INTRODUCTION TO

DENSITY FUNCTIONAL THEORY

Anusree S
IMSc Physics
Electron density

Number of electrons per unit volume at a given point r

Hohenberg–Kohn Theorems

• First theorem:

𝑈𝑒𝑥𝑡

Number of electrons Nucleus

?
ρ (r)
• Total energy = kinetic energy of electron + interaction among electrons +
interaction between electron and nuclei
• Kinetic energy of electron and interaction among electrons are system
independent represent them as universal functional F[ρ(r)]
• External potential varies from 1 system to another depending on the kind of
nuclei
• Then different Hamiltonians differ only by their external potential
• If there are 2 different external potential that yields same ground state
electron density, it will contradict

Electron density alone defines external potential

First theorem: There is an unique external potential determines solely by the
ground state density
Second HK theorem

• Assume we have some well-behaved candidate density

• Density determines a candidate wave function and Hamiltonian
• Evaluate expectation value of energy

< ψ𝑐𝑎𝑛 |𝐻𝑐𝑎𝑛 |ψ𝑐𝑎𝑛 > = 𝐸𝑐𝑎𝑛 ≥ 𝐸0

• Repeat with different densities

• The lowest energy obtained will be closer to true ground state energy
Problems!

oHow to choose improved candidate density rationally?

ρ𝑐𝑎𝑛 ?
o𝐸𝑐𝑎𝑛 = < ψ𝑐𝑎𝑛 |𝐻𝑐𝑎𝑛 |ψ𝑐𝑎𝑛 > Not an improvement from
early First principle methods
Kohn-Sham approach

Interacting system Non-interacting system

of electrons of electrons

Hamiltonian Eigen functions = slator Eigen values =

= sum of 1 determinant of the sum of 1 electron
electron
individual 1 electron eigen values
hamiltonian
eigen functions
Schematic of the Kohn–Sham approach
Energy terms
• The interacting n-electron energy of the HF approach

• In KS approach all the interacting effects are identified as

• Regroup all the interacting terms together as exchange-correlation energy,

Exc

• Then, the final expression of the total energy

Energy terms
1-Non interacting kinetic energy 𝑛
𝑛𝑜𝑛 −1
𝐸𝑘𝑖𝑛 = ෍ ϕ∗𝑖 (𝑟) ∇2 ϕ𝑖 (𝑟)
2
𝑖=1

• ϕ𝑖 - KS orbitals
• Orbitals are directly related to electron density

ρ(𝑟) = ෍ |ϕ𝑖 𝑟 |2
𝑖

The name DFT is still valid

2-External energy

3-Hartree energy
4-Exchange-correlation energy

• The XC energy can be viewed easily with the introduction of the XC

hole in an electronic system

Exchange hole
XC
hole Correlation hole
• Correlation hole forms both
positive and negative directions
• Correlation hole changes shape
of XC hole
Treating XC Energy

Assumptions:

1. XC energy – Local or semi-local functionals of

electron density

2. XC hole is spherical in three dimensions

• The local XC energy per electron electrostatic interaction
energy of an electron at r
with XC hole density at r′

• XC Energy functional

• Thus, the treatment of the XC hole is basically the same as the Hartree
interaction
Kohn-Sham equations

• Total energy of the system

• Applying second HK theorem – variation principle

• Apply chain rule

• Substitute values
𝑛
of each term
𝑛𝑜𝑛 1
𝐸𝑘𝑖𝑛 = − ෍ ϕ∗𝑖 (𝑟) ∇2 ϕ𝑖 (𝑟)
2
𝑖=1

ρ = ϕ∗ ϕ
1 2
0= − 𝛻 + 𝑢𝑒𝑥𝑡 + 𝑢𝐻 + 𝑢𝑥𝑐 − λ𝑖 ϕ𝑖 (𝑟)
2
 1 2
0 = − 𝛻 + 𝑢𝑒𝑓𝑓 + λ𝑖 ϕ𝑖 (𝑟)
2

• This is similar to Schrödinger equation with the corresponding KS

Hamiltonian,
1 2
− 𝛻 + 𝑢𝑒𝑓𝑓 𝑟 ϕ𝑖 (𝑟) = 𝜀𝑖 ϕ𝑖 𝑟
2

• For a given system, therefore, actual calculations are performed on this

Hamiltonian and it is required to solve this set of KS equations
simultaneously
Solving Kohn–Sham equations

Self-consistency

KS orbitals electron densities KS Hamiltonian

Therefore, to achieve meaningful results, we have to find a set of KS

orbitals that leads to a KS Hamiltonian whose solutions are the KS
orbitals we started with. This is called self consistency.
Iterative diagonalization
Local density approximation

Schematic of LDA in two dimensions. The actual electron-density (left)

distribution is approximated by four local elements of uniform electron
densities (right).
• Homogeneous electron gas – even distribution of electrons in a
uniform positive external potential, preserving the overall charge
neutrality
• The exchange energy and potential functionals are

• The correlation energy for a simple homogeneous electron gas at the

high density limit is

rs - Wigner–Seitz radius related to electron density

It is the radius of a sphere containing exactly one electron
• The values of per volume of constant ρ for all densities are
parameterized

• Then, the XC energy of the LDA can be calculated by multiplying

by the local electron density and integrating it over the space

• Corresponding XC potential of the LDA is

Drawbacks of LDA

• Overbinds (underestimates the lattice parameters) and thus overestimates

the cohesive energy and bulk modulus of solids
• Calculates the adsorption energies too high
• Underestimates the spin and orbital moments
• Calculates the band gaps ~50% smaller (e.g., Si) or even no gap (e.g.,
Ge)
• Cannot describe transition metals or strongly correlated systems. It
predicts, for example, incorrectly that the ground states of Fe
(ferromagnetic) and Cr (antiferromagnetic) are both nonmagnetic.
• Does not work well for materials that involve weak hydrogen bonds or
van der Waals attraction
Generalised gradient approximation

• Exc depends on the electron density and its gradient at a given point

• The general form of potential Uxc GGA[ρ(r)] is

• There is no simple functional form that correctly represents the GGA data
• Therefore, the general form of GGA is expressed based on the LDA
with an additional enhancement factor F(s) that directly modifies the
LDA energy

s depends on both electron density and its gradient

In solids, the typical range of s = 0 – 3

General trends of GGA

• GGA works very well with almost all systems, giving most structural
properties within a 1 to 3% error
• GGA corrects most of the overbinding problems of LDA, producing an
increase in lattice constants and a decrease in cohesive energies. In fact,
GGA slightly overcorrects bond length, resulting in low adsorption
energies
• GGA also calculates the band gaps approximately 50% smaller, or even
with no gap
Hybrid functional

• GGA-type functionals combined with some (~25%) of the accurate

exchange energy from the HF method
• HF method account exchange energy but does not account for the
correlation energy
• DFT exchange energies can reduce the errors if one introduces the HF
exchange energy into Exc typically in the form of
Reference

• Computational Material Science an Introduction - June Gunn Lee –

CRC Press
• Essentials of Computational Chemistry – Christopher J Cramer –
WILEY publishers – Second edition
THANK YOU