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Density Functional Theory: - Instead of Ψ, look at electron density

Density functional theory (DFT) calculates the electron density rather than the wavefunction. The electron density is a functional of the ground state energy and is minimized to determine the exact ground state density. DFT maps a function (electron density) to a number (energy) using functionals. It approximates exchange-correlation terms and solves for the electron density rather than the full wavefunction. Common DFT functionals include B3LYP, PBE, and BP86 which approximate exchange and correlation terms differently.

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Krishna Bhati
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347 views9 pages

Density Functional Theory: - Instead of Ψ, look at electron density

Density functional theory (DFT) calculates the electron density rather than the wavefunction. The electron density is a functional of the ground state energy and is minimized to determine the exact ground state density. DFT maps a function (electron density) to a number (energy) using functionals. It approximates exchange-correlation terms and solves for the electron density rather than the full wavefunction. Common DFT functionals include B3LYP, PBE, and BP86 which approximate exchange and correlation terms differently.

Uploaded by

Krishna Bhati
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© © All Rights Reserved
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Density Functional Theory

• Instead of Ψ, look at electron density


– HF-SCF Theory is 4N dimensional
– Electron density is 3N dimensional (N = # e-’s)
• Get rid of one-dimension (spin)
– Hohenberg & Kohn (1964)
“The ground state energy E of an N-electron system is a
functional of the electronic density ρ, and E is a minimum when
evaluated with the exact ground state density”
• Also N = ∫ρ (r)dr
What is a “Functional”?
• The energy depends on a complicated
function, which is the e- density in 3-D
space
– A function whose argument is also a function
is called a functional
– The energy is a unique functional of ρ(r)
– a functional enables a function to be mapped
to a number
DFT Process
• The energy is minimized with respect to
variations in ρ, subject to the constraint of charge
conservation:
N    (r )dr
– Electron density is easier than dealing with Ψ

– Instead of attempting to calculate the full N-electron


wavefunction, DFT only attempts to calculate the total
electronic energy and the overall electron density
distribution
Problem
→ We have no idea of what the function describing the
electron density looks like!
– Kohn and Sham (1965): Look at specific components of the energy
functional:
E() = Tni() + Vne () +Vee () + T () + Vee ()
Where
Tni = kinetic energy of non -interacting electrons,
Vne = nuclear -electron attraction,
Vee = electron -electron repulsion,
T = correction to the kinetic energy from electron interaction, and
Vee = sum of all non -classical corrections to the electron electron
replusion energy
Solution
• The first three terms from the previous slide
have been seen before
– The last two terms are the troublesome ones
– They are usually combined together to form what is
called the exchange-correlation energy Exc
• This term includes effects of quantum mechanical exchange
and correlation
→The correlation energy is what was missing
from HF theory, and was a major limitation
Approaches to Exc
• Terminology of density functionals:
1. Local: Simple dependence of Exc on ρ(r)
2. Nonlocal, or gradient corrected: Exc depends on
both ρ(r) and the gradient of ρ(r), ρ(r)
Variational approach:
• Overall energy minimum corresponds to the exact ground
state electron density (all other densities give higher
energy)
Further constraint:
• Number of electrons is fixed N =∫ρ(r)dr
Differences Between HF-SCF and DFT

• DFT contains no approximations: It is exact


• All we need to know is Exc as a function of ρ
• As we will see, we must approximate Exc
• HF is a deliberately approximate theory so that
we can solve the equations exactly
• So,
– with DFT our theory is exact and the equations are
solved approximately,
– while with HF our theory is approximate but we can
solve the equations exactly
Some Common Functionals
• B3LYP: Becke, Lee, Parr, and Yang; uses a
hybrid exchange correlation energy functional
• B3PW91: Becke, Perdew, and Wang; The
PW91 correlation functional replaces LYP
• PBE-96: Perdew, Burke, and Ernzerhof; an
updated correlation functional
• VWN#5: Vosko, Wilk, and Nusair; another
correlation functional
• BP86: Becke and Perdew; uses the Becke 1986
exchange energy and the Perdew 1996 GC
correlation functional
Density Functional Theory
• Advantages:
– Scales as N3 (HF was N4)
– With few exceptions, DFT is the most cost-effective method to
achieve a given level of accuracy
– Electron correlation included with less expense

• Disadvantages:
– All e- are included
– Cost still be large for molecules of interest
– With Ψ’s apply the correct operator to determine the molecular
property of interest
– With DFT, must know how the molecular property depends on
the electron density

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