Density Function Theory

1. INTRODUCTION
2. BACKGROUND
3. QUANTUM METHODE

Introduction part
Density function theory (DFT) has revolutionized the quantum chemistry
development of the last 20 years
DFT allows to get information about the energy, the structure and the
molecular properties of molecules at lower costs that tradition approaches
based on the wave function
Background

1920 : Introduction of the Thomas fermi model .

1964: Hohenberg Kohnpaper proving existence of exact DF.
1965: Kohn Sham scheme introduction .
1970s and early 80s :LDA.DFT became useful .
1985: Incorporation of dft into molecular dynamics (car-parrinello),(now one of PRL top 10 cited paper )
1988: Becke and LYP Functionals .dft useful for some chemistry .
1998: Nobel prize awarded to Walter kohn in chemistry for develope

Quantum Methods

Wavefunctions Electron Density

The HF equation have to be solved iteratively because of v depend on the solution (the orbitals)

Hartree- FockParticles Schrodinger equation

The Many DFT

MP2-CI TD-DFT
 The N electron ,M nuclei Schrodinger (eigenvalue ) equation

(r1 , r2 ,..., rN , R1 , R2 ,..., RM ) E (r1 , r2 ,..., rN , R1 , R2 ,..., RM )

The N electron , M nuclei wave equation total energy

The N electron , M-nuclei Hamiltonian

M
2 N
2 2 1 M M Z I Z J e2 1 N N e2 M N
Z I e2
I
2
i
I 1 2 M I i 1 2m 2 I 1 J I RI RJ 2 i 1 j I ri rj I 1 i 1 RI ri

First term is the : Nuclear kinetic, second term is the Electron kinetic energy .third term is nuclear -
nuclear attraction term and forth term it can be consider is electron repulsion

The problem is completely parameter free but formidabIe. Cannot be solved analytical when N>1.

Too many variables for a 100 atom Pt cluster , the wave equation is a function of 23,000 variables

The born oppenheimer approximation

Electron mass is = 1/1800 times that of a nucleon mass

Hence ,nuclear degrees of freedom may be factor out
For a fixed configuration of nuclei ,nuclear kinetic energy is zero and nuclear -nuclear repulsion
is a constant thus

H elec (r1 , r2 ,..., rN ) Eelec (r1 , r2 ,..., rN )

N
2 2 1 N N e2 M N
Z I e2
H elec i
i 1 2 m 2 i 1 j I ri r j I 1 i 1 RI ri

1 M M
Z I Z J e2
E Eelec
2

I 1 J I RI RJ
 Now it can be solve this equation using density function theory .in our case we are study the bifeo3
material are a many body electron system it cannot be solve normally so it can be solve
by the using density function theory .

DENSITY FUNCTION THEORY

DFT is a reformulation of Schroodingers quantum mechanics
In Schroodinger s quantum mechanics ,observables are a function of (r1,r2,..rn).for e.g .
,E=<(r1,r2.rn)|H|(r1,r2,rn)>
Note : A DFT is a reformulation of Schrodingers quantum mechanics
In Schrodingers quantum mechanics, observables are functionals of (r1,r2,,rN). For e.g., E =
<(r1,r2,,rN)|H|(r1,r2,,rN)>
Note: A functional is a function of a function; e.g., E[f(r)] is a functional of f(r), but f(r) is a function
of r
i.e., for different choices of the functional form of f(r), E will take on different values!
In DFT, the total energy of a system (or any property, including (r1,r2,,rN)) is a unique functional

of the total electronic charge density, n(r) is the Theorem 1

The correct n(r) minimizes the total energy equivalent to the Variational theorem [Theorem 2]

e2
d rd r' v(r)n(r)d 3 r E xc [n(r)]
n(r)n(r') 3 3
E elec T[n(r)]
2 r r'
Total energy= it equation consider the first term is kinetic energy and density change
function of different sate of electron and third term is the external potential and the last term is
exchange correlation energy

Theorem 2: The correct n(r) minimizes E ; Thus:

elec
E /n(r) = 0 correct ground state E
elec elec

So What ? the wave function of 3N variables ,but the charge density is a function of only 3 variables !
However ,the functional form of E [n(r)] is not specified .

Density function theory [kohn sahm (1965)]

.A unique one-to-one mapping is established between a system containing N interacting electrons with charge
density n(r) moving in an external potential, and a fictitious system of N non-interacting electrons also with the same
change density n(r)

What is so great about this?

The problem of N non-interacting electrons is solvable!
Each of the N non-interacting electrons exists in an external effective potential that contain the
information about the interactions that have been removed.

DIFFICULT PROBLEM Unique mapping (with) Solvable problem

N interacting electrons, with N noninteracting electrons, with

charge density n(r) charge density n(r
V (potential due to nuclei external fields

The kohn sham 1 electron equation

Kohn sham Hamiltonian Non interacting electron Non interacting

Wave function electron energy
2
2 veff ( r ) i ( r ) i i ( r )
2m

n( r ' ) E xc [ n ( r )]
veff ( r ) v ( r ) e 2 r r'
d 3 r '
n ( r )
Nuclear potential , electromagnetic potential ,etc

If it can be consider vxc (r) since this is not the case ,vxc is approximation (here in lines the division
between DFT and Quantum chemistry methods ..)

The total energy

Similar to the hartree treatment ,the Kohn Sham equation are solved self consistently
_ why ? Because veff (r) depends on n (r) which depends on the wave function
The resulting self consistence i and i may be used to compute the total energy as follows

The total energy :-

 1 Z I Z J e2
E Eelec
2 I J I RI RJ
N
d rd r ' n(r ) xc [n(r )] vxc [n(r )]d 3r
1 n( r ) n( r ' ) 3 3
Eelec i e 2
i 1 2 r r'

Note : E xc [n( r )] n( r ) xc [n( r )]d 3r

The Hohenberg kohn sham prescription for the total energe :-

Guess i(r) for all the electrons

Remember that i(r) is a 1-electron wave function

occ
n ( r ) 2 i ( r )
2

2 2
veff ( r ) i (r ) i i (r )
2 m
No
Solve!
Is new i(r) close to old i(r) ?

Yes

Calculated total energy

N
d rd r ' n(r ) xc [n(r )] v xc [n(r )]d 3 r
1 n( r ) n( r ' ) 3 3
Eelec i e 2
i 1 2 r r'
E Eelec nuclear repulsion energy