Density Functional Theory

II
Thus, in a molecule, the external potential is the attraction to the nuclei
given by the usual expression.
 HohenbergKohn existence theorem
(I theorem)
To establish a dependence of the energy on the density, (in the
HohenbergKohn theorem the ground-state density is employed) it is
sufficient to show that this density determines the Hamiltonian operator.
 HohenbergKohn existence theorem
(I theorem)

To establish a dependence of the energy on the density, (in the

HohenbergKohn theorem the ground-state density is employed) it is
sufficient to show that this density determines the Hamiltonian operator.

Integration of the density gives the number of electrons, so all that remains
to define the operator is determination of the external potential (i.e., the
charges and positions of the nuclei).

The proof that the ground-state density determines the external potential
proceeds via reductio ad absurdum, that is, we show that an assumption to
the contrary generates an impossible result.
 The first HohenbergKohn theorem
The electron density r(r ) determines the external
potential

This theorem establishes the existence of a (universal and

unique) energy functional of the density

Relation between the electron density and the external potential

For a given number of electrons, different densities

correspond to different nuclear positions and/or
atomic numbers and hence to different external
potentials and electronic Hamiltonians
Different external potentials will always
produce different densities.

Therefore, there is a one-to-one

correspondence between densities and
external potentials
 HohenbergKohn I theorem

In short
Thus, let us assume that two different external potentials can each be
consistent with the same non degenerate ground-state density 0.

We are left with an impossible result (that the sum of the two energies
is less than itself), which must indicate that our initial assumption was
incorrect.

So, the non-degenerate ground-state density must determine the external

potential, and thus the Hamiltonian, and thus the wavefunction.

Note moreover that the Hamiltonian determines not just the ground-state
wave function, but all excited-state wave functions as well, so there is a
tremendous amount of information coded in the density.
It should therefore be possible to write the electronic energy entirely as a
functional of the density:

Electronic kinetic interelectronic Electron-nuclei attraction

energy operator repulsion Operator operator external potential

Hohenberg and Kohn showed that a universal functional (does not depend on
external potential) FHK[n] exists

Unfortunately, no explicit formula is known for this functional

 HohenbergKohn theorem

In this form it is not practically useful, but it does provide the first step
for deriving the computational techniques on which DFT is based

These techniques make use of a variational principle for DFT, which is

known as the second H-K theorem

These theorems are considered to be amongst the greatest

developments in quantum theory since the Schrdinger equation in
1926
The second HohenbergKohn theorem

Any approximate density r which provides the

external potential n(r ), determines its own
wavefunction

The second HK theorem can be used to establish a variational

principle for DFT, although it restricts the theory to ground
states
 HohenbergKohn II theorem

A variational theorem for the density follows directly from the

variational theorem for the wavefunctions

Only the ground state density n(1) of Hel(1) minimizes the value of its
ground state energy functional (this is the second H-K theorem)
HohenbergKohn II theorem
 DFT calculations with the Hohenberg-Kohn approach

We need an expression for this

functional (even an approximate
expression)

Based on the variational principle for the density we can then calculate
the electronic energy by searching for the density that minimizes Eel[n]

This is the simplest way to do DFT calculations

(often called pure DFT)
 The separation of the electronic energy into components in conventional
quantum theory

Eel = Ekin + ECoul + EX + EC + Eext

Kinetic Coulomb Exchange Correlation External potential

energy energy energy energy energy

In the same way, it is assumed that the Hohenberga nd Kohn functional

can be split into a sum of functionals
 The Kohn-Sham self consistent field
methodology
Replacing one problem with another

Shortcomings of orbital-free DFT

Pure (orbital-free) DFT attempts to compute the energy of interacting electrons as a
functional of the density
In principle the approach is correct, but in practice it is not very accurate
This is due to the lack of accurate approximation for the kinetic functional

Kohn and Sham proposed an alternative approach in

order to overcome this problem
 The Kohn-Sham self consistent field
methodology
Replacing one problem with another

Kohn and Sham proposed to work with a

system of non-interacting electrons

In general, the wavefunction of non-interacting electrons is different from that of
interacting ones, and so is the density.
However, in the Kohn-Sham approach, a fictitious non-interacting system is constructed, in
such a way, that its density is the same as that of the interacting electrons.
 The Kohn-Sham self consistent field
methodology
Replacing one problem with another

The challenge is then shifted from finding the universal H-K functional to finding the
fictitious system of non-interacting electrons which has the same density as the real
one with the interacting electrons
This allows to set up more accurate DFT calculations, as expression for the kinetic energy
of non-interacting electrons is known (no need for approximate kinetic energy functionals
of the density)
In order to see how it works we first need to examine the Schrdinger equation for non-
interacting electrons.
 Interacting electrons

Construct and solve Schrdinger eq to

obtain the exact wavefunction for
interacting electrons
 Non-interacting electrons

Construct and solve Schrdinger eq for one electron.

Combine many one-electron wavefunctions (molecular
orbitals) to obtain approximate wavefunction for all
electrons

With non-interacting electrons you dont

need to compute integrals like this:
Kohn-Sham non-interacting electrons

Construct and solve Schrdinger eq for one electron.

Combine one-electron wavefunctions (molecular
orbitals) to obtain approximate wavefunction for all
electrons
 The Kohn-Sham self consistent field
methodology
Replacing one problem with another

Real system
(difficult to simulate, with
interacting electrons)

Model system Exchange-Correlation Functional

Vxc[(r)]
(easy to simulate, with
non interacting electrons) (its aim is to make (r)model =(r)system)
Wavefunction for non-interacting electrons
 Orbital-free vs Kohn-Sham DFT

Orbital-free Kohn-Sham

Not in this course

The exchange-correlation potential

While DFT in principle gives a good description of ground state properties,

practical applications of DFT are based on approximations for the so-called
exchange correlation potential.

The exchange-correlation potential describes the effects of the Pauli

principle and the Coulomb potential beyond a pure electrostatic interaction
of the electrons. Possessing the exact exchange-correlation potential means
that we solved the many-body problem exactly.

A common approximation is the so-called

local density approximation (LDA)
which locally substitutes the exchange-correlation energy density of an
inhomogeneous system by that of an electron gas evaluated at the local
density.
The exchange-correlation potential

The LDA approximation assumes that the density is slowly varying and the
inhomogeneous density of a solid or molecule can be calculated using the
homogeneous electron gas functional.

While many ground state properties (lattice constants, bulk moduli, etc.) are
well described in the LDA, the dielectric constant is overestimated by 10-40% in
LDA compared to experiment.

This overestimation stems from the neglect of a polarization-dependent

exchange correlation field in LDA compared to DFT.

The method can be improved by including the gradient of the density into the
functional.
The generalized gradient approximation GGA is an example of
this type of approach.
Tesi di dottorato: Davide Presti
Local density approximation (LDA)
 BLYP
(an example of GGA functional)
 B3LYP
(an example of Hybrid/Hyper-GGA functional)
 DFT vs post-HF
DFT-Hybrids Post-HF (MP2)
Accuracy

DFT-GGA

DFT-LDA
Hartree-Fock

Computational burden