Bond alternation in carbyne and polyacetylene

• The Peierls theorem states that a one-dimensional system with an incompletely filled
band distorts in such a way as to open up a gap at the Fermi level.

• Metallic to semiconductor

• Solid-state analogue of the molecular Jahn-Teller theorem

• Intrinsic conductivity of polyacetylene is low; the spectacular metallic conductive

properties emerge only upon doping.
 Two-Dimensional Systems
Reciprocal Lattice
g2
Y M

y X
τ g1
a2

a1 x
τ = 0, 0
X = π/a, 0 (0.5, 0.0)
Y = 0, π/a
M = π/a, π/a (0.5, 0.5)
square lattice; a=b; X = Y
τ = 0, 0 M = π/a, π/a (0.5, 0.5)

X = π/a, 0 (0.5, 0.0) Y = 0, π/a

 2-D square network of Carbon

s-orbital

a2

a1
px py

pz
 τ = 0, 0 M = π/a, π/a (0.5, 0.5)

σ* π σ π*

X = π/a, 0 (0.5, 0.0) Y = 0, π/a

σπ
x σ* π*
τ = 0, 0 M = π/a, π/a (0.5, 0.5)

σ π*
σ* π

X = π/a, 0 (0.5, 0.0) Y = 0, π/a

σπ
σ* π*
 Graphene – Hexagonal Lattice

τ = 0.0, 0.0, 0.0

M = 0.5, 0.0, 0.0
K = 0.333, 0.667, 0.0
K = 1/3, 2/3, 0.0 = 2π/3a, 4π/3a, 0
 K = 1/3, 2/3, 0.0 = 2π/3a, 4π/3a, 0

𝑁−1

ψ𝑘 = 𝑒𝑖𝑘𝑟𝑎 χ𝑟
𝑟=0

2𝜋
• At k = ; 𝑒𝑖𝑘𝑟𝑎 = 𝑒𝑖2𝜋𝑟/3
3𝑎
𝑁−1
= 0.333 + 𝑖0.866 𝑟
ψ𝑘 = χ𝑟 = χ0 + 𝑎1χ1 + 𝑎2χ2 + χ3 + … … . .
𝑟=0
4𝜋 𝑖𝑘𝑟𝑎
• At k = ;𝑒 = 𝑒𝑖4𝜋𝑟/3
3𝑎
= 0.333 − 𝑖0.866 𝑟
τ = 0.0, 0.0, 0.0 M = 0.5, 0.0, 0.0 K = 0.333, 0.667, 0.0