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
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