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Alternatively,
dr
| i < h | H
| i = h | H
+ V
V
| i
E = h | H
= E +
dr
| []i = T [] + U []
F [] = h [] | T + U
As shown above, the energy can be expressed as
E [] = F [] +
dr(r)v(r)
+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.
6
Z
dr(r) N
E []
=0
(r)
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
1
dr(r)v(r) +
2
(r)(r )
drdr
+ Exc []
|rr |
(r)dr = N ; (i)N
i=1 / i | j = ij /(r) =
N
X
i(r)i(r)
i=1
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 |
Its
(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
11
xc[]
1. Devise: Exc [] vxc (r) = (
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
12
Eee =
2(r, r )
drdr
|r r|
N (N 1)
2(r1, r2) =
2
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 }
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|
1
dr(r)v(r) + J [] +
2
(r1)xc(r1, r2)
dr1r2
|r1 r2|
16
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.
17
(r) xc[(r)]dr
Z R1
1
0 xc (r1 , r2)d dr
xc[(r1)] =
2
2
|r1 r2|
3 3(r)
4
!1/3
WN
V
[] = F []
c
18
dr(r)xc , , , , , , . . .
Jacobs ladder
DFT heaven
...
...
...
meta-GGA: . . . , (r)
GGA: . . . , (r)
LSDA: (r)
Hartree world
Exc
=
dr1(r1)
Exc =
"Z
Z 1
0
xc (r1 , r2)
|r1 r2|
dr2
d
Exc
20
21
Doubly Hybrid Functionals: (final) fifth-rung functionals because they add information about the
unoccupied Kohn-Sham orbitals.
22
M
P
2
LDA
Ec
+ c3 Ec
+ c4EcGGA
Y.
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)
24
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
Wavefunction and Density Approaches to Get the Best of both Worlds, Phys.
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)
25