FOUNDATIONS OF DENSITY-FUNCTIONAL

THEORY
J. Hafner

Materialphysik and Center for Computational Material

Institut fur
Science
Universitat Wien, Sensengasse 8/12, A-1090 Wien, Austria

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 1

Overview I
Hohenberg-Kohn theorem
Hellmann-Feynman theorem
Forces on atoms
Stresses on unit cell
Local-density approximation: density only
Thomas-Fermi theory and beyond
Local-density approximation: Kohn-Sham theory
Kohn-Sham equations
Variational conditions
Kohn-Sham eigenvalues

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

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Overview II
Exchange-correlation functionals
Local-density approximation (LDA)
Generalized gradient approximation (GGA), meta-GGA
Hybrid-functionals
Limitations of DFT
Band-gap problem
Overbinding
Neglect of strong correlations
Neglect of van-der-Waals interactions
Beyond LDA
LDA+U

GW, SIC,

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

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Density-functional theory - HKS theorem

Hohenberg-Kohn-Sham theorem:


 

(1) The ground-state energy of a many-body system is a unique functional

of the particle density, E0 E r .

 


 

(2) The functional E r has its minimum relative to variations n r of the

particle density at the equilibrium density n0 r ,

 

nr


 

min E r

 



   

J. H AFNER , A B - INITIO

no r

(1)

 
 



E n r
n r

 

E n0 r

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Proof - HKS theorem

Reductio ad absurdum:

Vee

(2)

 

is the Hamiltonian of a many-electron system in an external potential V r

and with an electron-electron interaction Vee . In the ground-state this system
0 H 0 and the particle density
has the energy E0 , with E0
n0 r
0 r 2 . Let us assume that a different external potential V leads
to a different ground-state 0 , but to the same particle density:
0 r 2 n0 r . According to the variational principle it follows
n0 r
that
E0
0 H 0
0 H V V 0
(3)
E 0 0 V V 0


 





 

 

 




 

 



 















J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 5

Proof - HKS theorem

n0 r V r

V r d3r

(4)


 
 
 
 
 

E0

E0

Starting from


 

(5)

 

n0 r it follows



 

and using n0 r

0 H 0

 

E0

V r d3r

n0 r V r

d3r

(6)





 

V r


 
 

 

E0

n0 r V r


 

 
 

 
 

E0

E0

 

 

in direct contradiction to the results obtained above. Hence n0 r and n0 r

must be different and V r is a unique functional of n r .

 

 

The variational property of the Hohenberg-Kohn-Sham functional is a direct

consequence of the general variational principle of quantum mechanics.
J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 6

HKS theorem - Variational principle

With
Vee

(7)


d3r



 

Vee

nrV r

  

 






Fnr



Enr


  

Fnr
it follows


 


n0 r V r d 3 r



  

  

E n0 r

(8)

 

0 V 0






  

Vee 0

0 T

F n0 r

n r V r d3r


 

 
 

Fn r

 

 




  
   



 
 

E n r

and hence




   

J. H AFNER , A B - INITIO

n0 r

(9)

 
 

nr


 

min E n r



E n r
n r

 

E n0 r

E0

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Hellmann-Feynman theorem: Forces and stresses



The external potential V is created by the ions located at the positions RI ,

V r
v r RI . The ground-state energy and wavefunction depend on

 
 



 

RI as parameters. The force FI acting on an

the ionic coordinates, R
atom located at RI is given by

 



(10)

0 H I 0



0 I H 0





 

0 R

 

 

I H R

 

0 R

I 0 H 0
0 R

H R

 

0 R

 

RI

I E 0 R

 

 

FI

First and third terms in the derivative vanish due to variational property of
Forces acting on the ions are given by the expectation
the ground-state
value of the gradient of the electronic Hamiltonian in the ground-state. The
ground-state must be determined very accurately: errors in the total energy
are 2nd order, errors in the forces are 1st order !
J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 8

Hellmann-Feynman theorem: Forces and stresses

The stress tensor i j describes the variation of the total energy under an
infinitesimal distortion of the basis vectors a k under a strain ti j :


 

i j


i j

ti j a k






J. H AFNER , A B - INITIO

ak

 




ti j H

i j

(11)



ak

E ak
ti j

MATERIALS SIMULATIONS

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DFT functional
Total-energy functional

 

V r n r d3r

 



E xc n



EH n



T n



En

(12)



T n
kinetic energy,
EH n
Hartree energy (electron-electron repulsion),
E xc n
exchange and correlation energies,
V r
external potential
- the exact form of T n and Exc is unknown !






 

Local density approximation - density only:

- Approximate the functionals T n and Exc n by the corresponding
energies of a homogeneous electron gas of the same local density
Thomas-Fermi theory

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 10

Thomas-Fermi theory
Kinetic energy:


 

t n r d3r

T n

(13)

32 2 3

5 3

nr


 

tn

3
h2
10m

where t n is the kinetic energy of a noninteracting homogeneous electron

gas with the density n.
Electron-electron interaction: Coulomb repulsion only
e2
2

nr nr 3 3
d rd r
r r

(14)



E n

 
 
  
   

Add exchange-correlation term in modern versions. Variation of E n with

leads to the Thomas-Fermi equation

nr
d3r
r r



 



 
  
 

2 3


 

5
Cnr
3

J. H AFNER , A B - INITIO

V r

MATERIALS SIMULATIONS

(15)

Page 11

Kohn-Sham theory
d 3 rd 3 r


     ! 

   " !  

 






 

 

T nr

nr nr
r r
E xc n r

e2
2

n r V r d3r



 

Enr

(16)

(1) Parametrize the particle density in terms of a set of one-electron orbitals

representing a non-interacting reference system
2

(17)





 

 

nr

 

(2) Calculate non-interacting kinetic energy in terms of the i r s, i.e.

T n T0 n ,

#$

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J. H AFNER , A B - INITIO

 

 

i r



T0 n

h2 2
i r d 3 r
2m

(18)

Page 12

Kohn-Sham theory II
(3) Local-density approximation for exchange-correlation energy
(19)

&


 

 

n r xc n r d 3 r



 

E xc n r


 

where xc n r is the exchange-correlation energy of a homogeneous

electron gas with the local density n r . For the exchange-part, a
Hartree-Fock calculation for a homogeneous electron gas with the density n
leads to
3e2
32 n r 1 3
(20)
x n r
4
(4) Determine the optimal one-electron orbitals using the variational
i j
condition under the orthonormality constraint i j

 



 




 

(21)

i j

i j

 

i j

i j





 

E nr

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 13

Kohn-Sham theory III



Kohn-Sham equations (after diagonalizing i j ):

 

(22)


   

Exc n r
n r



 

with the exchange-correlation potential xc n r

i i r



 

i r

xc n r


 

nr
d3r
r r

e2

 

   
 

V r


 

h2 2

2m

Total energy:
d3r


 



xc n r



 

n r xc n r

 

nr nr 3 3
d rd r
r r

1
2

 
 
  
   

'
() 

'* () 

sum of one-electron energies

double-counting corrections

(1)
(2)

(23)

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 14

Kohn-Sham theory IV
Variational conditions
Total energy E n

 

 
   
nr

n0 r

(24)

 
 

E n r
n r

Kohn-Sham eigenvalues i
j

(25)

(26)

0 with i j



i H KS i

Norm of residual vector Ri

app

app



R i

i H KS i



R i

&

H KS



R i

No orthogonality constraint !
J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 15

Kohn-Sham theory V
Interpretation of the one-electron energies i
Hartree-Fock theory - Koopmans theorem
0

E HF ni

 

E HF ni

HF
i

(27)

= Ionisation energy if relaxation of the one-electron orbitals is

HF
i
neglected.
Kohn-Sham theory:
Total energy is a nonlinear functional of the density
Koopmans theorem
not valid.
E n r
i ni r
i r r
(28)
ni r


 

 

%


 

&


 
   

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 16

Exchange-correlation functionals I
Definition of the exchange-correlation functional:

E xc n accounts for the difference between the exact ground-state energy

and the energy calculated in a Hartree approximation and using the
non-interacting kinetic energy T0 n ,

U xc n

(29)



T0 n

 

T n

-,

E xc n

&



exact and non-interacting kinetic energy functional

T n T0 n
U xc n
interaction of the electrons with their own exchange-correlation
hole nxc defined as (2 is the two-particle density matrix)



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 &
 &
 

J. H AFNER , A B - INITIO

nxc r s; r s





  

ns r ns r

 

,
 &
 &
 

2 r s; r s

(30)

Page 17

Exchange-correlation functionals II
Properties of the exchange-correlation hole
Locality
0



 &
 &
 

lim nxc r s; r s

(31)


" !

r r

Pauli principle for electrons with parallel spin

(32)

s s



(33)

(34)

 

ns r


 
&
 &
 

nxc r s; r s

Antisymmetric non-interacting wavefunction




 &
 &
 

nx r s; r s d 3 r

Normalization of two-particle density matrix

J. H AFNER , A B - INITIO

 &
 &
 

nc r s; r s d 3 r

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Page 18

Exchange-correlation functionals III

Properties of the exchange-correlation functional
Adiabatic connection formula
d r

nxc r; r
d
r r

 

   
  

d rn r



 

1
2

xc

(35)

Lieb-Oxford bound
3

1 68

1 44

&

r d3r

n4

 

.

E xc n

(36)

plus scaling relations,.......

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 19

Local (spin-)density approximation - L(S)DA

(37)

&


 

 

n r xc n r d 3 r



 

E xc n r


&
&2
 


1
&0
 

Exchange-functional (for spin-polarized systems,

nr
nr
n n n )

3
4 3

6
4
  
7
6
3
 
1 21 3

(38)

xp

xp

nr 4 3
nr
n n4 3 n n4 3
1 1 21 3
nr

8 
"6 6
 
: 
 7  "
6

9
5  

f
x

nr

32 1 3




&2
 
&
&0
 

x n r

3e2
4

n
n 2 for the paramagnetic (non-spinpolarized) and
with xp x n
f
nn
0 for the ferromagnetic (completely spin-polarized)
x x n
limits of the functional.
Correlation functional c n r
nr
fitted to the ground-state energy of
a homogeneous electron gas calculated using quantum Monte Carlo
simulations and similar spin-interpolations.

4 

3 &
 


&2
 
&
&0
 
J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 20

Semilocal functionals
Generalized gradient approximation - GGA
nr

n r

n r

d3r

&

f nr


&2
 
&
&0
 
&
2&
 
&
&0
 

nr



&2
 
&
&0
 

E xc n r

(39)

There are two different strategies for determining the function f :

(1) Adjust f such that it satisfies all (or most) known properties of the
exchange-correlation hole and energy.
(2) Fit f to a large data-set own exactly known binding energies of atoms
and molecules.
Strategy (1) is to be preferred, but many different variants: Perdew-Wang
(PW), Becke-Perdew (BP), Lee-Yang-Parr (LYP),
Perdew-Burke-Ernzernhof (PBE).

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 21

Semilocal functionals
Meta-GGA

 

Include in addition a dependence on the kinetic energy density r of the

electrons,
i r

 



 

nocc

i 1

(40)

In the meta-GGAs, the exchange-correlation potential becomes

orbital-dependent !

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 22

Hybrid functionals
General strategy: Mixing exact-exchange (i.e. Hartree-Fock) and
local-density energies, as suggested by the adiabatic connection formula

1 xc
U n
2 1



1 xc
U n
2 0

n d



Uxc

(41)

nonlocal exchange energy of Kohn-Sham orbitals

potential energy for exchange and correlation



U0xc n
U1xc n

xc



Example: B3LYP functional

1

c
c EVW
N

c
cELY
P

x
bEB88

x
aEexact

x
a ELSDA




E xc n

(42)

&

&

x stand for the exchange part of the Becke88 GGA functional,

where EB88
c
ELY
P for the correlation part of the Lee-Yound-Parr local and GGA
c
functional, and EVW
N for the local Vosko-Wilk-Nusair correlation
functional. a b and c are adjustable parameters.
J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 23

Limitations of DFT I

Band-gap problem:
- HKS theorem not valid for excited states
band-gaps in
semiconductors and insulators are always underestimated
- Possible solutions: - Hybrid-functionals lead to better gaps
- LDA+U, GW, SIC increase correlation gaps

Overbinding:
- LSDA: too small lattice constants, too large cohesive energies, too high
bulk moduli
- Possible solutions: - GGA: overbinding largely corrected (tendency too
overshoot for the heaviest elements)
- The use of the GGA is mandatory for calculating adsorption energies, but
the choice of the correct GGA is important.

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 24

Limitations of DFT II

Neglect of strong correlations

- Exchange-splitting underestimated for narrow d- and f -bands
- Many transition-metal compounds are Mott-Hubbard or charge-transfer
insulators, but DFT predicts metallic state
- Possible solutions: - Use LDA+U, GW, SIC,

Neglect of van-der Waals interactions

- vdW forces arise from mutual dynamical polarization of the interacting
not included in any DFT functional
atoms
- Possible solution: - Approximate expression of dipole-dipole vdW forces
on the basis of local polarizabilities derived from DFT ??

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 25

Beyond DFT
DFT+U
Describe on-site Coulomb-repulsion by Hubbard-Hamiltonian
J

nm s nm



" 

m m s

(43)


<



mm s

nm s nm

U
2

where nm s is the number operator for electrons with the magnetic quantum
number m and spin s, U E d n 1 E d n 1 2E d n and J a screened
exchange energy.

"

 

The DFT+U Hamiltonian includes contributions already accounted for in

subtract double-counting, adopt rotationally
the DFT functional
invariant formulation
U J
EDFT U EDFT
Tr s s s
(44)

2
s

on-site density matrix sij of the d electrons

J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 26

Beyond DFT II
Calculate quasiparticle-excitation energies by low-order many-body
perturbation theory.
GW: Self-energy approximation approximated by
i
2


 &
 


 &
 

G r r ; W r r ; d

 &
 

r r ;

(45)
1

"

where G is the full interacting Greens function and W the dynamically

screend Coulomb intreraction, described by the inverse dielectric matrix
and the bare Coulomb potential v,
r d3r

"

In practice, approximate forms of G and

 &
 

r r ; v r


 

"




 &
 

W r r ;

(46)

have to be used.

SIC: Self-interaction corrections.

GW, SIC are not implemented in VASP. Results largely equivalent to
LDA+U.
J. H AFNER , A B - INITIO

MATERIALS SIMULATIONS

Page 27