Density Functional Theory (DFT)

DFT is an alternative approach to the theory of electronic structure; electron

density plays a central role in DFT.

Why a new theory?

HF method scales as K4 (K - # of basis functions)
CI methods scale as K6-K10
MPn methods scale as >K5
CC methods scale as >K6

Correlated methods are not feasible for medium and large sized molecules!

Alternative: DFT

The electron density

- it is the central quantity in DFT
- is defined as:
The electron density
Properties of the electron density

Function: y=f(x) ρ= ρ(x,y,z)

Functional: y=F[f(x)] E=F[ρ(x,y,z)]

Hohenberg–Kohn Theorems

ρ(r)

∫ ρ(r)dr = N
First HK Theorem:
The external potential Vext(r) is (to within a constant) a
unique functional of ρ(r). N ν(r)
Since, in turn Vext(r) fixes H, the full many particle ground state is
a unique functional of ρ(r).
Thus, the electron density uniquely determines the Hamiltonian
operator and thus all the properties of the system. )
H

Hˆ Ψ = EΨ

E
Proof: by reductio ad absurdum
Ψ’ as a test function for H:

Ψ as a testfunction for H’:

Summing up the last two inequalities:

Contradiction!
Variational Principle in DFT
Second HK Theorem
The functional that delivers the ground state energy of the system,
delivers the lowest energy if and only if the input density is the true
ground state density.

- variational principle

For any trial density ρ(r), which satisfies the necessary boundary conditions such as:

ρ(r)≥0 and

and which is associated with some external potential Vext, the energy obtained from the
functional of FHK represents an upper bound to the true ground state energy E0.
Thomas-Fermi model (1927)

r 3 L.H. Thomas, Proc. Camb. Phil. Soc., 23, 542-548 (1927)

2 2/3 5/3 r r
TTF [ρ(r )] = (3π ) ∫ ρ (r )dr E. Fermi, Rend. Acad., Lincei, 6, 602-607 (1927)
10
r r r
r 3 2 2/3 5/3 r r ρ(r ) r 1 ρ ( r1 )ρ ( r2) r r
ETF [ρ ( r )] =
10
(3 π ) ∫ ρ (r )d r − Z ∫ r d r + 2 ∫∫ r 12 d r1d r2
Next step
r r r
E[ ρ] = ENe [ρ] + T[ ρ] + Eee [ρ] = ∫ ρ( r )VNe ( r )d r + FHK [ρ]
with
FHK ???
FHK [ρ] = T[ ρ] + Eee
r r
1 ρ ( r1 )ρ ( r2) r r
Eee [ρ] = ∫∫ d r1 d r2 + Enon_cl [ρ] = J[ ρ] + Enon_cl [ρ]
2 r 12

Only J[ρ] is known!

The explicit form of T[ρ] and Enon-cl[ρ] is the major challenge of DFT
T[ρ] – kinetic energy of the system

Kohn and Sham proposed to calculate the exact kinetic energy of a non-interacting
system with the same density as for the real interacting system.

1 N TKS – kinetic energy of a fictitious non-interacting

TKS = − ∑ Ψi ∇2 Ψi system of the same density ρ(r)
2 i=1 Ψi - are the orbitals for the non-interacting system
(KS orbitals)

T=TKS+(T-TKS)

FHK [ρ] = TKS [ρ] + J[ ρ] + Enon - cl [ρ]

E[ ρ] = ENe [ρ] + TKS [ρ] + J[ ρ] + Exc [ρ] =
N M
ZA
-∑ ∫∑
2
ϕ i (r1 ) dr1
i=1 A = 1 r1A

1 N Exc[ρ] includes everything which is

− ∑ ϕi ∇ 2 ϕi
2 i =1 unknown:
1 N N 2 1 2 - exchange energy
+ ∑ ∑ ∫∫ ϕ i (r1 ) ϕ j (r2 ) dr1 dr2
2 i =1 j =1 r12 - correlation energy
+ Exc [ρ] - correction of kinetic energy (T-TKS)
Kohn-Sham Equations:

Minimize E[ρ] with the conditions: ∫ ρ(r)dr = N

ϕi ϕ j = δij

 1 2 ρ(r2 ) M
ZA 
 − ∇ + ∫ dr2 + v (r
xc 1 ) − ∑ ϕi = εiϕi
 2 r12 A=1 r1A 

with:
 Kohn-Sham Formalism

 1 2 
 − ∇ + v(r) + ρ(r') dr' − ∑ Ki (r) ϕ j = εjϕ j
Kohn-Sham  2 ∫ r − r' 
equations  i 
Hartree-Fock equations
Exc[ρ] = ??

Local Density Approximation (LDA)

Exc [ρ] = ∫ ρ(r)εxc (ρ(r))dr εxc only depends on the density at r

For the correlation part:
Monte-Carlo simulations – Ceperly and Alder

Good for solids

Generalized Gradient Approximation (GGA)

Exc [ρ] = ∫ ρ(r)εxc (ρ(r), ∇ρ(r),...)dr εxc depends on the density and its
gradient at r
(1) Adjust εxc such that it satises all (or most) known properties of the exchange-
correlation hole and energy.
PW91, PBE…
(2) Fit εxc to a large data-set own exactly known binding energies of atoms and molecules.
BLYP, OLYP, HCTH…
Meta-GGAs

No major improvements!

Hybrid Functionals

Exchyb [ρ] = αExKS + (1 − α)Exc

GGA

EXKS-the exact exchange calculated with the exact KS wave function

α- fitting parameter
Exchange and Correlation Functionals

In practice: BLYP, B3LYP, BPW91, …

Different functionals for different properties
Atomization energies:

Ionization energy: - B3LYP – the best!

Electron afinities:

Vibrational frequencies: - (BLYP), B3LYP, …

MO5-2X - bond dissociation energies, stacking and hydrogen-bonding

interactions in nucleobase pairs
Kohn-Sham orbitals