Motivation Formalism 3G DFT + example

Introduction to Density Functional Theory

S. Sharma
Institut fr Physik u Karl-Franzens-Universitt a Graz, Austria

19th October 2005

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Synopsis
Motivation : where can one use DFT Formalism :
1

1 2

Elementary quantum mechanics

1 2 3

Schrdinger equation o Born-Oppenheimer approximation Variational principle Wave function methods: Hartree-Fock method Modern DFT : Kohn-Sham Exchange correlation functionals (LDA, GGA ....)

Solving Schrdinger equation o

1 2 3

3 4

Third generation DFT Example

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Motivation
Walter Kohn was awarded with the Nobel Prize in Chemistry in 1998 for his development of the DFT.

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Motivation
The following gure shows the number of publications where the phrase DFT appears in the title or abstract (taken from the ISI Web of Science).

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Motivation
Where can DFT be applied:
1

DFT is presently the most successful (and also the most promising) approach to compute the electronic structure of matter. Its applicability ranges from atoms, molecules and solids to nuclei and quantum and classical uids. Chemistry: DFT predicts a great variety of molecular properties: molecular structures, vibrational frequencies, atomization energies, ionization energies, electric and magnetic properties, reaction paths, etc The original DFT has been generalized to deal with many dierent situations: spin polarized systems, multicomponent systems, systems at nite temperatures, superconductors, time-dependent phenomena, Bosons, molecular dynamics ...........

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Elementary quantum mechanics

Schrdinger equation o Hi (x1 , x2 ...xN , R1 , R2 ...RM ) = Ei i (x1 , x2 , ...xN , R1 , R2 ...RM ) x {r, }

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Schrdinger equation o

Kinetic energy 1 H= 2
N 2 i i

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Schrdinger equation o
Coloumb interaction 1 H= 2
N 2 i i N N j=i

+
i

1 rij

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Schrdinger equation o

Nuclear electron interaction 1 H= 2

N 2 i i N N j=i

+
i

1 rij

N i

M A

ZA riA

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Schrdinger equation o

Nuclear terms 1 H= 2 1 2
N 2 i i M i N N j=i M 2 A

+
i

1 rij
M

N i

M A

ZA riA

1 MA

+
A B=A

ZA ZB RAB

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Elementary quantum mechanics

Born-Oppenheimer approximation Due to their masses the nuclei move much slower than the electrons. So we can consider the electrons as moving in the eld of xed nuclei. 1 H= 2
N 2 i i N N j=i

+
i

1 rij

N i

M A

ZA = T + VN e + Vee riA

Hi (x1 , x2 ...xN ) = Ei i (x1 , x2 , ...xN )

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Elementary quantum mechanics

Variational principle The variational principle states that the energy computed from a guessed wave function is an upper bound to the true ground-state energy E0 . Full minimization of E with respect to all allowed N-electrons wave functions will give the true ground state. E0 [0 ] = min E[] = min |T + VN e + Vee |

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Elementary quantum mechanics

Energy E0 [] = |H| = (x)H(x)dx

Wave function : example of two fermions Pauli exclusion principle results in an antisymmetric wave function (x1 , x2 ) = 1 (x1 )2 (x2 ) 1 (x2 )2 (x1 ) This looks like a determinant 1 (x1 ) 2 (x1 ) 1 (x2 ) 2 (x2 )
S. Sharma Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Wave function method: Hartree-Fock

The ground state wave function is approximated by a Slater determinant:

1 HF (x1 , x2 ....xN ) = N!

.. . 1 (xN ) 2 (xN )

1 (x1 ) 1 (x2 ) . . .

2 (x1 ) 2 (x2 ) . . .

N (x1 ) N (x2 ) . . . N (xN )

The Hartree-Fock approximation is the method whereby the orthogonal orbitals i are found that minimize the energy. The variational principle is used. EHF = min E[HF ]
HF
S. Sharma Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Problems with wave function methods

I. Visualization and probing The conventional wave function approaches use wave function as the central quantity, since it contains the full information of a system. However, is a very complicated quantity that cannot be probed experimentally and that depends on 3N variables, N being the number of electrons.

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Problems with wave function methods

II. Time consuming The interactions are very dicult to calculate for a realistic system, in fact this is most time consuming part.
N N j=i

Vee =
i

1 rij

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Problems with wave function methods

III. Inecient One Slater determinant does a rather bad job for expanding the many-body wave function. (x, y) 1 (x)2 (y)

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Two Slater determinants

(x, y)

1 (x)2 (y) + 3 (x)4 (y)

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Eight Slater determinants

(x, y)

1 (x)2 (y) + 3 (x)4 (y)......15 (x)16 (y)

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Density Functional Theory

Experiments probe density (r1 ) = (x1 , x2 , .....xN )(x1 , x2 , .....xN )dx2 ....dxN

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Hohenberg-Kohn theorems

I Hohenberg-Kohn theorem H = T + VN e + Vee This rst theorem states that the VN e is (to within a constant) a unique functional of density (); since, in turn this potential xes H we see that the full many particle ground state is a unique functional of density.

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Hohenberg-Kohn theorems

II Hohenberg-Kohn theorem The second H-K theorem states that 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. This is nothing but the variational principle,but this time with density and not wave function E0 [0 ] = min E[] = min T [] + EN e [] + Eee []

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Modern DFT
Energy as a functional of density E[] = T [] + EN e [] + Eee [] E[] = T [] + EN e [] + EH [] + Ex [] + Ec []

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Modern DFT: Kohn-Sham

The system is replaced by a ctitious non-interaction system with same density as the real system. Kohn-Sham non-interacting system E[] = T [] + EN e [] + EH [] + Ex [] + Ec [] T [] = EN e [] + EH [] = Z 1 i | 2 |i 2 (r) 1 (r1 )(r2 ) dr1 dr2 dr r 2 r12

Local Density Approximation Based on the properties of uniform electron gas XC potential is approximated as: 3 Exc [] = (3 2 )1/3 4/3 (r)dr 4
S. Sharma Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Elementary QM Solving SE: HF Solving SE: DFT

Modern DFT: Kohn-Sham

The system is replaced by a ctitious non-interaction system with same density as the real system. Kohn-Sham non-interacting system E[] = T [] + EN e [] + EH [] + Ex [] + Ec [] T [] = EN e [] + EH [] = Z 1 i | 2 |i 2 (r) 1 (r1 )(r2 ) dr1 dr2 dr r 2 r12

Local Density Approximation Based on the properties of uniform electron gas XC potential is approximated as: 3 Exc [] = (3 2 )1/3 4/3 (r)dr 4
S. Sharma Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Third generation DFT: Exact exchange

Treating exchange term exactly E[] = T [] + EN e [] + EH [] + Ex [] Using the Fock integral and its functional derivative the exchange term can be treated exactly . This method is called EXX or OEP. S. Sharma, J. K. Dewhurst and C. Ambrosch-Draxl Phys. Rev. Lett. 95 136402 (2005)

S. Sharma

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Phase transition in Ce using LDA

-0.7

Energy (Ha)

-0.705

-0.71

-0.715

140

160 3 volume (a.u.)

S. Sharma

180

200

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

New physics captured with EXX

-8845

Energy (Ha)

-8846

Ce
-8847

Ce

-8848

8.8

9.2

9.4 9.6 9.8 Lattice constant (a.u.)

S. Sharma

10

10.2

10.4

Introduction to Density Functional Theory

Motivation Formalism 3G DFT + example

Many thanks to

1 2 3 4

Funding agency : FWF and Exciting EU network Dr. J. K. Dewhurst D. Rankin and S. Hinchley EXCITING code: http://exciting.sourceforge.net/

S. Sharma

Introduction to Density Functional Theory