Outline of the lecture

Introduction
Density functional theory
Born-Oppenheimer approximation
Hartree and Hartree-Fock approximation
Density functional theory and local density
approximation
Kohn-Sham equation

Plane-wave Pseudopotential method

Ab-initio pseudopotentials
Plane-wave basis

Applications of DFT to surface calculations.

Density functional theory

- Born-Oppenheimer approximation
- Single-electron approximation
- Hartree approximation
- Hartree-Fock approximation
- Density functional theory
- Kohn-Sham equation

Quantum Mechanics of Crystals

Materials are composed of nuclei {Z , M , R} and electrons {ri}
the interactions are known

Kinetic energy
Nucleus-Nucleus
Electron-Electron
of nuclei
interaction
interaction
Kinetic energy
Electron-Nucleus
of electrons
interaction

H = E
Ab-initio (first principles) Method
ONLY Atomic Numbers {Zi} as input parameters

Born-Oppenheimer Approximation I
Hamiltonian of the coupled electron-ion system

Many-body Schrdinger equation

Difference in time scales of ionic and electronic motions
Electrons respond instantaneously to slow ionic motion

mN m p

1839
me me

Born-Oppenheimer Approximation II
Decoupled Schrdinger equations

Adiabatic approximation
Electrons quickly respond to changes of nuclei, thus
allowing the electronic system to remain in its ground
state
Ions move on the potential-energy surface of the
electronic ground state

Single-particle Approximation
We still have to solve many-electron problem.
Exchange property: Pauli exclusion principle
Correlation property: interacting electrons

 Single-particle approach in an effective potential

XC effects are treated in an average way

Hartree approximation
Hartree-Fock approximation
Density functional theory

Hartree Approximation
Electrons treated as non-interacting particles
Total energy of the system

Single-particle Hartree equation

Variational Principle
Variation in the many-body wavefunction will give
zero variation in the energy.

Since this has to be true for any

Hartree-Fock Approximation
Incorporation of fermionic nature of electrons

Total energy with the HF wavefunction

Single-particle HF equation

Density Functional Theory (DFT)

1998 Nobel prize for W. Kohn with J.A. Popple
Density instead of many-body wave functions
The ground-state energy of a many-body system
is a functional of the electron density, n(r).
The functional E[n(r)] has its minimum at the
equilibrium density n0(r).

Hohenberg-Kohn Theorem I
The electron density n(r) is uniquely
determined by the external potential V(r).

Hohenberg-Kohn Theorem II

For a given V(r), the correct nGS(r) minimizes the ground-state

energy functional E[n(r)] and this minimum E[nGS(r)] is the ground
state energy.

GS

GS

GS

GS

GS

where F[n(r)] = < |T+W| > must be a universal funtional of the density
since T and W are common to all electronic systems.

Kohn-Sham Hamiltonian

Derivation of Kohn-Sham Equation

Variational procedure

E[n(r )]
0 subject to the condition

n(r ) n0 ( r)

Kohn-Sham equation

n(r )dr N

How to treat Exchange-Correlation

Local density approximation (LDA)

hom
E xc [n(r )] n(r ) xc [n(r )]dr n(r ) xc [n(r )]dr
Quantum Monte-Carlo simulations for homogeneous electron gas.

Generalized gradient approximation (GGA)

Algorithm of Self-Consistent Calculation

INPUT
atomic number
coordinates

setting-up
Hamiltonian
solving Kohn-Sham equation

updating electron density

no

Self-consistent ?
yes

New coordinates
no

Calculating QM force

Converged ?

yes

OUTPUT
final coordinates
total energy
energy eigenvalue
electron density

Implementations of the Kohn-Sham Method

FLAPW all-electron method

Plane-wave pseudopotential method
- ab-initio pseudopotentials
- Plane-wave basis
- Energy cutof
- Brillouin zone and k-point sampling

Pseudopotentials Basic idea

Core electrons are localized and therefore
chemically inactive (inert)
Valence electrons determine chemical
properties of atoms and SOLIDS
Describe valence states by smooth
wavefuctions

How to get smooth pseudo-valence-wavefunctions

from atomic valence wavefunctions?

Pseudopotentials Philips-Kleinman Method

Within the core region (0 r rc)

V ps V core ( E Ec ) | c c |
c

V core

Outside the core region (r > rc)

Z se2
V ps
r

v v

Norm Conserving Pseudopotentials

Norm-conserving Pseudopotentials

Pseudopotential shallow, nonlocal

Pseudo-wave function nodeless, slowly varying

Benefits of Pseudopotential Approach

Reduction of computational time
Only valence electrons
Smaller number of eigenstates
Smoother potential and nodeless wavefunctions
Smaller plane-wave-basis set

Plane Waves Formalism

Wavefunction

Bloch theorem

Kohn-Sham equation

Fourier series

Translational symmetry
Bloch theorem

Fourier expansion

How to solve eigenvalue problem

Eigenvalue equation

Plane-wave Basis
Systematic improvement of the accuracy of the
calculation with increasing cutoff energy Ecutoff
Efficient use of fast Fourier transformation (FFT)
in evaluating H
Basis set is independent of atom positions
(unbiased)
Easy calculation of Hellmann-Feynman forces

Charge density & k-point sampling

Charge density, (r)

Example of k-point sampling

2D square lattice
44 k-point grid
Only 3 inequivalent k-points

Applications of DFT
to surface calculations

Modeling Surface Slab vs. Cluster

Real system

Cluster model

Repeated slab model

Low index Surfaces of Si

(001)

Square lattice

(110)

Rectangular lattice

(111)

Hexagonal lattice

Relaxation and Reconstruction

a
Relaxation
Preserve (1x1)

2a
Reconstruction
(1x1)
(2x1)

Reconstruction - Si(001) Surface

ideal

c(4x2)

(2x1) sym

(2x2)

(2x1) asym

c(4x2)

Surface states at Si(001)-(2x1)

Potential-energy surface of Na on In/Si(111)

Atomic structure

Potential-energy surface

Prediction of binding energy, diffusion barrier, binding site

Reaction pathways of acrylonitrile on Si(001)

Energy profiles for the three reaction pathways
energy barrier

(a) 0.30 eV, [2+2]

(b) 0.32 eV, [4+2]-1
(c) 0.09 eV, [4+2]-II

Formation of the [4+2]-II structure is kinetically favored over

the [2+2] or [4+2]-I structure by a factor of ~10 4 at 300 K.