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# 1

Jesus M. Ugalde
Kimika Fakultatea, Euskal Herriko Unibertsitatea and Donostia
International Physics Center (DIPC); P.K. 1072, 20080 Donostia,
http://www.ehu.es/chemistry/theory

## Advanced Density Functional Theory for

Electronic Structure Calculations.
Jesus M. Ugalde
Kimika Fakultatea, Euskal Herriko Unibertsitatea, and Donostia
International Physics Center (DIPC); P.K. 1072, 20080 Donostia,
http://www.ehu.es/chemistry/theory

## The Hohenberg-Kohn Theorem

and H
be nondegenerate,
Let the ground states of H
| i < h | H
| i = h | H
+V
V
| i
E = h | H
= E+

Alternatively,

dr

| i < h | H
| i = h | H
+ V
V
| i
E = h | H
= E +

dr

## where in the last line we have used the assumption that

h | | i = (r) = h | | i
Adding the two inequalities we obtain
E + E < E + E
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## The HohenbergKohn theorem shows that the electron density

uniquely determines the external potential. But the external potential uniquely determines the wave function, through the Schr
odinger
equation. Thus, the electron density uniquely determines the wave
function, i.e: can be seen as a functional of .

## The Energy Variational Principle

Let us define:
h

| []i = T [] + U []
F [] = h [] | T + U
As shown above, the energy can be expressed as
E [] = F [] +

dr(r)v(r)

## Now consider another electrondensity (r) 6= (r), associated through

the above demonstrated onetoone relationship with another external
potential v . Then:
Z
h i
h i
h
i

## E = F + dr (r)v(r) Since is N representable

h i h
i
h i
h
i

+V
| i > h [] | T + U
+V
| []i = E []
= h | T + U

The functional Ev [] achieves its minimum value for the true ground
state electron density associated with the external potential v.
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## The Euler Equation of DFT

Variational functional:
= E []
Euler equation:

Z

dr(r) N

E []
=0
(r)

## The Chemical Potential:

E [N, (r)] E [N, v(r)]
Consequently,


E
dN +
dE =
N v

E
v(r)dr
v(r)

Use
Z

E
E
dr(r) = dN ; =
;
= (r)
N v
v(r)
to obtain the fundamental equation for the chemical reactivity:
dE = dN +

(r)v(r)dr

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## The Kohn-Sham formulation

Recall the Euler equation:
E []
= 0 ; E [] = T [] +
(r)

1
dr(r)v(r) +
2

(r)(r )

drdr
+ Exc []

|rr |

## Theorem. (T. L. Gilbert, Phys. Rev. B 12, 2111 (1975))

(r) 0,

(r)dr = N ; (i)N
i=1 / i | j = ij /(r) =

N
X

i(r)i(r)

i=1

## Consider the non-interacting system described by the single Slater de,

orbitals
and
estimate
its
kinetic
energy
i=1
namely:
N
X

1 2
hi | | ii
Ts =
2
i=1
and express the energy of the real system as:
E [] = Ts [] +

1
(r)v(r)dr +
2

)
(
r
)(
r
+ Exc []
drdr
| r r |

## Exc [] = Exc [] + (T [] Ts [])

The exchange-correlation functional contains some
undetermined kinetic energy

Its

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## The expression for the Euler equation is:

Ts []
+ v(r) +
(r)
|

(r)dr
Exc []
= s
+

|rr |
(r)
{z
vef f (r)

The Kohn-Sham presciption: Determine Exc [] to obtain a workable expression for vef f (r). Then, the (r) can be obtained by solving the
non-interacting system:
h

i
1
2
2 i + vef f (r) i = ii; i = 1, N

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## The Kohn-Sham Implementation

E

xc[]
1. Devise: Exc [] vxc (r) = (
r)

## 2. Make a guess for the Kohn-Sham orbitals {i}N

i=1
R (r)dr
Build: vef f (r) = v(r) + |rr| + vxc (r)

Solve:

i
1
2
2 i + vef f (r) i = ii, i = 1, N ; until consistency

3. Calculate: E [] = Ts [] +

R
(r)(r)
1

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Eee =

2(r, r )
drdr
|r r|

N (N 1)
2(r1, r2) =
2

## |(r1, r2, . . . , rN )|2 dr3 . . . drN

2(r1, r2) =

1
Eee [] =
2

1
(r1) [(r2) + xc(r1, r2)]
2

(r)(r ) 1
(r)xc (r, r )
+
= J []+
drdr
drdr
|r r|
2
|r r|

E
[ ]
| xc{z }

## [Exc [](T []Ts [])]

13

= T + V
+ U
, 0 1
H

14

= T + V
+ U
, 0 1
H

V / |
|

=0 = vef f (r), V
=1 = v(r)
= (r), . Hence :V

Z 1
E

=
dH

E
d =

dr(r)

H
d =

d = E=1 E=0

d
d + U

1
1
d + dJ [] + d
2
2

(r1)
xc (r1 , r2 )
dr1r2
|r1 r2|
15

E=1E=0 =

dr(r)

Z 1
0

1
1
d+ J []+
2
2

E=0 = TS +

E=1 = TS +

R
(r1) 01
xc (r1 , r2)d
dr1r2
|r1 r2|

dr(r)V =0

1
=1
dr(r)V
(r) + J [] +
2

(r1)
xc(r1, r2)
dr1r2
|r1 r2|

## But, recall that the original expresson for E=1 E

E=T +

1
dr(r)v(r) + J [] +
2

(r1)xc(r1, r2)
dr1r2
|r1 r2|
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## Same expressions upon consideration of the following equivalencies:

R1

TS xc(r1, r2) = 0
xc(r1, r2)d
T xc(r1, r2)
The adiabatic connection has adsorbed the excess kinetic energy term into an exchangecorrelation hole description.

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## The Local Density Approximation

Exc[(r)] =

(r) xc[(r)]dr

Z R1
1
0 xc (r1 , r2)d dr
xc[(r1)] =
2
2
|r1 r2|

LDA
[] =
x

3 3(r)
4

!1/3

WN
V
[] = F []
c

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## Practical Approximate Exchange-Correlation Functionals

Exc =

dr(r)xc , , , , , , . . .

DFT heaven
...
...
...
meta-GGA: . . . , (r)
GGA: . . . , (r)
LSDA: (r)
Hartree world

## And he dreamed, and behold a ladder set up on the earth, and

the top of it reached to heaven... (Gen 28:12)
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Exc
=

dr1(r1)

Exc =

"Z

Z 1
0

xc (r1 , r2)
|r1 r2|

dr2

d
Exc

20


1  =0
=1
Exc + Exc
Exc
2

## =0 Hartree-Fock like exchange with the Kohn-Sham orbitals

Exc
=1 Exchange-correlation functional
Exc

## Better Approximate Hybrid Functionals:

Hybrid = (1 a )E DF T + a E HF + E DF T
Exc
x
x x
x
c

## B3LYP Approximate Hybrid Functional:

B3LY P
LDA
Exc
= Exc
+a0(ExHF ExLDA)+ax(ExB88 ExLDA)+ac(EcLY P EcLDA)

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Doubly Hybrid Functionals: (final) fifth-rung functionals because they add information about the
unoccupied Kohn-Sham orbitals.

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## Doubly hybrid density functional for accurate descriptions of

nonbond interactions, thermochemistry, and thermochemical
kinetics
R5 = E LDA
Exc
[ ]
xc


HF
LDA
+ c1 Ex Ex
+ c2ExGGA


M
P
2
LDA
Ec
+ c3 Ec
+ c4EcGGA

Y.

## Zhang, X. Xu and W. A. Goddard III; PNAS, 106, 4963 (2009)

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Computational Performance
Method
HF
DFT/LDA
DFT/GGA
DFT/Hybrid
NOF
NOF-PT
MP2
MP4
CCSD
CCSD(T)
CCSDT
CIS
CISD
CISDT
CISDTQ
MRCI
MCSCF
full CI

VE

SE

DEC
*
*
**
*
**
*
**
**
***
***
**
**
***
***
*
exact

NDEC

***
***

*
*
**

*
***
***
***
exact

CS
K 3-K 4
K 3-K 4
K 3-K 4
K 3-K 4
n K4
n K4
K5
K7
K6
K7
K8
K4
K6
K7
K8
n K6
n K6
K!

size
50 100
50 500
50 500
50 500
2030
2030
2030
1020
1030
1030
515
50100
< 10
<10
<10
<10
1525
< 5

J.M. Mercero, J.M. Matxain, X. Lopez, D.M. York, A. Largo, L. A. Eriksson, J.M. Ugalde
Int. J. Mas. Spectr. 240, 37 (2005)
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Validation
1. Sebastian Kozuch and Jan M. L. Martin, Spin-component-scaled double hybrids:
An extensive search for the best fifth-rung functionals blending DFT and perturbation theory, J. Compt. Chem. (2013), DOI: 10.1002/jcc.23391
2. J. C. Sancho-Garca and C. Adamo, Double-Hybrid density Functionals: Merging
Chem. Chem. Phys. 15, 14581 (2013)
3. Suranjan Shil, Debojit Bhattacharya, Sonali Sarkar and Anirban Misra, Performance of the Widely Used Minnesota Density Functionals for the Prediction of
Heat of Formations, Ionization Potentials of Some Benchmarked First Row Transition Metal Complexes, J. Phys. Chem. A, 117, 4945 (2013)
4. Christopher J. Cramer and Donald G. Truhlar, Density functional theory for transition metals and transition metal chemistry, Phys. Chem. Chem. Phys. 11,
10757 (2009)
5. S
ergio Filipe Sousa and Pedro Alexandrino Fernandes and Maria Jo
ao Ramos,
General Performance of Density Functionals, J. Phys. Chem. A. 111, 1049
(2007)
6. Kasper P. Jensen, Bj
orn O. Roos and Ulf Ryde, Performance of density functionals
for first row transition metal systems, J. Chem. Phys. 126 14103 (2007)
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