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