KohnSham Equations
HK density functional:
Thus,
The corresponding Euler equation:
KohnSham separated F[n(r)] into three parts.
where T
s
[n(r)] is the kinetic energy of a noninteracting electron gas
of density n(r) (not the same as that of the interacting system), and the
second term of Eq. (3) is the classical electrostatic (Hartree) energy.
E
xc
[n(r)] is the exchangecorrelation energy and contains (i) the
difference between the exact and noninteracting kinetic energies and
(ii) the nonclassical contribution to the electronelectron interactions,
of which the exchange is a significant part. E
xc
[n] is usually a small
fraction of the total energy. is unaffected by mapping.
+ = )] ( [ ) ( ) ( )] ( [ r r r r r n F d n V n E
ext
( )   ) 1 ( .......... 0 ) ( ) ( ) ( )] ( [ =
+ N d n n V d n F
ext
r r r r r r
) 2 ( ....... ) (
) (
)] ( [
r
r
r
ext
V
n
n F
+ =
) 3 ( ..... .......... )] ( [
) ( ) (
2
1
)] ( [ )] ( [ r
r r
r r
r r r r n E
n n
d d n T n F
XC S
+
+ =
) (r
ext
V
KohnSham Equations
Applying the Euler equation [i.e., Eq. (2)] to Eq. (3), one obtains.
in which the KohnSham potential, V
ks
(r), is given by
where the exchangecorrelation potential V
xc
(r) is defined by
The crucial point to note here is that Eq. (4) is precisely the same
equation which would be obtained for a noninteracting system of
particles moving in an external potential, V
ks
(r).
(Original Paper) W. Kohn and L. J. Sham, Selfconsistent equations including
exchange and correlation effects, Phys. Rev. 140, A11331138 (1965).
) 4 ( . .......... .......... .......... ) (
) , (
)] ( [
= + r
r
r
ks
S
V
n
n T
) 5 ( .... .......... .......... ) ( ) (
) (
) ( r r
r r
r
r r
ext xc ks
V V
n
d V + +
=
) 6 ( .......... .......... ..........
) , (
)] ( [
) (
r
r
r
n
n E
V
xc
xc
=
KohnSham Equations
Considering the relation given in Eq. (4), one can construct the
following hamiltonian for the auxiliary independent particle (non
interacting) system:
The density of this auxiliary noninteracting particle system can be
constructed by the sum of squares of the orbitals for each spin.
where is the spin variable.
The independentparticle kinetic energy is given by
) 8 ( .... .......... ) ( ) ( 2
) ( ) ( ) ( ) , ( ) (
1
2
1
2
1 1
2
2
= 
\

=
=
=
=
= =
= =
occ
N N
i
i
i
i
N
i
i i
N
i
i
n r n
r r
r r r r
*
) 7 ( ..... ) (
2
1
) (
2
2
] [
2
2
r r
ks ks aux
V V
m
H H
AU ks
+ + =
h
+ = =
N N N N
=
+ =
= =
= =
= = =
N
i
i i
N
i
i i
N
i
i
N
i
i i
N
i
i i S
d d
d T
1
2 *
2
1
2 *
2
1 1
2 *
1
2
) 9 ( ..... .......... ) ( ) (
2
1
) ( ) (
2
1
) ( ) (
2
1
2
1
r r r r r r
r r r
The density of this auxiliary
particle system is the same as the
groundstate density of the full
interacting system as V
ext
remains
unchanged under the mapping.
KohnSham Equations
From the 2
nd
expression of Eq. (9):
From Eq. (8):
The eigenstates for can be found by the variational
principle subjected to the constraint of orthonormality, namely,
Thus, variation of the bra leads to:
where Using Eqs. (7) and (13), one can establish
) 10 ( ...... ) (
2
1
) (
2
*
r
r
i
i
S
T
=
) 11 ( ......... .......... .......... .......... .......... ) (
) (
) (
*
r
r
r
i
i
n
=
( )
i
)
ks aux
H H =
i
( )   ) 12 ( ... .......... 0 1
=
i i i aux i
i
H
) 13 ( ......
i i i aux
H =
.
ks aux
H H =
KohnSham Equation
) 14 ( .......... .......... ) ( ) ( ) (
2
1
) ( ) ( ) (
2
2
2
2
r r r
r r r
i i i ks
i i ks
V
V
m
AU
i
=
)
`
+
=
)
`
+
h
KohnSham Equations
Here is called the KohnSham (KS) wavefunction or orbital.
The groundstate density is obtained by solving these N non
interacting Schrdingerlike equations (Nindependent particle
equations). These equations would lead to the exact groundstate
density and energy for the real interacting system if the exact
functional V
xc
(r) (or E
xc
[n]) were known.
The most important property (or experimental observable) is the
total energy. From this quantity, one can obtain various properties,
such as equilibrium atomic structures, band structures, density of
states, phonon dispersion curves ( vs. k), etc.
i
) 16 ( ........ .......... ) ( ) (
) ( ) (
2
1
)] ( [ )] ( [
) 15 ( ..... .......... .......... )] ( [ ) ( ) ( ] [
r r r
r r
r r
r r r r
r r r r
d n V
n n
d d n T n F and
n F d n V n E
xc
s
ext
+ =
+
=
KohnSham Equations
Using the last expression of Eq. (9), Eq. (15) can be rewritten as
The sum of the singleparticle KS energy does not give the
total energy (E) because this overcounts the Hartree electronelectron
interaction energy.
where
and
where E
nn
(R) represents the interaction between ions, and .
) 17 ( .. .......... .......... )] ( [
) ( ) (
2
1
) ( ) ( ) (
2
) ( )] ( [
1
2
*
r
r r
r r
r r
r r r r r r r
n E
n n
d d
d n V d n E
xc
ext i
Nocc
i
i
+
=
=
( )
=
=
occ
i
i
1
) 18 ( .... .......... ) (
) ( ) (
2
1
1
R
r r
r r
r r
nn
Nocc
i
i
E
n n
d d E +
=
=
) 19 ( .....
) (
) ( , 2 ) (
2
1
potential Hartree
n
d V
Nocc
i
N
i
H i i
=
=
r r
r
r r
) 20 ( .... .......... .......... .......... .......... ) (
,
R R
R
z z
E
nn
. N N
occ
=
KohnSham Equations
The infinite sum in Eq. (20) converges very slowly since the Coulomb
interaction is very long ranged. There is, however, a useful technique
(a trick due to Ewald) that allows us to circumvent this problem and
to evaluate Eq. (20). I will describe this in a later chapter on the k
space formalisms of the total energy.
Since Eq. (21) is the formula actually
implemented in most DFT codes. This expression of (or )
would be exact if the exact functional were known.
+ +
)
`
+ = =
=
occ
N
i
nn xc xc H i ks
E E n V V d E E
1
) 21 .....( ) ( ) ( ) ( ) (
2
1
R r r r r
. ) ( ) ( )] ( [
= r r r r d n V n E
xc xc
ks
E
i
] [n E
xc
KohnSham Equations
Schematic
representation
of the self
consistent loop
for the solution
of KohnSham
equation. In
general, one
must iterate
two such loops
simultaneously
for the two
spins, with the
potential for
each spin.
initial guess
) ( ), ( ) ( r r r
o o
n n or n
o
+
2
) ( ) ( =
N
i
i
n r r
KohnSham Equations
* Detailed Explanations of the Computational Procedure
(1) Supply an adequate model density to start the iterative procedure.
In a solidstate system or a molecule, one could construct n
o
(r) from a
sum of atomic densities, namely,
where R
is the atomic
density of the nucleus .
(2) The external potential is typically a sum of nuclear potentials
centered at the atomic positions.
V
R r r
= n n
o
, / ) ( r z r V
=
z
) 23 ( ....... ) ( ) (
R r r
= V V
ext
KohnSham Equations
(3) The Hartree potential is given by the following integral form;
We have a couple of techniques to evaluate this integral, either by
direct integration or by solving the equivalent Poissons equation,
namely,
(4) Finally, has to be evaluated.
Numerous approximate xc functionals have appeared in the literature
over the past 30 years. Among these, the local density approximation
(LDA) is simplest of all and most commonly used.
where is the exchangecorrelation energy per electron in a
homogeneous electron gas of the density, n(r).
) 19 ( .... .......... ..........
) ( ) (
) (
3
=
r r
r
r r
r
r r
n
r d
n
d V
H
) 24 ( ... .......... .......... .......... ) ( 4 ) (
2
r r n V
H
=
) (r
xc
V ) 6 ( .....
) , (
)] ( [
) (
r
r
r
n
n E
V
xc
xc
  ) (r n
xc
= ) 25 ( ........ ) ( )] ( [ ) ( )] ( [
3
) ( r r r r r n n r d n n d E
xc xc xc
LDA
KohnSham Equations
The exchangecorrelation potential, V
xc
(r), then takes the following
form:
(5) Now that we have the KohnSham potential, we are able to solve
the KohnSham equation and to obtain the p lowest eigenstates of the
Hamiltonian, In most cases (except for an atom with a
1D differential equation), one has to diagonalize Conventional
diagonalization schemes scale N
3
with the dimension of the matrix N
which is roughly proportional to the number of atoms in the
calculations. A significant improvement in the diagonalization of
matrix (more exactly a direct minimization of the total energy) had
been achieved by Payne et al. Their iterative method scales much
better with the dimension of the matrix. Nonetheless, diagonalizing
the hamiltonian ( ) is usually the most timeconsuming part of an
ordinary KohnSham calculation.
( )
( )
) 26 ( ....... ..........
) , (
] [
) ( ] [
) (
)] ( [
) (
r
r
r
r
r
n
n
n n
n
n E
V
xc
xc
xc
xc
+ =
).
aux ks
H H =
.
ks
H
ks
H
ks
H
KohnSham Equations
(References for diagonalization or minimization) (1) M. C. Payne, M. P. Teter, D.
C. Allan, T. A. Arias, and J. D. Joannopoulos, Iterative Minimization Techniques for
ab initio TotalEnergy Calculations: Molecular Dynamics and Conjugate Gradients,
Review of Modern Physics, Vol. 64, pp. 10451097 (1992). (2) G. Kresse and D.
Joubert, From Ultrsoft Pseudopotentials to the Projector AugmentedWave Method,
Phys. Rev. B, Vol. 59, pp. 17581775 (1999).
(6) Once the KS equation is solved, one can compute the electronic
density by The selfconsistency cycle is stopped
when some convergence criterion is reached. The two most common
criteria are based on the difference of total energies or densities from
iteration i and i1. The cycle is stopped when
or where designate user defined tolerances.
If, on the contrary, the criteria have not been fulfilled, one has to
restart the self consistency cycle with a new density. The simplest
but useful approach is a linear mixing scheme given by
. ) ( ) (
2
=
Nocc
i
i
n r r
E
i i
E E <
) 1 ( ) (
,
) 1 ( ) ( 3
n
i i
n n r d <
KohnSham Equations
This is the best choice in the absence of other information.
(7) At the end of the calculations, one can evaluate several
observables, the most important of which is the total energy given by
Eq. (21). From this quantity, one can obtain many useful physical
observables that include equilibrium atomic configurations, band
structures, orbitalresolved density of states, 3D electrondensity
contours, phonon dispersion curves, dielectric responses, and
ionization potentials, to name a few.
) 27 ( ....... ) ( ) 1 (
1
in
i
out
i
in
i
in
i
out
i
in
i
n n n n n n + = + =
+