O Mtodo de Hartree-Fock

CF740 Tpicos Especiais de Fsica Atmica e Molecular

Clculos de Estrutura Eletrnica Utilizando Funcionais de Densidade

Departamento de Fsica
Universidade Federal do Paran

CF740 (UFPR)

PG Fsica

1 / 41

Mtodo Variacional
E0 = h0 |H|0 i, onde |0 i = |1 2 . . . a b . . . N i

H o hamiltoniano eletrnico (na aproximao de Born-Oppenheimer), dado por:

H=

N
N M
N X
X
X
1 2 X X
ZA
1
i
+
2
|r

R
|
|r

rj |
i
i
A
i=1
i=1 A=1
i=1 j>i

A energia total ento escrita na forma de um funcional dos spin-orbitais:

E0 [{a }] =

N
X

[a|h|a] +

a=1

N N
1XX
[aa|bb] [ab|ba]
2 a=1 b=1

onde
Z

dx1 a (x1 )b (x1 ) = [a|b] = ha|bi = ab

Vamos minimizar E0 [a , a ] = E0 [{a }] em relao aos spin orbitais {a } , mantendo o

vnculo acima, ou seja [a|b] = ab . Para isso vamos construir o funcional
L[{a }] = E0 [{a }]

N
N X
X

a=1 b=1

ba ([a|b] ab )

onde ba so os multiplicadores de Lagrange.

CF740 (UFPR)

PG Fsica

2 / 41

Mtodo Variacional

L[{a }] real e portanto ba = ab ([a|b] = [b|a] ).

Vamos fazer

a a + a
e impor que L[{a }] seja estacionrio, ou seja
L[{a }] = E0 [{a }]

N X
N
X

ba [a|b] = 0

a=1 b=1

Como resultado obtemos

L[{a }] =

N
X

[a |h|a ] +

a=1

CF740 (UFPR)

N X
N
X

a=1 b=1

N X
N
X

a=1 b=1

[a a |b b ] [a b |b a ]

ba [a |b ] + complexo conjugado = 0

PG Fsica

3 / 41

Mtodo Variacional

Os operadores de Coulomb Jb (1) e de troca (exchange) Kb (1) so definidos como


Z
1
b (2) a (1)
Jb (1)a (1) =
dx2 b (2)
r12
Z

1
Kb (1)a (1) =
dx2 b (2)
a (2) b (1)
r12
tal que
ha (1)|Jb (1)|a (1)i = [aa|bb]; ha (1)|Kb (1)|a (1)i = [ab|ba]
Assim L[{a }] = 0 resulta em
L[{a }] =

N Z
X

a=1

CF740 (UFPR)

dx1 a (1)

h(1)a (1) +

N
X

b=1

PG Fsica

[Jb (1) Kb (1)] a (1)

N
X

b=1

ba b (1)

+complexo conjugado = 0

4 / 41

Mtodo Variacional

Como as variaes a (1) (e a (1)) so arbitrrias o termo entre chaves se anula (o

mesmo acontence com o c.c.), resultando em
)
(
N
N
X
X
[Jb (1) Kb (1)] a (1) =
ba b (1); a = 1, 2, . . . , N
h(1) +
b=1

b=1

Definimos o operador de Fock f (1) como

f (1) = h(1) +

N
X

b=1

[Jb (1) Kb (1)]

tal que
f |a i =

N
X

b=1

ba |b i

A expresso acima representa uma equao de autovalores, mas que no est na forma
padro.

CF740 (UFPR)

PG Fsica

5 / 41

Equaes de Hartree-Fock
Vamos rodar os spin-orbitais atravs de uma transformao unitria U (U = U 1 )
X
a =
b Uba
b

Neste caso
|0 i = det(U )|0 i = exp(i)|0 i, f (1) = f (1)
o que resulta em
f |a i = a |a i
Vamos considerar as equaes de Hartree-Fock na forma cannica como
f |a i = a |a i, f = f
ou
(

h(1) +

N
X

b=1

[Jb (1) Kb (1)]

a (1) = a a (1); a = 1, 2, . . . , N

que um conjunto de equaes ntegro-diferenciais acopladas.

CF740 (UFPR)

PG Fsica

6 / 41

Autovalores
Uma vez definido o operador de Fock f temos
f |j i = j |j i, j = 1, 2, . . . ,
Qual o significado dos autovalores j ?
Considere
hi |f |j i = j hi |j i = i ij

ou

hi |f |i i

=
Em particular

hi |h +

N
X

b=1

hi|h|ii +

[Jb Kb ] |i i = hi |h|i i +

N
X

[hib|ibi hib|bii] = hi|h|ii +

b=1

a = ha|h|ai +

N
X

b6=a

b=1
N
X


hi |J b |i i hi Kb |i i =

hib||ibi = i

b=1

[hab|abi hab|bai], haa||aai = 0

r = hr|h|ri +
CF740 (UFPR)

N
X


N
X

[hrb|rbi hrb|bri]

b=1

PG Fsica

7 / 41

Autovalores

Somando
N
X

a =

a=1

N
X

ha|h|ai +

a=1

N X
N
X

[hab|abi hab|bai]

a=1 b=1

que no igual a E0
E0 =

N
X

ha|h|ai +

a=1

CF740 (UFPR)

N N
1 XX
[hab|abi hab|bai]
2 a=1 b=1

PG Fsica

8 / 41

Teorema de Koopmans

A interpretao dos autovalores do operador de Fock i dada pelo Teorema de Koopmans:

IP = EaN1 E0N = a ; EA = E0N ErN+1 = r
onde EaN1 e ErN+1 so as energias totais da molcula com (N-1)-eltrons e (N+1)-eltrons
respectivamente, obtidas com os mesmos orbitais utilizados no clculo de E0 .
|N1 a i = |1 2 . . . a1 a+1 , . . . N i
|N+1 r i = |1 2 . . . N r i

CF740 (UFPR)

PG Fsica

9 / 41

Teorema de Brillouin

Teorema de Brillouin
Excitaes simples |ra i no interagem diretamente com o estado de referncia
Hartree-Fock |0 i, isto h0 |H|ra i = 0.
h0 |H|ra i = ha|h|ri +

CF740 (UFPR)

N
X

hab||rbi = ha|f |ri = 0

b=1

PG Fsica

10 / 41

Sistemas com Camada Fechada

Para sistemas com camada fechada, podemos somar as equaes de Hartree-Fock sobre os
spins, obtendo

f (r1 )j (r1 ) = h(r1 )j (r1 ) + 2

N/2 Z

N/2 Z

r2 c (r2 )

c=1

d3 r2 c (r2 )

c=1

O operador de Fock neste caso fica

1
c (r2 ) j (r1 )
r12

1
j (r2 ) c (r1 ) = j j (r1 )
r12

N/2

f (r1 ) = h(r1 ) +

[2Ja (r1 ) Ka (r1 )]

a=1

onde
Z

d3 r2 a (r2 )

1
a (r2 )
r12

Z

d3 r2 a (r2 )


1
i (r2 ) a (r1 )
r12

Ja (r1 ) =
e
Ka (r1 )i (r1 ) =
CF740 (UFPR)

PG Fsica

11 / 41

Sistemas com Camada Fechada

Ou, de forma simples

f (1)j (1) = j j (1)
E0 fica
N/2

E0 = 2

N/2 N/2

haa +

a=1

X X

a=1 b=1

[2Jab Kab ]

i fica
N/2

i = hii +

b=1

CF740 (UFPR)

PG Fsica

[2Jib Kib ]

12 / 41

Equaes de Hartree-Fock-Roothaan

A soluo das equaes de Hartree-Fock obtida expandindo-se os orbitais moleculares i

em termos de um conjunto (no completo) composto por K orbitais atmicos { }:
i (~
r) =

K
X

Ci (~
r ); S =

=1

d~
r1 (1) (1)

Representao de funes Gaussianas Cartesianas:

~
(A)

~ 2

lmn = Nlmn (x Ax )l (y Ay )m (z Az )n e|~rA|

s : l + m + n = 0; p : l + m + n = 1; d : l + m + n = 2
Equao de Hartree-Fock-Roothaan, onde as incgnitas passam a ser os coeficientes reais
Ci .
FC = SC

CF740 (UFPR)

K
X

F Ci = i

=1

K
X

S Ci , i = 1, 2 . . . K

=1

PG Fsica

13 / 41

Equaes de Hartree-Fock-Roothaan
Matriz de Fock F
F =

core
dr~1 (1)f (1) (1) = H
+ G

Termo do core
core
core
H
= T + V

Energia cintica
T =



1
dr~1 (1) 21 (1)
2

Potencial nuclear
core
V
=

dr~1 (1)

"

M
X

=1

#
Z
(1)
|~
r1 ~
r |

Matriz G
G =

P [(|)

1
(|)]
2

Integrais de dois eltrons

(|) =

CF740 (UFPR)

Z Z

d~
r1 d~
r2 (1) (1)

PG Fsica

1
(2) (2)
|~
r1 ~
r2 |
14 / 41

Equaes de Hartree-Fock-Roothaan

Matriz densidade
N

P = 2

2
X

Ci Ci

i=1

Energia eletrnica
E0 =

1XX
core
P H
+ F
2

Energia total
Etot = E0 +

CF740 (UFPR)

X X ZA ZB
RAB
A B>A

PG Fsica

15 / 41

Etapas do processo SCF (clculo ab initio)

1
2
3
4
5
6

~ A }, {ZA }, N , e definir a base { } a ser utilizada.

Especificar a molcula, fornencendo {R
core , (|).
Calcular todas as integrais primitivas: S , H

Diagonalizar S para obter a matriz de transformao X.

P N/2
).
Fornecer um chute inicial para P (P = 2 a=1 Ca Ca
PK PK
Calcular G, usando P e (|) (G = =1 =1 P [(|) 1/2(|)]).
Formar F a partir de G e Hcore (F = Hcore + G).

Calcular F = X FX.

Diagonalizar F para obter C e .

Calcular C = XC .

10
11
12

P N/2
).
Formar nova P usando C (P = 2 a=1 Ca Ca


P
P
K
K
1
core + F
Calcular E0 e Etot (E0 = 2 =1 =1 P H
).
Determinar se o processo convergiu.

CF740 (UFPR)

PG Fsica

16 / 41

Self-consistent field (SCF)

CF740 (UFPR)

PG Fsica

17 / 41

Funes Gaussianas Cartesianas

The choice of a basis is more of an art than a science (Szabo-Ostlund).

MO-LCAO
i (~
r) =

K
X

Ci (~
r ); S =

=1

d~
r1 (1) (1)

Representao de funes Gaussianas Cartesianas:

~
(A)

~ 2

lmn = Nlmn (x Ax )l (y Ay )m (z Az )n e|~rA|

s : l + m + n = 0; p : l + m + n = 1; d : l + m + n = 2
Bases contradas:
(CGF )

~ A) =
(~
rR

CF740 (UFPR)

L
X

p=1

~ A ); gp (GF
~ A ) primitivas
dp gp (GF
rR
rR
p , ~
p , ~

PG Fsica

18 / 41

Bases contradas

(CGF )

~ A) =
(~
rR

g1s (, ~
r) =

g1px (, ~
r) =

g1dxy (, ~
r) =

p=1

83
3

~ A)
dp gp (p , ~
rR

 1/4

exp(r 2 )

1285
3

 1/4

x exp(r 2 )

20487
3

 1/4

xy exp(r 2 )

L
X

Conjuntos de base (internas ao pacote GAMESS): STO-3G, 3-21G, 4-31G, 6-31G, 6-31G ,
6-31G , 6-311G, 6-311G , 6-311G , DZV, TZV . . .

CF740 (UFPR)

PG Fsica

19 / 41

Contraes
Exemplo: contrao (4s)/[2s] para o hidrognio de Huzinaga.
primitivas (4s):
1s =

0.50907g1s (0.123317, ~r)

+

0.47449g1s (0.453757, ~r)

0.13424g1s (2.0133, ~r)

0.01906g1s (13.3615, ~r)

contraindo a (4s)/[2s]:
1 (~
r) =

g1s (0.123317, ~r )

2 (~
r) =

1s 1s =

0.817238g1s (0.453757, ~r)

+

0.231208g1s (2.0133, ~r)

0.032828g1s (13.3615, ~r)

1 + 2

tomos pesados: (9s5p)/[3s2p]

tomos pesados + hidrognio: (9s5p/4s)/[3s2p/2s]
CF740 (UFPR)

PG Fsica

20 / 41

(8s4p/4s)/[3s2p/2s] - 4-31G
Hidrognio:

1s

3
X

di,1s g1s (i,1s , ~

r)

4
X

di,1s g1s (i,1s , ~

r)

i=1

1s

1s

g1s (1s , ~
r)

Para Li at F:

i=1

2s

2s

2p

3
X

di,2s g2s (i,2s , ~

r)

3
X

di,2p g2p (i,2p , ~

r)

i=1

g2s (2s , ~
r)

i=1

2p
CF740 (UFPR)

g2p (2p , ~
r)
PG Fsica

21 / 41

6-31G e 6-31G

: funo do tipo d no tomo pesado

: funo do tipo d no tomo pesado e funo do tipo p no hidrognio.

Hierarquia das bases: STO-3G, 4-31G, 6-31G, 6-31G e 6-31G
Outras bases: DZV, TZV, 6-311G . . .
Notao: 6-311+G(1d), 6-311++G(1d)
+: funes difusas do tipo s e do tipo p no tomo pesado.
++: funes difusas do tipo s e do tipo p no tomo pesado e funo difusa do tipo s no
hidrognio.

CF740 (UFPR)

PG Fsica

22 / 41

Base mnima STO-3G

(A B |C D ) =

d~
r1

B
d~
r2 A
(1) (1)

~ A) =
GF
rR
1s (, ~

 3/4

1
C (2)D
(2)
|~
r1 ~
r2 |

h
i
~ A |2
exp |~
rR

~ A )GF
~ B ) = KAB GF
~P )
GF
rR
rR
rR
1s (, ~
1s (, ~
1s (p, ~
KAB =

2
( + )

 3/4


exp

~P =
p = + , R
(A B |C D ) = KAB KCD

CF740 (UFPR)

d~
r1

~A R
~ B |2
|R
( + )

~ A + R
~B
R
+

~P )
d~
r2 GF
r1 R
1s (p, ~

PG Fsica

1
~ Q)
GF (q, ~
r2 R
|~
r1 ~
r2 | 1s

23 / 41

Base mnima STO-3G

(CGF )

L
X

~ A) =
(~
rR

p=1

CGF
( = 1.0, ST O 3G) =
1s

~ A)
dp p (GF
rR
p , ~

0.4446351s ( = 0.109818)
+

0.5353281s ( = 0.405771)

0.1543291s ( = 2.22766)

Fator de escala dos expoentes: H = 1.24, He = 2.0925

exp[(r)] exp[( r)2 ]

CF740 (UFPR)

 1/2

= ( = 1.0) 2

PG Fsica

24 / 41

Base mnima STO-3G

H : CGF
( = 1.24, ST O 3G) =
1s

0.4446351s ( = 0.168856)
+

0.5353281s ( = 0.623913)

0.1543291s ( = 3.42525)

He : CGF
( = 2.0925, ST O 3G) =
1s

0.4446351s ( = 0.229794)
+

0.5353281s ( = 0.849076)

0.1543291s ( = 4.661379)

No GAMESS He = 1.69:
CGF
( = 1.69, ST O 3G) =
1s

CF740 (UFPR)

0.4446351s ( = 0.0.313651)
+

0.5353281s ( = 1.158922)

0.1543291s ( = 6.362420)

PG Fsica

25 / 41

Base mnima: H2

Vimos em aula, que no modelo de base mnima para a molcula de H2 temos:

1 = p

1
2(1 + S12 )

C=

(1 + 2 ); 2 = p
1
2(1+S12 )
1
2(1+S12 )

P=

S =

CF740 (UFPR)

1
1 + S12

1
1

1
2(1 S12 )

2(1S12 )
1
2(1S12 )

1
1

~ A )CGF (~
~B) =
d~
r CGF
(~
rR
rR

PG Fsica

(1 2 )

L X
L
X

dp dq Spq

p=1 q=1

26 / 41

Base mnima: H2

S=

 1s

 S12


1
0.6593
0.6593 1

S12 
= 0 s = 1 S12
1s 

s1 = 1.6593, s2 = 0.3407


0.7763 0
0
1.7133


1
1
1
U=
1 1
2

s1/2 =

CF740 (UFPR)

PG Fsica

27 / 41

Base mnima: H2

Vamos utilizar a otogonalizao cannica X = Us1/2



0.5489
1.2115
X=
0.5489 1.2115


0.5489
1.2115
C=
0.5489 1.2115


0.6027 0.6027
P=
0.6027 0.6027

CF740 (UFPR)

PG Fsica

28 / 41

H2

SCF CALCULATION FOR H2

MOLECULE

THE MAXIMUM NUMBER OF ITERATIONS IS EQUAL TO 10

THE CONVERGENCE CRITERION IS

STO-3G FOR ATOMIC NUMBERS

CF740 (UFPR)

0.10E-09

1.00 AND

PG Fsica

1.00

29 / 41

H2

ZETA1

ZETA2

S12

T11

1.400000

1.240000

1.240000

0.659319

0.760033

T12

T22

V11A

V12A

V22A

0.236455

0.760033

V11B

V12B

-0.653828

-0.597418

-1.226615

V22B
-1.226615

-0.597418

V1111

V2111

0.774608

0.444109

V2121

V2211

V2221

V2222

0.297029

0.569678

0.444109

0.774608

CF740 (UFPR)

-0.653828

PG Fsica

30 / 41

H2

THE S

ARRAY
1
2

THE X

1
0.1000000000E+01
0.6593189894E+00

2
0.6593189894E+00
0.1000000000E+01

ARRAY
1
2

THE H

1
0.5489339108E+00
0.5489339108E+00

2
0.1211465466E+01
-0.1211465466E+01

ARRAY
1
2

1
-0.1120410675E+01
-0.9583811907E+00

CF740 (UFPR)

2
-0.9583811907E+00
-0.1120410675E+01

PG Fsica

31 / 41

H2
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(

1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2

THE P

1
1
1
1
2
2
2
2
1
1
1
1
2
2
2
2

1
1
2
2
1
1
2
2
1
1
2
2
1
1
2
2

1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2

)
)
)
)
)
)
)
)
)
)
)
)
)
)
)
)

0.774608
0.444109
0.444109
0.569678
0.444109
0.297029
0.297029
0.444109
0.444109
0.297029
0.297029
0.444109
0.569678
0.444109
0.444109
0.774608

ARRAY
1
2

1
0.0000000000E+00
0.0000000000E+00

CF740 (UFPR)

2
0.0000000000E+00
0.0000000000E+00

PG Fsica

32 / 41

H2

START OF ITERATION NUMBER =

THE G

ARRAY
1
2

THE F

1
0.0000000000E+00
0.0000000000E+00

2
0.0000000000E+00
0.0000000000E+00

ARRAY
1
2

1
-0.1120410675E+01
-0.9583811907E+00

ELECTRONIC ENERGY =

CF740 (UFPR)

2
-0.9583811907E+00
-0.1120410675E+01

0.000000000000E+00

PG Fsica

33 / 41

H2

THE F
1
2
THE C
1
2
THE E

ARRAY
1
-0.1252798214E+01
-0.8044780120E-16

2
0.2602085214E-17
-0.4756046848E+00

ARRAY
1
0.1000000000E+01
-0.3348053113E-17

2
-0.3348053113E-17
-0.1000000000E+01

ARRAY
1
2

1
-0.1252798214E+01
0.0000000000E+00

CF740 (UFPR)

2
0.0000000000E+00
-0.4756046848E+00

PG Fsica

34 / 41

H2

THE C

ARRAY
1
2

THE P

1
0.5489339108E+00
0.5489339108E+00

2
-0.1211465466E+01
0.1211465466E+01

ARRAY
1
2

1
0.6026568769E+00
0.6026568769E+00

2
0.6026568769E+00
0.6026568769E+00

DELTA(CONV OF DENSITY MATRIX) = 0.602656876933E+00

CF740 (UFPR)

PG Fsica

35 / 41

H2

START OF ITERATION NUMBER =

THE G

ARRAY
1
2

THE F

1
0.7548735870E+00
0.3644955252E+00

2
0.3644955252E+00
0.7548735870E+00

ARRAY
1
2

1
-0.3655370883E+00
-0.5938856654E+00

ELECTRONIC ENERGY =

CF740 (UFPR)

2
-0.5938856654E+00
-0.3655370883E+00

-0.183100093420E+01

PG Fsica

36 / 41

H2

THE F
1
2
THE C
1
2
THE E

ARRAY
1
-0.5782027204E+00
0.1100465205E-16

2
0.1371515748E-16
0.6702709280E+00

ARRAY
1
0.1000000000E+01
-0.1098554022E-16

2
-0.1098554022E-16
-0.1000000000E+01

ARRAY
1
2

1
-0.5782027204E+00
0.0000000000E+00

CF740 (UFPR)

2
0.0000000000E+00
0.6702709280E+00

PG Fsica

37 / 41

H2

THE C

ARRAY
1
2

THE P

1
0.5489339108E+00
0.5489339108E+00

2
-0.1211465466E+01
0.1211465466E+01

ARRAY
1
2

1
0.6026568769E+00
0.6026568769E+00

2
0.6026568769E+00
0.6026568769E+00

DELTA(CONV OF DENSITY MATRIX) = 0.000000000000E+00

CF740 (UFPR)

PG Fsica

38 / 41

H2

CALCULATION CONVERGED
ELECTRONIC ENERGY =

-0.183100093420E+01

TOTAL ENERGY =

-0.111671521992E+01

THE PS

ARRAY
1
0.1000000000E+01
0.1000000000E+01

1
2
TRACO DE PS =

CF740 (UFPR)

2
0.1000000000E+01
0.1000000000E+01

2.0000

PG Fsica

39 / 41

GAMESS

!...Exemplo de input para H2...

$CONTRL SCFTYP=RHF COORD=CART UNITS=BOHR $END
$SYSTEM MEMORY=10000000 TIMLIM=60000 $END
$SCF
DIRSCF=.TRUE. $END
$BASIS GBASIS=STO NGAUSS=3 $END
$DATA
...H2-RHF/STO-3G...
Dnh 2
H 1.0 0.0
H 1.0 0.0
$END

0.0 0.7
0.0 -0.7

CF740 (UFPR)

PG Fsica

40 / 41

Resultados

1
2

H
H

1
2

S
S

1
-0.5782
AG
0.548934
0.548934

2
0.6703
B1U
1.211464
-1.211464

ONE ELECTRON ENERGY =

-2.5055941252
TWO ELECTRON ENERGY =
0.6745940858
NUCLEAR REPULSION ENERGY = 0.7142857143
TOTAL ENERGY =
-1.1167143251

CF740 (UFPR)

PG Fsica

41 / 41