Funtionals in DFT PDF

Functionals in DFT
Miguel A. L. Marques
1
LPMCN, Universit e Claude Bernard Lyon 1 and CNRS, France
2
European Theoretical Spectroscopy Facility
Les Houches 2012
M. A. L. Marques (Lyon) XC functionals Les Houches 2012 1 / 63
Overview
1
Introduction
2
Jacobs ladder
LDA
GGA
metaGGA
Hybrids
Orbital functionals
3
What functional to use
4
Functional derivatives
5
Functionals for v
xc
6
Availability
Outline
1
Introduction
2
Jacobs ladder
LDA
GGA
metaGGA
Hybrids
Orbital functionals
3
4
5
Functionals for v
xc
6
Availability
What do we need to approximate?
In DFT the energy is written as
E = T
s
+
d
3
r v
ext
(r)n(r) + E
Hartree
+ E
x
+ E
c
In Kohn-Sham theory we need to approximate E
x
[n] and
E
c
[n]
In orbital-free DFT we also need T
s
[n]
The questions I will try to answer in these talks are:
Which functionals exist and how are they divided in
families?
How to make a functional?
Which functional should I use?
E = T
s
+
d
3
r v
ext
(r)n(r) + E
Hartree
+ E
x
+ E
c
x
[n] and
E
c
[n]
s
[n]
families?
E = T
s
+
d
3
r v
ext
(r)n(r) + E
Hartree
+ E
x
+ E
c
x
[n] and
E
c
[n]
s
[n]
families?
Outline
1
Introduction
2
Jacobs ladder
LDA
GGA
metaGGA
Hybrids
Orbital functionals
3
4
5
Functionals for v
xc
6
Availability
The families Jacobs ladder
Marc Chagall Jacobs dream
Cmical Hean
Cmical Hean
LDA
Cmical Hean
LDA
GGA
Cmical Hean
LDA
GGA
mGGA
Cmical Hean
LDA
GGA
mGGA
Occ. orbitals
Cmical Hean
LDA
GGA
mGGA
Occ. orbitals
All orbitals
Cmical Hean
LDA
GGA
mGGA
Occ. orbitals
All orbitals
Many-body
Semi-empirical
The true ladder!
(M. Escher Relativity)
Lets start from the bottom: the LDA
In the original LDA from Kohn and Sham, one writes the xc
energy as
E
LDA
xc
=
d
3
r n(r)e
HEG
xc
(n(r))
The quantity e
HEG
xc
(n), exchange-correlation energy per unit
particle, is a function of n. Sometimes you can see appearing
HEG
xc
(n(r)), which is the energy per unit volume. They are
related
HEG
xc
(n) = n e
HEG
xc
(n)
The exchange part of e
HEG
is simple to calculate and gives
e
HEG
x
=
3
4
3
2
2/3
1
r
s
with r
s
the Wigner-Seitz radius
r
s
=
3
4n
1/3
What about the correlation
It is not possible to obtain the correlation energy of the HEG
analytically, but we can calculate it to arbitrary precision
numerically using, e.g., Quantum Monte-Carlo.
D. M. Ceperley and B. J. Alder, Phys. Rev. Lett. 45, 566 (1980)
The ts you should know about
1980: Vosko, Wilk & Nusair
1981: Perdew & Zunger
1992: Perdew & Wang (do not mix with the GGA from 91)
These are all ts to the correlation energy of Ceperley-Alder.
They differ in some details, but all give more or less the same
results.
There are also versions of PZ and PW tted to the more recent
(and precise) Monte-Carlo results of Ortiz & Ballone (1994).
But how does one make such ts?
results.
results.
results.
An example: Perdew & Wang
The strategy:
The spin [ = (n
)/n] dependence is taken from VWN,

that obtained it from RPA calculations.
The 3 different terms of this expression are t using an
educated functional form that depends on several
parameters
Some of the coefcients are chosen to fulll some exact
conditions.
The high-density limit (RPA).
The low-density expansion.
The rest of the parameters are tted to Ceperley-Alder
numbers.
An example: Perdew & Wang
Perdew and Wang parametrized the correlation energy per unit
particle:
e
c
(r
s
, ) = e
c
(r
s
, 0) +
c
(r
s
)
f ()
f
(0)
(1
4
) + [e
c
(r
s
, 1) e
c
(r
s
, 0)]f ()
4
The function f () is
f () =
[1 + ]
4/3
+ [1 ]
4/3
2
2
4/3
2
,
while its second derivative f
(0) = 1.709921. The functions e

c
(r
s
, 0),
e
c
(r
s
, 1), and
c
(r
s
) are all parametrized by the function
g = 2A(1 +
1
r
s
) log
1 +
1
2A(
1
r
1/2
s
+
2
r
s
+
3
r
3/2
s
+
4
r
2
s
)

How good are the LDAs
In spite of their simplicity, the LDAs yield extraordinarily good
results for many cases, and are still currently used. However,
they also fail in many cases
Reaction energies are not to chemical accuracy
(1 kcal/mol).
Tends to overbind (bonds too short).
Electronic states are usually too delocalized.
Band-gaps of semiconductors are too small.
Negative ions often do not bind.
No van der Waals.
etc.
Many of these two problems are due to:
The LDAs have the wrong asymptotic behavior.
The LDAs have self-interaction.
How good are the LDAs
In spite of their simplicity, the LDAs yield extraordinarily good
results for many cases, and are still currently used. However,
they also fail in many cases
Reaction energies are not to chemical accuracy
(1 kcal/mol).
Tends to overbind (bonds too short).
Electronic states are usually too delocalized.
Band-gaps of semiconductors are too small.
Negative ions often do not bind.
No van der Waals.
etc.
Many of these two problems are due to:
The LDAs have the wrong asymptotic behavior.
The LDAs have self-interaction.
The wrong asymptotics
For a nite system, the electronic density decays asymptotically
(when one moves away from the system) as
n(r) e
r
where is related to the ionization potential of the system. As
most LDA are simple rational functions of n, also e
LDA
xc
and the
v
LDA
xc
decay exponentially.
However, one knows from very simple arguments that the true
e
xc
(r)
1
2r
Note that most of the more modern functionals do not solve this
problem.
The wrong asymptotics
For a nite system, the electronic density decays asymptotically
(when one moves away from the system) as
n(r) e
r
where is related to the ionization potential of the system. As
most LDA are simple rational functions of n, also e
LDA
xc
and the
v
LDA
xc
decay exponentially.
However, one knows from very simple arguments that the true
e
xc
(r)
1
2r
Note that most of the more modern functionals do not solve this
problem.
The self-interaction problem
For a system composed of a single electron (like the hydrogen
atom), the total energy has to be equal to
E = T
s
+
d
3
r v
ext
(r)n(r)
which means that
E
Hartree
+ E
x
+ E
c
= 0
In particular, it is the exchange term that has to cancel the
spurious Hartree contribution.
The rst rung where it is possible to cancel the self-interaction
is the meta-GGA.
Beyond the LDA: the GEA
To go beyond the LDA, for many years people tried the
so-called Gradient Expansion Approximations. It is a
systematic expansion of e
xc
in terms of derivatives of the
density. In lowest order we have
e
GEA
xc
(n, n, ) = e
LDA
xc
+ a
1
(n)|n|
2
+
Using different approaches, people went painfully to sixth order
in the derivatives.
Results were, however, much worse than the LDA. The reason
was, one knows now, sum rules!
Beyond the LDA: the GEA
To go beyond the LDA, for many years people tried the
so-called Gradient Expansion Approximations. It is a
systematic expansion of e
xc
in terms of derivatives of the
density. In lowest order we have
e
GEA
xc
(n, n, ) = e
LDA
xc
+ a
1
(n)|n|
2
+
Using different approaches, people went painfully to sixth order
in the derivatives.
Results were, however, much worse than the LDA. The reason
was, one knows now, sum rules!
the GGAs
The solution to this dilemma was the Generalized Gradient
Approximation:
Soften the requirement of having rigorous derivations and
controlled approximations, and dream up a some more or
less justied expression that depends on n and some
free parameters.
Or, mathematically
E
GGA
xc
=
d
3
r n(r)e
GGA
xc
(n(r), n)
Probably the rst modern GGA for the xc was by Langreth &
Mehl in 1981.
the GGAs
The solution to this dilemma was the Generalized Gradient
Approximation:
Soften the requirement of having rigorous derivations and
controlled approximations, and dream up a some more or
less justied expression that depends on n and some
free parameters.
Or, mathematically
E
GGA
xc
=
d
3
r n(r)e
GGA
xc
(n(r), n)
Probably the rst modern GGA for the xc was by Langreth &
Mehl in 1981.
How to design an GGAs
Write down an expression that obey some exact constrains
such as
reduces to the LDA when n = 0.
is exact for some reference system like the He atom
has some known asymptotic limits, for small gradients,
large gradients, etc.
obeys some known inequalities like the Lieb-Oxford bound
E
x
[n]
E
LDA
x
[n]

etc.
Exchange functionals
Exchange functionals are almost always written as
E
GGA
x
[n] =
d
3
r n(r)e
LDA
(n(r))F(x(r))
with the reduced gradient
x(r) =
|n(r)|
n(r)
4/3
Furthermore, they obey the spin-scaling relation for exchange
E
x
[n
, n
] =
1
2
(E
x
[2n
] + E
x
[2n
])
It is relatively simple to come up with and exchange GGA, so it
is not surprising that there are more than 50 different versions
in the literature.
Example: B88 exchange
Beckes famous 88 functional reads
F
B88
x
(x
) = 1 +
1
A
x
x
2
1 + 6x
arcsinh(x
)
,
where
For small x fullls the gradient expansion.
The energy density has the right asymptotics.
The parameter was tted to the exchange energies of
noble gases.
By far the most used exchange functional in quantum
chemistry.
Example: PBE exchange
The exchange part of the Perdew-Burke-Erzernhof functional
reads:
F
PBE
x
(x
) = 1 +
1

+ s
2
,
where
The parameter s = |n|/2k
F
n.
To recover the LDA response, =
2
/3 0.21951.
Obeys the local version of the Lieb-Oxford bound.
F
PBE
x
(s) 1.804.
(Note that Becke 88 violates strongly and shamelessly this
requirement.)
By far the most used exchange functional in physics.
Local behavior
Unfortunately, locally most GGA exchange functionals are
completely wrong
Correlation functionals
Correlation functionals are much harder to design, so there
are many less in the literature (around 20).
For correlation there is no spin sum-rule, so the spin
dependence is much more complicated.
Even if the correlation energy is 5 smaller than
exchange, it is important as energy differences are of the
same order of magnitude.
Example: LYP correlation
The starting point is the Colle-Salvetti correlation functional
From an ansatz to the many-body wave-function.
Approximate the one- and two-particle density matrices.
Approximate the Coulomb hole.
Fudge the resulting formula and perform a dubious t to the
He atom.
The results is a meta-GGA (i.e. it depends on ).
Lee-Yang-Parr transformed the meta-GGA of Colle-Salvetti
by using the gradient expansion of the kinetic energy
density leading to a functional depending on
2
n.
Later it was found that the
2
n term could be rewritten by
integrating by parts, leading to the current LYP GGA
functional.
He atom.
2
n.
2
functional.
He atom.
2
n.
2
functional.
He atom.
2
n.
2
functional.
He atom.
2
n.
2
functional.
He atom.
2
n.
2
functional.
He atom.
2
n.
2
functional.
He atom.
2
n.
2
functional.
Example: PBE correlation
Conditions:
Obeys the second-order gradient expansion.
In the rapidly varying limit correlation vanishes.
Correct density scaling to the high-density limit.
E
PBE
c
=
d
3
r n(r)
e
HEG
c
+ H
where
H =
3
log
1 +

t
2
1 + At
2
1 + At
2
+ A
2
t
4
and
A =

exp{e
HEG
c
/(
3
)} 1
1
The metaGGAs
To go beyond the GGAs, one can try the same trick and
increase the number of arguments of the functional. In this
case, we use both the Laplacian of the density
2
n and
the kinetic energy density
=
occ.
i
1
2
||
2
Note that there are several other possibilities to dene
that lead to the same (integrated) kinetic energy, but to
different local values.
Often, the variables appear in the combination
W
,
where
W
=
|n|
2
8n
is the von Weizs acker kinetic energy.
This is also the main quantity entering the electron
localization function (ELF).
The electron localization function
A. Savin, R. Nesper, S. Wengert, and T, F. F assler, Angew. Chem. Int. Ed. Engl. 36, 1808 (1997)
The most used metaGGAs
TPSS (Tao, Perdew, Staroverov, Scuseria) John
Perdews school of functionals, i.e, many sum-rules and
exact conditions. It is based on the PBE.
M06L (Zhao and Truhlar) This comes from Don Truhlars
group, and it was crafted for main-group thermochemistry,
transition metal bonding, thermochemical kinetics, and
noncovalent interactions.
VSXC (Van Voorhis and Scuseria) Based on a density
matrix expansion plus tting procedure.
etc.
Hybrid functionals
The experimental values of some quantities lie often between
they Hartree-Fock and DFT (LDA or GGA) values. So, we can
try to mix, or to hybridize both theories.
1
Write an energy functional:
E
xc
= aE
Fock
[
i
] + (1 a)E
DFT
[n]
2
Minimize energy functional w.r.t. to the orbitals:
v
xc
(r, r
) = av
Fock
(r, r
) + (1 a)v
DFT
(r)
Note: for pure density functionals, minimizing w.r.t. the orbitals
or w.r.t. the density gives the same, as:
F[n]
F[n]
n
n
=
F[n]
n

A short history of hybrid functionals
1993: The rst hybrid functional was proposed by Becke,
the B3PW91. It was a mixture of Hartree-Fock with LDA
and GGAs (Becke 88 and PW91). The mixing parameter is
1/5.
1994: The famous B3LYP appears, replacing PW91 with
LYP in the Becke functional.
1999: PBE0 proposed. The mixing was now 1/4.
2003: The screened hybrid HSE06 was proposed. It gave
much better results for the band-gaps of semiconductors
and allowed the calculation of metals.
What is the mixing parameter?
Let us look at the quasi-particle equation:
2
2
+ v
ext
(r) + v
H
(r)
QP
i
(r)+
d
3
r
(r, r
;
QP
i
)
QP
i
(r
) =
QP
i

QP
i
(r
)
And now let us look at the different approximations:
COHSEX:
=
occ
QP
i
(r)
QP
i
(r
)W(r, r
; = 0) + (r r
)
COH
(r)
Hybrids
=
occ
QP
i
(r)
QP
i
(r
)a v(r r
) + (r r
)(1 a) v
DFT
(r)
So, we infer that a 1/
!
Does it work (a = 1/
)?

0

5

1
0

1
5

2
0
0 5 10 15 20
T
h
e
o
r
e
t
i
c
a
l

g
a
p

(
e
V
)
Experimental gap (eV)
y=x
PBE
PBE0
PBE0
Errors: PBE (46%), Hartree-Fock (230%), PBE0 (27%), PBE0
(16.53%)
Problems with traditional hybrids
Hybrids certainly improve some properties of both molecules
and solids, but a number of important problems do remain. For
example:
For metals, the long-range part of the Coulomb interaction
leads to a vanishing density of states at the Fermi level due
to a logarithmic singularity (as Hartree-Fock).
For semiconductors, the quality of the gaps varies very
much with the material and the mixing.
For molecules, the asymptotics of the potential are still
wrong, which leads to problems, e.g. for charge transfer
states.
Splitting of the Coulomb interaction
The solution is to split the Coulomb interaction in a short-range
and a long-range part:
1
r
12
=
1 erf(r
12
)
r
12
. .. .
short range
+
erf(r
12
)
r
12
. .. .
long range
We now treat the one of the terms by a standard DFT functional
and make a hybrid out of the other. There are two possibilities
1
DFT: long-range; Hybrid: short-range. Such as HSE, good
for metals.
2
DFT: short-range; Hybrid: long-range. The LC functionals
for molecules.
A screened hybrid: the HSE
The Heyd-Scuseria-Ernzerhof functional is written as
E
HSE
xc
= E
HF, SR
x
() + (1 )E
PBE, SR
x
() + E
PBE, LR
x
() + E
PBE
c
The most common version of the HSE chooses = 0.11 and
= 1/4. Mind that basically every code has a different
version of the HSE.
For comparison, here are the average percentual errors for the
gaps of a series of semiconductors and insulators
PBE HF+c PBE0 HSE06 G
0
W
0
47% 250% 29% 17% 11%
Gaps with the HSE

0

5

1
0

1
5

2
0
0 5 10 15 20
T
h
e
o
r
e
t
i
c
a
l

g
a
p

(
e
V
)
N
e
A
r
,

L
i
F
K
r
X
e
C
S
i
,

M
o
S
2
G
e
L
i
C
l
M
g
O
B
N
,

A
l
N
G
a
N
G
a
A
s
S
i
C
,
C
d
S
,
A
l
P
Z
n
S
Z
n
O
S
i
O
2
y=x
PBE
PBE0
PBE0
PBE0
mix
TB09

0

5

1
0

1
5

2
0
0 5 10 15 20
T
h
e
o
r
e
t
i
c
a
l

g
a
p

(
e
V
)
N
e
A
r
,

L
i
F
K
r
X
e
C
S
i
,

M
o
S
2
G
e
L
i
C
l
M
g
O
B
N
,

A
l
N
G
a
N
G
a
A
s
S
i
C
,
C
d
S
,
A
l
P
Z
n
S
Z
n
O
S
i
O
2
y=x
HSE06
HSE06
mix
Parenthesis: Mind the GAP!
The band gap of CuAlO
2
The agreement of
LDA+U and HSE06
hybrid functional to the
experiment is accidental
ScGW shows that the
band gaps are much
higher
Experimental data are
for optical gap: exciton
binding energy 0.5 eV
Agreement with
experiment can only be
achieved by the addition
of phonons.
LDA LDA+U B3LYP HSE03 HSE06 G
0
W
0
scGW scGW+P
0
1
2
3
4
5
6
E
g

[
e
V
]
E
g
indirect
E
g
direct
=E
g
direct
-E
g
indirect
exp. direct gap
exp. indirect
gap
3.5 eV (exp) = 5eV (el. QP)
- 0.5 eV (excitons)
- 1 eV (phonons)
F. Trani et al, PRB 82, 085115 (2010);
J. Vidal et al, PRL 104, 136401 (2010)
The band gap of CuAlO
2
The agreement of
LDA+U and HSE06
hybrid functional to the
experiment is accidental
ScGW shows that the
band gaps are much
higher
Experimental data are
for optical gap: exciton
binding energy 0.5 eV
Agreement with
experiment can only be
achieved by the addition
of phonons.
LDA LDA+U B3LYP HSE03 HSE06 G
0
W
0
scGW scGW+P
0
1
2
3
4
5
6
E
g

[
e
V
]
E
g
indirect
E
g
direct
=E
g
direct
-E
g
indirect
exp. direct gap
exp. indirect
gap
3.5 eV (exp) = 5eV (el. QP)
- 0.5 eV (excitons)
- 1 eV (phonons)
F. Trani et al, PRB 82, 085115 (2010);
J. Vidal et al, PRL 104, 136401 (2010)
CAM functionals
For LC functionals to have the right asymptotics they need
= 1. This value is however too large in order to obtain good
results for several molecular properties. To improve this
behavior one needs more exibility
1
r
12
=
1 [ + erf(r
12
)]
r
12
. .. .
short range
+
+ erf(r
12
)
r
12
. .. .
long range
The asymptotics are now determined by + . Note that this
form leads to a normal hybrid for = 0 and to a screened
hybrid for = 0.
CAM-B3LYP
The most used CAM functional is probably CAM-B3LYP that is
constructed in a similar way to B3LYP, but with
= 0.19 = 0.46 = 0.33
This functional gives very much improved charge transfer
excitations. Note that in any case + = 0.65 = 1, which
means that the asymptotics are still wrong.
The problem, as it often happens in functional development, is
that CAM-B3LYP is better for change transfer, but worse for
many other properties...
CAM-B3LYP
The most used CAM functional is probably CAM-B3LYP that is
constructed in a similar way to B3LYP, but with
= 0.19 = 0.46 = 0.33
This functional gives very much improved charge transfer
excitations. Note that in any case + = 0.65 = 1, which
means that the asymptotics are still wrong.
The problem, as it often happens in functional development, is
that CAM-B3LYP is better for change transfer, but worse for
many other properties...
Orbital functionals
Self-interaction correction:
E
SIC
xc
[] = E
LDA
xc
[n
, n
i
E
LDA
xc
[|
i
(r )|
2
, 0]
1
2
d
3
r
d
3
r
|
i
(r )|
2
|
i
(r
)|
2
|r r
|
Exact-exchange:
E
exact
x
[n, ] =
1
2
jk
d
3
r
d
3
r
j
(r )
k
(r
)
k
(r )
j
(r
)
|r r
|
Outline
1
Introduction
2
Jacobs ladder
LDA
GGA
metaGGA
Hybrids
Orbital functionals
3
4
5
Functionals for v
xc
6
Availability
If you are a physicist!
You are running
Solids
If problem is small enough and code available use HSE
Otherwise use PBE SOL or AM05
However, whenever you can just stick to GW and BSE
Molecules
van der Waals: use the Langreth-Lundqvist functional (or a
variant)
Charge transfer: no good alternatives here
If problem is small enough and code available use PBE0
Time-dependent problem try LB94
Otherwise use PBE
Note that if you want to calculate response, you are basically
stuck with standard GGA functionals. In any case, stick to
functionals from the J. Perdew family.
If you are a chemist!
You are running
Solids
You are a physicist, so go back to the previous slide
Molecules
van der Waals: you might escape with Grimmes trick
Charge transfer: CAM-B3LYP
If problem is small enough use B3LYP
Otherwise use BLYP
Note that you also have a chance of getting your paper
accepted if you use a functional by G. Scuseria or D. Truhlar.
Outline
1
Introduction
2
Jacobs ladder
LDA
GGA
metaGGA
Hybrids
Orbital functionals
3
4
5
Functionals for v
xc
6
Availability
What do we need for a Kohn-Sham calculation?
The energy is usually written as:
E
xc
=
d
3
r
xc
(r ) =
d
3
r n(r )e
xc
(r )
and the xc potential that enters the Kohn-Sham equations is
dened as
v
xc
(r) =
E
xc
n(r)
if we are trying to solve response equations then also the
following quantities may appear
f
xc
(r, r
) =

2
E
xc
n(r)n(r
)
k
xc
(r, r
, r
) =

3
E
xc
n(r)n(r
)n(r
)
And lets not forget spin...
What do we need for a Kohn-Sham calculation?
The energy is usually written as:
E
xc
=
d
3
r
xc
(r ) =
d
3
r n(r )e
xc
(r )
and the xc potential that enters the Kohn-Sham equations is
dened as
v
xc
(r) =
E
xc
n(r)
if we are trying to solve response equations then also the
following quantities may appear
f
xc
(r, r
) =

2
E
xc
n(r)n(r
)
k
xc
(r, r
, r
) =

3
E
xc
n(r)n(r
)n(r
)
And lets not forget spin...
Derivatives for the LDA
For LDA functionals, it is trivial to calculate these functional
derivatives. For example
v
LDA
xc
(r ) =
d
3
r
n(
r)e
HEG
xc
(n(
r))
n(r)
=
d
3
r
d
dn
ne
LDA
xc
(n)
n=n(
r )
(r
r)
=
d
dn
ne
LDA
xc
(n)
n=n(r )
Higher derivatives are also simple:
f
LDA
xc
(r ) =
d
2
d
2
n
ne
LDA
xc
(n)
n=n(r )
k
LDA
xc
(r ) =
d
3
d
3
n
ne
LDA
xc
(n)
n=n(r )
Derivatives for the GGA
For the GGAs it is a bit more complicated
v
GGA
xc
(r ) =
d
3
r
n(
r)e
GGA
xc
(n(
r), n(
r))
n(r)
=
d
3
r

n
ne
GGA
xc
(n, n)
n=n(
r )
(r
r)
+ n

n
e
GGA
xc
(n, n)
n=n(
r )
(r
r)
=

n
ne
LDA
xc
(n, n)
n=n(r )

(n)
ne
LDA
xc
(n, n)
n=n(r )
with similar expressions for f
xc
and k
xc
.
Derivatives for the meta-GGAs
Meta-GGAs are technically orbital functions due to the
functional dependence on . Therefore, to calculate correctly
v
xc
within DFT one has to resort to the OEP procedure (see
next slide). However, the expression that one normally uses is
v
mGGA
xc,i
(r) =
1
i
(r)
E
xc
i
(r)
This denition gives the correct potentials for the case of an
LDA or a GGA, as
1
i
(r)
E
xc
[n]
i
(r)
=
1
i
(r)
d
3
r
E
xc
[n]
n(
r)
n(
r)
i
(r)
=
1
i
(r)
d
3
r
E
xc
[n]
n(
r)

i
(
r)(r
r)
=
E
xc
[n]
n(r)
The optimized effective method
If E
xc
depends on the KS orbitals, we have to use the chain-rule
E
xc
n(r)
=
d
3
r
E
xc
v
KS
(r)
v
KS
(r)
n(r)
The second term is the inverse non-interacting density
response function. Using again the chain-rule
E
xc
n(r)
=
d
3
r
d
3
r

j
E
xc
j
(r
j
(r
)
v
KS
(r)
v
KS
(r)
n(r)
The second term can be calculated with perturbation theory.
Now, multiplying by and after some algebra, we arrive at:
The OEP equation
The OEP integral equation is then written as
d
3
r
Q(r, r
)v
OEP
xc
= (r)
where
Q(r, r
) =
N
j =1
j
(r
)G
j
(r
, r)
j
(r ) + c.c
(r) =
N
j =1
d
3
r
j
(r
)u
xc,j
(r
)
j
(r ) + c.c
and
G
j
(r
, r) =
k=j
k
(r
k
(r)
j

k
u
xc,j
(r
) =
1
j
(r
)
E
xc
j
(r
)
The KLI approximation
One way of performing this approximation consists in
approximating
G
j
(r
, r)
k=j
k
(r
k
(r)
=
1
(r r
)
j
(r)
j
(r
which leads to a very simple expression for the xc potential

v
KLI
xc
=
j
n
j
(r)
n(r)
u
xc,j
(r) +

v
KLI
xc,j

u
KLI
xc,j
The KLI approximation is often an excellent approximation to

the OEP potential.
Outline
1
Introduction
2
Jacobs ladder
LDA
GGA
metaGGA
Hybrids
Orbital functionals
3
4
5
Functionals for v
xc
6
Availability
The van Leeuwen-Baerends GGA
It can be proved that it is impossible to get, at the same time,
the correct asymptotics for E
x
and v
x
using a GGA form. Most
of the functionals are concerned by the energy, but it is also
possible to write down directly a functional for v
xc
.
This was done by van Leeuwen and Baerends in 1994 that
used a form similar to Becke 88
v
LB94
xc
(x
) = v
LDA
xc
n
1/3
x
2
1 + 3x
arcsinh(x
)
,
This functional is particularly useful when calculating, e.g.,
ionization potentials from the value of the HOMO, or when
performing time-dependent simulations with laser elds.
The Becke-Roussel functional
Meta-GGA energy functional (depends on
n, n,
2
n, ).
Models the exchange hole of hydrogenic
atoms.
Correct asymptotic 1/r behavior for nite
systems.
Excellent description of the Slater part of
the EXX potential.
Exact for the hydrogen atom
AD Becke and MR Roussel, Phys. Rev. A 39, 3761 (1989)
The Becke-Johnson functional
At this point, it is useful to write the (KS) exchange potential as
a sum
v
x
(r) = v
SL
x
(r) + v
OEP
x
(r)
The BJ potential is a simple approximation to the OEP
contribution
v
OEP
x
(r) v
BJ
x
(r) = C
v
(r)
n
(r)
where C
v
=
5/(12
2
)
Exact for the hydrogen atom and for the HEG.
Yields the atomic step structure in the exchange potential
very accurately.
It has the derivative discontinuity for fractional particle
numbers.
Goes to a nite constant at . Not gauge-invariant.
AD Becke and ER Johnson, J. Chem. Phys. 124, 221101 (2006)
The Becke-Johnson functional
At this point, it is useful to write the (KS) exchange potential as
a sum
v
x
(r) = v
SL
x
(r) + v
OEP
x
(r)
The BJ potential is a simple approximation to the OEP
contribution
v
OEP
x
(r) v
BJ
x
(r) = C
v
(r)
n
(r)
where C
v
=
5/(12
2
)
Exact for the hydrogen atom and for the HEG.
Yields the atomic step structure in the exchange potential
very accurately.
It has the derivative discontinuity for fractional particle
numbers.
Goes to a nite constant at . Not gauge-invariant.
AD Becke and ER Johnson, J. Chem. Phys. 124, 221101 (2006)
Extensions the Tran and Blaha potential
By looking at band gaps of solids, Tran and Blaha proposed
v
TB
x
(r) = cv
BR
x
(r) + (3c 2)C
v
(r)
n
(r)
where c is obtained from
c = +
1
V
cell
cell
d
3
r
|n(r)|
n(r)
1/2
Band-gaps are of similar quality as G
0
W
0
, but at the
computational cost of an LDA!
Value of c is always larger than one, as the BJ gaps are
too small.
and are tted parameters.
Parameter c creates problems of size-consistency.
F Tran and P Blaha, Phys. Rev. Lett. 102, 226401 (2009)
Extensions the Tran and Blaha potential
By looking at band gaps of solids, Tran and Blaha proposed
v
TB
x
(r) = cv
BR
x
(r) + (3c 2)C
v
(r)
n
(r)
where c is obtained from
c = +
1
V
cell
cell
d
3
r
|n(r)|
n(r)
1/2
Band-gaps are of similar quality as G
0
W
0
, but at the
computational cost of an LDA!
Value of c is always larger than one, as the BJ gaps are
too small.
and are tted parameters.
Parameter c creates problems of size-consistency.
F Tran and P Blaha, Phys. Rev. Lett. 102, 226401 (2009)
Some solutions - the RPP functional
R as anen, Pittalis, and Proetto (RPP) proposed the following
correction to the BJ potential
v
RPP
x
(r) = v
BR
x
(r) + C
v
(r)
n
(r)
where the function D is
D
(r) =
(r)
1
4
|n
(r)|
2
n
(r)

j
2
(r)
n
(r)
It is exact for all one-electron systems (and for the e-gas).
It is gauge-invariant.
It has the correct asymptotic behavior for nite systems.
E R as anen, S Pittalis, and C Proetto, J. Chem. Phys. 132, 044112 (2010)
Some solutions - the RPP functional
R as anen, Pittalis, and Proetto (RPP) proposed the following
correction to the BJ potential
v
RPP
x
(r) = v
BR
x
(r) + C
v
(r)
n
(r)
where the function D is
D
(r) =
(r)
1
4
|n
(r)|
2
n
(r)

j
2
(r)
n
(r)
It is exact for all one-electron systems (and for the e-gas).
It is gauge-invariant.
It has the correct asymptotic behavior for nite systems.
E R as anen, S Pittalis, and C Proetto, J. Chem. Phys. 132, 044112 (2010)
Benchmark of the mGGAs
Test-set composed of 17 atoms, 19 molecules, 10 H
2
chains,
and 20 solids.
LDA PBE LB94 BJ RPP TB
Ionization potentials
atoms 41 42 3.7 14.4 7.4
molecules 35 36 8.0 19 5.7
Polarizabilities
molecules 6.1 5.3 9.8 2.0 8.9
H
2
chains 56 46 54 36 28
Band gaps
52 47 35 33 7.6
(mean average relative error in %)
M. Oliveira et al, JCTC 6, 3664-3670 (2010)
Problems with these functionals
It may seem like a very nice idea to model directly v
xc
(or f
xc
).
However, it can be proved that these functionals are not the
functional derivative of an energy functional. This opens a
theoretical Pandoras box.
No unique way of calculating the energy by integration.
The energy depends on the path used. Results can vary
dramatically.
Energy is not conserved when performing a TD simulation
Zero-force and zero-torque theorems broken. Spurious
forces and torques appear during a TD simulation.
...
In any case, and even if we dont have the energy, we can have
access to all derivatives of the energy, i.e., all response
properties of the system.
Outline
1
Introduction
2
Jacobs ladder
LDA
GGA
metaGGA
Hybrids
Orbital functionals
3
4
5
Functionals for v
xc
6
Availability
Availability of functionals
The problem of availability:
There are many approximations for the xc (probably of the
order of 200250)
Most computer codes only include a very limited quantity
of functionals, typically around 1015
Chemists and Physicists do not use the same functionals!
It is therefore difcult to:
Reproduce older calculations with older functionals
Reproduce calculations performed with other codes
Perform calculations with the newest functionals
Availability of functionals
The problem of availability:
There are many approximations for the xc (probably of the
order of 200250)
Most computer codes only include a very limited quantity
of functionals, typically around 1015
Chemists and Physicists do not use the same functionals!
It is therefore difcult to:
Reproduce older calculations with older functionals
Reproduce calculations performed with other codes
Perform calculations with the newest functionals
Our solution: LIBXC
The physics:
Contains 27 LDAs, 123 GGAs, 25 hybrids, and 13 mGGAs
for the exchange, correlation, and the kinetic energy
Functionals for 1D, 2D, and 3D
Returns
xc
, v
xc
, f
xc
, and k
xc
Quite mature: in 14 different codes including OCTOPUS,
APE, GPAW, ABINIT, etc.
The technicalities:
Written in C from scratch
Bindings both in C and in Fortran
Lesser GNU general public license (v. 3.0)
Automatic testing of the functionals
Just type LIBXC in google!
Our solution: LIBXC
The physics:
Contains 27 LDAs, 123 GGAs, 25 hybrids, and 13 mGGAs
for the exchange, correlation, and the kinetic energy
Functionals for 1D, 2D, and 3D
Returns
xc
, v
xc
, f
xc
, and k
xc
Quite mature: in 14 different codes including OCTOPUS,
APE, GPAW, ABINIT, etc.
The technicalities:
Written in C from scratch
Bindings both in C and in Fortran
Lesser GNU general public license (v. 3.0)
Automatic testing of the functionals
Just type LIBXC in google!

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Functionals in DFT

)/n] dependence is taken from VWN,

(0) = 1.709921. The functions e

M. A. L. Marques (Lyon) XC functionals Les Houches 2012 12 / 63

which leads to a very simple expression for the xc potential

The KLI approximation is often an excellent approximation to

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