KH Computational Physics- 2009 Hartree-Fock Method

Hartree-Fock
It is probably the simplest method to treat the many-particle system. The dynamic many
particle problem is replaced by an effective one-electron problem: electron is moving in an
effective static potential eld.
It can be viewed as a variational method where the full many-body wave function is
replaced by a single Slater determinant. The elements of the determinant are one electron
orbitals with orbital and spin part.
It can also be viewed as the lowest order term in perturbative expansion (linear in U) with
respect to interaction between electrons.
These two views will be substantiated below by equations. But rst we will use decoupling
method to derive the Hartree-Fock equations.
Kristjan Haule, 2009 1
KH Computational Physics- 2009 Hartree-Fock Method
In the second quantization, the many electron problem takes the form
H =
_
dr

(r)[
1
2

2
+V
ext
(r)](r)+
1
2
_
drdr

(r)

(r

)v
c
(rr

)(r

)(r)
(1)
where (r) is the eld operator of electron, V
ext
(r) is the potential of nucleous and
v
c
(r r

) is the Coulomb interaction 1/|r r

|. We assumed Born-Oppenheimer
approximation for nuclei motion (freezing them since their kinetic energy is of the order of
M
nuclei
/m
e
).
The Hartree-Fock approximation replaces the two-body interaction term by an effective one
body term

(r)

(r

)(r

)(r)

(r)(r)

(r

)(r

) +

(r

)(r

(r)(r) (2)

(r)(r

(r

)(r)

(r

)(r)

(r)(r

) (3)
With the generalized density (r, r

) =

(r)(r

) the effective Hartree-Fock

(r)
__

1
2

2
+ V
ext
(r) +
_
dr

(r

, r

)v
c
(r

r)
_
(r r

)
(r

, r)v
c
(r

r)} (r

) (4)
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KH Computational Physics- 2009 Hartree-Fock Method
H
eff
is a one-particle Hamiltonian
The effective potential is non-local (very different from the LDA approximation)
Higher order terms in perturbative expansion are completely neglected (so-called
correlation part in Density Functional Theory)
If we write the eld operator in one electron basis
(r) =

(r)c

(5)
where c

creates an electron in one electron state

(r) we get
H
eff
=

H
eff

(6)
where
H
eff

= H
0

ab
(U
ab
U
ab
)n
ab
(7)
with n
ab
= c

a
c
b
and matrix elements
H
0

|
1
2

2
+ V
ext
|

(8)
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KH Computational Physics- 2009 Hartree-Fock Method
U

(r)

(r

)|v
c
(r r

)|

(r)

(r

) (9)
If the one electron orbitals

are othogonal, we are done.

according to Eq. (7) and nally we can diagonalize the matrix H

. In
Eq. (7) the sum over a and b runs over all occupied states only (since n
ab
=
ab
n
a
is 0 for
unoccupied and 1 for occupied eigenstates). Weather the orbital is occupied or not, we
know only after we calculate the one-electron levels, i.e., diagonalize H
eff

by

|H
eff
|

= 0. Hence, the system of equations needs to be solved

(r)
_
H
0
(r)(r r

) + (r, r

)
_
(r

) (10)
From Eq. (4) we can see that
(r, r

) = (r r

)
_
dr

(r

, r

)v
c
(r

r) (r

, r)v
c
(r

r) (11)
This term is just the lowest order term in perturbation expansion of self-energy in powers of
Coulomb repulsion and its diagrammatic representation in terms of Feyman diagrams is
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KH Computational Physics- 2009 Hartree-Fock Method
Derivation for beginners
We mentioned in the previous chapter (second quantization) that Hartree Fock
approximation corresponds to the approximation where one nds single properly
symmetrized Slater determinant that minimizes the total energy for the interacting
Hamiltonian
E =
n
1
n
2
,n
N
|H|
n
1
n
2
,n
N
(12)
We can vary one-electron basis functions with constraint that they are normalized.
In previous chapter we called one-electron basis functions u
k
(x). Here, we called them
(x) therefore we will stick to later denition. We remember from previous lecture
E =

(x)H
0
(x)

(x)dx +
1
2

_
dxdx

(x)

(x

)v
C
(x x

(x)

(x

1
2

_
dxdx

(x)

(x

)v
C
(x x

(x)

(x

)
Kristjan Haule, 2009 6
KH Computational Physics- 2009 Hartree-Fock Method
We would like to minimize
E

_
dx

(x)

(x) = min (15)

, so we will vary the functional with respect to

0 =
E

= H
0
(x)

(x) +
_

_
dx

(x

)v
C
(x x

(x

)
_

(x) (16)

_
dx

(x

)v
C
(x x

(x

(x)

(x) (17)
We can multiply the equation by

(x) and integrate over x to get

(x)H
0
(x)

(x)dx +

_
dxdx

(x)

(x

)v
C
(x x

(x

(x) (18)

_
dxdx

(x)

(x

)v
C
(x x

(x

(x)

(x)

(x)dx (19)
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KH Computational Physics- 2009 Hartree-Fock Method
or
H
0

occupied
(U

) =

(20)
This is equivalent to Eq.(7). One needs to be carefull and sum only over occupied states .
This is because in this derivation we worked with xed number of particles N and all states
of the Slater determinant must be occupied. This is hardly a surprise since the minimization
gives ground state only, thus, this is zero temperature analog of the above more general
perturbation formalism.
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KH Computational Physics- 2009 Hartree-Fock Method
Nonorthogonal base
In actual calculation, the one electron orbitals are choosen very carefully because we would
like to get (at least) the ground state with only few orbitals (The computation time increases
as N
3
, where N is the number of orbitals - solving eigenvalue problem). Those optimally
chosen orbitals are almost never orthogonal!
One way around would be to orthogonalize basis functions rst. This is a time consuming
task and also leads to basis functions which are less localized. It is more convenient to
generalize the equations to non-orthogonal basis functions than to orthogonalize basis
functions.
Let us call the non-orthogonal basis functions
p
(r). Further, let us write the
transformation from non-orthogonal base to eigenbase-base as

(r) =

p
A
p

p
(r) (21)
We want to solve

|H
eff
|

= 0 (22)
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KH Computational Physics- 2009 Hartree-Fock Method
and using Eq. (21) we get
A

p
(H
eff
pq
O
pq
)A
q
= 0 (23)
where O
pq
is the overlap matrix O
pq
=
p
|
q
. This is the generalized eigenvalue
problem H
eff
A = OA, where H is Hermitian and O is positive denite matrix. The
eigenvectors A are not orthogonal, but rather satisfy the relation A

OA = 1 which can be
deduced from the relation

.
We also need the density matrix in the non-orthogonal base. It follows from
(r, r

) =

(r)(r

) =

(r)n

(r

) =

pq,

p
(r)A

p
n

A
q

q
(r

),
(24)
and since n

f(

) we conclude
qp
= A

p
A
q
f(

).
The total energy of the system is not

! The right total energy in the eigen-base is

H
0

+
1
2

a
(U
aa
U
aa
)n
a
n

=
1
2
Tr[(H
eff
+ H
0
)n] (25)
Kristjan Haule, 2009 10
KH Computational Physics- 2009 Hartree-Fock Method
In the non-orthogonal basis, the total energy takes the form
E =
1
2

+
1
2

(A

H
0
A)

=
1
2

+
1
2

pq
H
0
pq

qp
(26)
Now we sketch algorithm to solve the general Hartree-Fock problem
1 Pick a set of one electron orbitals
p
(r) and add them the spin part of the wave
function to get
p
(r) =
p
(r)|s.
2 Calculate H
0
and U matrix elements from
H
0
pq
=
p
|
1
2

2
+ V
ext
|
q
(27)
U
pqrs
=
p
(r)
q
(r

)|v
c
(r r

)|
r
(r)
s
(r

) (28)
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KH Computational Physics- 2009 Hartree-Fock Method
3 Calculate H
eff
by
H
eff
pq
= H
0
pq
+

rs
(U
rpsq
U
rpqs
)
rs
(29)
(30)
4 Solve the generalized eigenvalue problem

q
(H
eff
pq

O
pq
)A
q
= 0
with normalization A

OA = 1
5 Determin the chemical potential by requiring N =

f(

).
6 Calculate the new density matrix and new total energy by

pq
=

A
p
f(

)A

q
(31)
E =
1
2

f(

) +
1
2

qq
H
0
pq

qp
(32)
7 Return to 3 with updated
pq
as long as total energy is changing
Kristjan Haule, 2009 12
KH Computational Physics- 2009 Hartree-Fock Method
Every index p corresponds to spin and orbital index. Treating spin index explicitely results in
more tractable equations for computation. We have
H
0
pq

= H
0
pq

= H
0
pq

(33)
U

1
,
2
,
3
,
4
pqrs
= U

1
,
2
,
1
,
2
pqrs

1
,
3

2
,
4
= U
pqrs

1
,
3

2
,
4
(34)
H
eff
pq

= H
0
pq
+

rs
_
U
rpsq
(

rs
+

rs
) U
rpqs

rs

(35)
Two methods can be used
Restricted Hartree-Fock :

=

Non-Restricted Hartree-Fock:

=

Restricted HF is better if the number of electrons is even the symmetry between and
is preserved. For Restricted HF we simply have
H
eff
pq
= H
0
pq
+

rs
[2U
rpsq
U
rpqs
]
rs
(36)
where p and q run over orbital index only and not over spin.
The algorithm for restricted HF is simplied to
Kristjan Haule, 2009 13
KH Computational Physics- 2009 Hartree-Fock Method
1 Pick a set of one electron orbitals
p
(r)
2 Calculate H
0
and U matrix elements from
H
0
pq
=
p
|
1
2

2
+ V
ext
|
q
(37)
U
pqrs
=
p
(r)
q
(r

)|v
c
(r r

)|
r
(r)
s
(r

) (38)
3 Calculate H
eff
by
H
eff
pq
= H
0
pq
+

rs
(2U
rpsq
U
rpqs
)
rs
(39)
(40)
4 Solve the generalized eigenvalue problem

q
(H
eff
pq

O
pq
)A
q
= 0
with normalization A

OA = 1
5 Determin the chemical potential by requiring N =

2f(

) where N is the
number of all electrons.
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KH Computational Physics- 2009 Hartree-Fock Method
6 Calculate the new density matrix and total energy by

pq
=

A
p
f(

)A

q
(41)
E =

f(

) +

qq
H
0
pq

qp
(42)
7 Return to 3 with updated
pq
until the total energy is changing
Example: He atom and H
2
molecule
For practical computation, we need to specify basis functions. One possible choice are the
Hydrogen-like orbitals (Slater Type Orbitals - STO) of the form
(r) = r
m
P
l
(x, y, z)e
|r|
. (43)
They are less practical for molecule calculations. A better choice are Gaussian Type
Orbitals (GTO)
(r) = P
l
(x, y, z)e
r
2
. (44)
since the product of Gaussian functions is Gaussian. The polinomials P
l
are the same as
for hydorgen atom, i.e.
Kristjan Haule, 2009 15
KH Computational Physics- 2009 Hartree-Fock Method
s : 1
p : x,y,z
d: xy,yz,xz,x
2
y
2
,3z
2
r
2
. The exponents need to be determined by minimization of the total energy.
For the moment, we will take coefcients from literature. For Hydrogen and He we need
only few (four) 1s-like orbitals with coefcients
H : 13.00773,1.962079,0.444529,0.1219492
He: 0.298073,1.242567,5.782948,38.47497
With the basis functions of the form

p
(r) = e

p
r
2
(45)
or in Dirac notation
|
p
R
p
(r R) = e

p
(rR)
2
(46)
the matrix elements become
Kristjan Haule, 2009 16
KH Computational Physics- 2009 Hartree-Fock Method
O
p1,q2

p
R
1
|
q
R
2
=
_

p
+
q
_
3/2
e

pq
(R
1
R
2
)
2

p
R
1
|
1
2

2
|
q
R
2
= O
p1,q2

pq
[3 2
pq
(R
1
R
2
)
2
]

p
R
1
|
1
|r R
N
|
|
q
R
2
= 2 O
p1,q2
_

p
+
q

F
0
[(
p
+
q
)(R
N
R
pq,12
)
2
]

p
R
1

q
R
2
|
1
r r

|
r
R
3

s
R
4
= 2 O
p1,r3
O
q2,s4
_

pr,qs

F
0
[
pr,qs
(R
pr,13
R
qs,24
)
where
pq
=

p

p
+
q
, R
pq,12
=

p
R
1
+
q
R
2

p
+
q
and
pr,qs
=
(
p
+
r
)(
q
+
s
)

p
+
q
+
r
+
s
F
0
[x] =
1

x
_

x
0
dye
y
2
=

erf(

x)
2

x
(47)
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KH Computational Physics- 2009 Hartree-Fock Method
With the above described Hartee-Fock method we get for the ground state energy of He
atom -2.85516 Hartree while the exact ground state energy is -2.86166 Hartree.
The equlibrium distance for the Hydrogen molecule H
2
in the Hartee-Fock calculation is
R
0
= 1.388, while the exact one is 1.401.
0 0.5 1 1.5 2 2.5 3
Distance [au]
-1
-0.8
-0.6
-0.4
E
n
e
r
y
-
H
2
[
R
y
]
Equlibrium = 1.388
Figure 1: The energy versus distance for H
2
molecule
Kristjan Haule, 2009 18
KH Computational Physics- 2009 Hartree-Fock Method
-1 -0.5 0 0.5 1
-1
-0.5
0
0.5
1
Untitled1 1
Figure 2: The electron density of H
2
molecule at equilibrium distance
Kristjan Haule, 2009 19
KH Computational Physics- 2009 Hartree-Fock Method
Homework:
The Python implementation of Hartree-Fock Eq. for He and H2 were started in our lecture.
Finish one of the two projects.
Kristjan Haule, 2009 20