Propriedades Quânticas de

Nanomateriais utilizando a Teoria

do Funcional
Densidade (DFT)
Pedro Venezuela & Marcio Costa
Instituto de Física
Universidade Federal Fluminense
Niterói, RJ
Brazil

AULA 6
 Kohn–Sham equations

Strictly speaking the Kohn–Sham wavefunctions are only a mathematical

tool for building the charge density:

DFT is a theory of the total energy, the electron density and their relation in
the ground state, and it does not tell us anything about the uses and
meaning of Kohn–Sham energies and wavefunctions.
Do Kohn–Sham energies and wavefunctions
carry some kind of physical meaning?
Approximately yes

Solid answer - Quantum field theory

Mattuck, R. D. (1976). A guide to Feynman diagrams in the

many-body problem (2nd edn). McGraw-Hill, New York
Do Kohn–Sham energies and wavefunctions
carry some kind of physical meaning?

Solid answer - Quantum field theory

Mattuck, R. D. (1976). A guide to Feynman diagrams in the

many-body problem (2nd edn). McGraw-Hill, New York
Do Kohn–Sham energies and wavefunctions
carry some kind of physical meaning?
Approximately yes

Solid answer - Quantum field theory

Mattuck, R. D. (1976). A guide to Feynman diagrams in the

many-body problem (2nd
edn). McGraw-Hill, New York

In many cases Kohn–Sham states and energies

happen to be reasonably good starting points for
describing things such as the electrical and optical
properties of materials.
 Kohn–Sham energies and wavefunctions

DFT electronic total energy

 Kohn–Sham energies and wavefunctions

DFT electronic total energy

 Kohn–Sham energies and wavefunctions

Starting from a system of N electrons with energy EN, and

adding one electron in the (previously unoccupied) state φi.
The resulting total energy can be denoted EN+1,i.

Changing , eingevalues also change.

Solids or large nanostructures - number of electrons is

typically so large that the change in density will be very
small.
First approximation, eigenvalue is independent of the
occupation.
 Calculation of band structures using DFT

Bloch theorem - Single-particle electronic wavefunctions in a

crystal = product of a function periodic in the unit cell and a
plane wave:

‘Crystal version’ of the Kohn–Sham equations

 Calculation of band structures using DFT

We solve KS equations only inside one crystalline unit cell

and apply periodic boundary conditions

Solutions for are simply duplicates of the solutions for

We solve KS equations only for k in first Brillouin zone

Calculation of band structures using DFT
Calculation of band structures using DFT

Sum in a grid of
k points in the
1st BZ
Band structure of Cu

Ambient conditions: Cu crystallizes

in a fcc lattice with one atom per unit
cell and lattice constant a = 3. 61 A.

Electronic configuration: [Ar]4s1 3d10 =

11 valence electrons per unit cell

Angle-resolved
photoelectron
spectroscopy
 Band structure of Cu

Ambient conditions: Cu crystallizes

in a fcc lattice with one atom per unit
cell and lattice constant a = 3. 61 A.

Electronic configuration: [Ar]4s1 3d10 =

11 valence electrons per unit cell

1) Electron density is determined

self-consistently

2) are determined,
usually at high symmetry points in
the BZ
Band structure of Cu

Ambient conditions: Cu crystallizes

in a fcc lattice with one atom per unit
cell and lattice constant a = 3. 61 A.

Electronic configuration: [Ar]4s1 3d10 =

11 valence electrons per unit cell
Band structure of Cu

Ambient conditions: Cu crystallizes

in a fcc lattice with one atom per unit
cell and lattice constant a = 3. 61 A.

Electronic configuration: [Ar]4s1 3d10 =

11 valence electrons per unit cell
 Band structure of Cu

Fermi Surfaces: