Hartree-Fock Theory

The HF approximation plays a crucial role in chemistry and constitutes the starting point for more elaborate treatments
of electron correlation. Furthermore, many semi-empirical methods are developed by making certain approximations on
integrals derived from HF theory.
In the simplest case of a closed-shell system (or an open-shell system with all the unpaired electrons having the same
spin) we assume that the N-electron wave function can be written as a single Slater determinant, and we nd the best set
of spin-orbitals (in a variational sense) by minimizing the expectation value [

H[) upon variations of the spin-orbitals.
We will see that in doing so the optimal spin-orbitals satisfy the Hartree-Fock equations:

f(r)
i
(x) =
i

i
(x) (1)
where in Eq. (1)

f(r
i
) is an hermitean operator called the one-particle Fock Hamiltonian of the form:

f(r) =
1
2

K=1
Z
A
[r R
K
[
+v
HF
(r). (2)
In Eq. (2), v
HF
(r) is an eective single-particle potential, which is built from the Fock orbitals
i
(x) in a self-consistent
manner.
We now proceed to a derivation of the Hartree-Fock equations.
I. DERIVATION OF THE HARTREE-FOCK EQUATIONS
A. The energy of a Slater determinant
We consider a single Slater determinant wave function [) = [
i
(x
1
)
j
(x
2
)
k
(x
N
)), where as usual only the diagonal
of the determinant is explicitly shown. The electrostatic Hamiltonian can be written as:

H
e
=
N

i=1

h(r
i
) +
N

i<j=1
g(r
i
, r
j
) (3)
where

h(r
i
) =
1
2

2
i

M

K=1
Z
k
[r
i
R
K
[
(4)
and
g(r
i
, r
j
) =
1
[r
i
r
j
[
(5)
i.e. a sum of one-electron and two electron operators. The expectation value of the Hamiltonian for a single Slater
determinant can therefore be readily calculated by using the Slater-Condon rules as follows:
[

H
e
[) =
N

m=1

m
(1)[

h(1)[
m
(1)) +
1
2
N

mn

m
(1)
n
(2)[[
m
(1)
n
(2)) (6)

Lecture notes for CHEM489, Computational Chemistry, Department of Chemistry, Middle East Technical University, 06531, Ankara, Turkey,
Electronic mail: [email protected]
where as a convention the coordinates of electron-one and electron-two have been used. We assume in the following
that the set of N spin-orbitals are orthonormal, i.e.

m
(x)
n
(x)dx =
mn
. (7)
B. Minimization of the energy functional
We want to nd the minimum of the expectation value, Eq. (6) upon variation of the spin-orbitals, with the constraint
that the spin-orbitals must remain orthogonal. Using the method of the Lagrange undetermined multipliers we need to nd
the (unconstrained) minimum of the functional:
L =
N

m=1

m
(1)[

h(1)[
m
(1)) +
1
2
N

mn

m
(1)
n
(2)[[
m
(1)
n
(2))

ij

ij
(
i
[
j
)
ij
). (8)
Since the Lagrangian of Eq. (8) has to be real, the Lagrange multipliers are elements of an hermitean matrix, i.e.
ij
=

ji
.
We note that the condition of stationarity of the Lagrangian of Eq. (8) with respect to variation on the Lagrange
multiplier, i.e.
L

ij
= 0. (9)
correspond to the orthogonality requirement.
We now proceed by calculating the rst order variation of the Lagrangian of Eq. (8). The condition of minimum is
obtained by requiring that L = 0. We obtain in a straighforward manner:
L =
N

i=1
[
i
(1)[

h(1)[
i
(1)) +
i
(1)[

h(1)[
i
(1))]
+
1
2
N

ij
[
i
(1)
j
(2)[
i
(1)
j
(2)) +
i
(1)
j
(2)[
i
(1)
j
(2))
+
i
(1)
j
(2)[
i
(1)
j
(2)) +
i
(1)
j
(2)[
i
(1)
j
(2))

i
(1)
j
(2)[
j
(1)
i
(2))
i
(1)
j
(2)[
j
(1)
i
(2))

i
(1)
j
(2)[
j
(1)
i
(2))
i
(1)
j
(2)[
j
(1)
i
(2))

ij

ij
[
i
[
j
) +
i
[
j
)] (10)
Note that Eq. (11) can be rewritten in a more concise way by realizing that some terms are just one the complex conjugate
of the other. For example:

i
(1)[

h(1)[
i
(1)) =
i
(1)[

h(1)[
i
(1))

i
(1)
j
(2)[
i
(1)
j
(2)) =
i
(1)
j
(2)[
i
(1)
j
(2))

(11)
Also the following relation holds generally:

i
(1)
j
(2)[
i
(1)
j
(2)) =
j
(2)
i
(1)[
j
(2)
i
(1))
=
j
(1)
i
(2)[
j
(1)
i
(2)) (12)
since the integration variables are dummy indexes. The rst order variation of the Lagrangian can therefore be re-written
as:
2
L =
N

i=1
[
i
(1)[

h(1)[
i
(1)) +
N

i
(1)
j
(2)[
i
(1)
j
(2))
i
(1)
j
(2)[
j
(1)
i
(2))

ij

i
[
j
)] + c.c. (13)
where c.c. stands for complex conjugate. Introducing the following notation for the operators:

J
i

j
(x
1
) = [

i
(x
2
)
i
(x
2
)
r
12
dx
2
]
j
(x
1
)

K
i

j
(x
1
) = [

i
(x
2
)
j
(x
2
)
r
12
dx
2
]
i
(x
1
) (14)
we can re-write Eq. (13) even more concisely:
L =
N

i=1

dx
1

i
(x
1
)[

h(1)
i
(x
1
) +
N

j=1

J
j


K
j

i
(x
1
)

ij

j
] + c.c. = 0 (15)
Since the variations

i
and
i
can be regarded as independent, we obtain the following condition for the extremum of
the functional, Eq. (11):
[

h(1) +
N

j=1

J
j


K
j
]
i
(x
1
) =

ij

j
(x
1
) (16)
which are the Hartree-Fock equations. A few words on the operators: the operator

J
i
is called Coulomb operator, and
one can readily see that the Coulomb integrals are simply expectation values of spin-orbitals with the Coulomb operator:

i
[

J
j
[
i
) =

i
(x
1
)

j
(x
2
)
1
r
12

i
(x
1
)
j
(x
2
)dx
1
dx
2
J
ij
(17)
The Coulomb operators are an example of local operators: in order to evaluate their action on a given function at a
point in the congurational space, we need to know just the value of the function at the same point. Note that a dierent
meaning for the same terminology is currently in use in Density Functional Theory.
Lets now consider the expectation value for the exchange operator,

K
j
:

i
[

K
j
[
i
) =

i
(x
1
)

j
(x
2
)
1
r
12

i
(x
2
)
j
(x
1
)dx
1
dx
2
K
ij
. (18)
Analogously the expectiation value is the familiar exchange integral. Note that at variance with the Coulomb operators,
the exchange operators are non-local ; we need to know the value of the function
i
in all the congurational space in
order to calculate the result of the action of the echange operator on the function
i
,

K
j

i
in a single point in space.
The presence of the exchange operator in the Hartree-Fock equations is a consequence of the antisymmetric nature of the
Slater determinant. In fact in the closely related Hartree theory, where the ansatz is a simple Hartree product, we do not
have exchange operators.
The Hartree-Fock equations can therefore be written as:

f(r)
i
(x) =

ij

j
(x). (19)
where

f(1) =

h(1) +
N

j=1
[

J
j


K
j
] (20)
and the sum in Eq. (20) is over the N occupied spin-orbitals of lower energy.
3
C. Canonical Hartree-Fock equations
It is easy to show that a Slater determinant is invariant, up to a constant purely imaginary phase factor, to a unitary
transformation of the constituent spin-orbitals.
Suppose that the set of transformed spin-orbitals are derived from the original ones with the transformation:

i
=

j
U
ji
(21)
such that the matrix U is unitary, i.e. also the set of spin-orbitals

i
are orthonormal if the original set is (this is true by
assumption). The inverse transformation of Eq. (21) reads:

i
=

j
(U

)
ji
. (22)
Now we assume that we have a Slater product built from a set of spin-orbitals:
(x
1
, x
2
, . . . , x
N
) =
1

N!

i
(x
1
)
j
(x
1
) . . .
k
(x
1
)

i
(x
2
)
j
(x
2
) . . .
k
(x
2
)
. . . . . . . . . . . .

i
(x
N
)
j
(x
N
) . . .
k
(x
N
)

. (23)
Consider the matrix A built from the original spin orbitals:
A =

i
(x
1
)
j
(x
1
) . . .
k
(x
1
)

i
(x
2
)
j
(x
2
) . . .
k
(x
2
)
. . . . . . . . . . . .

i
(x
N
)
j
(x
N
) . . .
k
(x
N
)

(24)
from which it follows that (x
1
, x
2
, . . . , x
N
) =
1

N!
[A[.
Consider now the matrix A

built from the set of

i
spin-orbitals:
A

i
(x
1
)

j
(x
1
) . . .

k
(x
1
)

i
(x
2
)

j
(x
2
) . . .

k
(x
2
)
. . . . . . . . . . . .

i
(x
N
)

j
(x
N
) . . .

k
(x
N
)

(25)
Inserting Eq. (21) we trivially obtain that A

= AU and therefore the Slater determinant built from the set of

i
can be
written as:
(x
1
, x
2
, . . . , x
N
) =
1

N!
[AU[ =
1

N!
[A[[U[. (26)
Now, since our transformation is unitary, [U[ = e
i
with R. As a results, the two Slater determinants dier by just a
phase factor, which is irrelevant for the computation of most properties (in fact the phase factor cancel when we take the
expectation values).
In order to derive the canonical (eigenvalue-type) Hartree-Fock equations, we now consider the eect of a unitary
transformation of the spin orbitals on the Fock operator, Eq. (20). Consider now how the Coulomb and exchange operators
changes:

i
(x
1
) =

i
[

i
(x
2
)

i
(x
2
)
r
12
dx
2
]
=

k
U

ji
U
ki
[

j
(x
2
)
k
(x
2
)
r
12
dx
2
]
=

j
[

j
(x
2
)
j
(x
2
)
r
12
dx
2
] (27)
4
due to the fact that U is unitary. For the exchange operator we have similar results, and it follows that the Fock operator
is invariant upon a unitary transformation of the spin-orbitals. Let us now consider the Lagrange multipliers. We already
saw that they are the elements of an hermitean matrix. Moreover one trivially shows that:

i
[

f[
j
) =

jk

i
[
k
) =
ji
. (28)
We can write:

i
[

f[

j
) =

ji
(29)
with

ji
=

kl
U

kj

kl
U
li
(30)
or, in matrix notation:

= U

U. It therefore follows that the two matrices are connected by a similarity transformation.
Since every hermitean matrix can be diagonalised by a unitary transformation, we can choose to express the Hartree Fock
Equations in the set of spin-orbitals obtained by the transformation Eq. (21), where the matrix U diagonalizes the matrix
of Lagrange multipliers. In such a set of spin-orbitals, we therefore obtain the canonical Hartree-Fock equations:

f(r)
i
(x) =
i

i
(x). (31)
which has the form of an eigenvalue equation. Form inspection of Eq. (20) and the form of the Coulomb and Exchange
operators, Eq. (14), one realizes that the solutions of the eigenvalue equation enter in the denition of the operator. For
this reason the Hartree-Fock equations are often referred to as pseudo-eigenvalue equations. A standard solution is to start
with a guess for the spin-orbitals, build the Fock operator, solve the eigenvalue equation, and then the procedure must be
repeated until the solutions are close enough to the spin-orbitals used for the construction of the operator. This method
of solution is often called self-consistent eld. The spin-orbitals of Eq. (31) are in general delocalized orbitals. Clearly
we are free to transform this set of canonical Hartree-Fock orbitals to a set of more localized orbitals by applying unitary
transformations on the spin-orbitals.
II. SOME GENERAL PROPERTIES OF THE HARTREE-FOCK SOLUTIONS
A. Interpretation of the orbital energies: The Koopmans theorem
The Fock operator is given by:

f =

h +
N

j=1
(

J
j


K
j
) (32)
where the Coulomb and exchange operators,

J and

K are dened by their action on a spin orbital in the following
manner:

J
j

i
(x
1
) =

j
(x
2
)
j
(x
2
)
r
12
dx
2

i
(x
1
) (33)
and

K
j

i
(x
1
) =

j
(x
2
)
i
(x
2
)
r
12
dx
2

j
(x
1
) (34)
Upon resolution of the self-consistent eld equations, Eq. (31) we obtain a set of one-particle orbitals, occupied in the
ground-state HF wave function. Furthermore one obtains a set of spin-orbitals which are not occupied in the reference HF
5
wave function. In fact, for a N-electron system, only the N spin-orbitals with lowest orbital energies
i
, i = 1, 2, . . . , N
enter in the HF determinant. The set of spin-orbitals which are not occupied in the ground-state are the virtual or particle-
HF spin-orbitals. It is customary to label occupied spin-orbitals with letters a, b, . . . , and virtual orbitals with letters r, s,
. . . . The SCF wave function can then be written as [) = [
i

j
. . .
k
) and the HF energy is given by:
E
HF
= [

H[) =
N

i=1

i
[

h[
i
) +
1
2
N

i=1
N

j=1

j
[[
i

j
) (35)
and can be easily derived by using the Slater-Condon rules.
Occupied and virtual spin-orbitals are eigenvectors of the HF operator:

f(r)
a
(x) =
a

a
(x), (36)
and

f(r)
r
(x) =
r

r
(x). (37)
and consequently orbital energies of occupied and virtual spin-orbitals are obtained as expectation values:

a
(x)[

f(r)[
a
(x)) =
a
, (38)
and

r
(x)[

f(r)[
r
(x)) =
r
. (39)
By using the Slater-Condon rules for matrix-element evaluations, we readily obtain the following expressions for
a
and

r
:

a
=
a
[

f[
a
) =
a
[

h[
a
) +
N

j=1

j
[[
a

j
)
=
a
[

h[
a
) +
N

j=a

j
[[
a

j
) (40)
since by denition,
a

a
[[
a

a
) = 0, and

r
=
r
[

f[
r
) =
r
[

h[
r
) +
N

j=1

j
[[
r

j
). (41)
We at once note that the HF energy, Eq. (35) is not simply given as a sum of the orbital energies of the occupied
spin-orbitals, i.e. E
HF
,=

N
a=1

a
.
We want to nd an interpretation of the HF orbital energies. Let suppose that we have obtained HF orbitals and energy
for a system consisting of N electrons. The N spin-orbitals with lower energy are occupied in the HF determinant. Consider
now a system of N1 electrons, obtained by removing an electron from an occupied orbital
a
of the system of N electrons.
If we assume that the SCF orbitals do not change upon ionization, the other N 1 electrons still occupying the same
orbitals, the total energy of the ionized system, with an electron vacancy in the spin orbital
a
can be evaluated to be:
E
N1
a
=
N

b=a

b
[

h[
b
) +
1
2
N

b=a
N

c=a

c
[[
b

c
) (42)
and we readily obtain for the ionization potential (IP):
6
E
N1
a
E
N
=
a
[

h[
a
)
1
2
N

a
[[
b

a
)
1
2
N

b
[[
a

b
)
= (
a
[

h[
a
) +
N

b
[[
a

b
)) =
a
. (43)
The result obtained in (43) has a very simple interpretation: in the assumption where the electronic structure of the
system is unaected by the ionization, the ionization potential is simply given as the negative of the HF orbital energy
for the ionized level. The relaxation eects, i.e. the re-arrangement of the electronic structure of the ion following the
ionization, is completely neglected. While this can be a good approximation for the outmost valence levels, it is a bad
approximation for core levels and inner valence levels. In fact, from an analysis of the photoionization spectra (line positions
and intensities) a break-down (sometimes complete) of the single particle approximation is apparent, with the appearance
of satellite lines of intensity sometimes larger than that of the main lines.
In the same spirit also the energies of the virtual orbitals have a simple interpretation. Let consider a system of N + 1
electrons where an electron has been added to our system and occupies a virtual orbital (the orbitals and energies of the
remaining N electrons being unaected by the attachment process). We can write for the system of N + 1 electron:
E
N+1
r
=
N

b
[

h[
b
) +
r
[

h[
r
) +
1
2
N

b
N

c
[[
b

c
) +
1
2
N

b
[[
r

b
) +
1
2
N

r
[[
b

r
) (44)
from which it follows that:
E
N+1
r
E
N
=
r
[

h[
r
) +
N

b
[[
r

b
)) =
r
. (45)
In other words, the energies of the virtual orbitals are approximations to the electron anities. The HF approximation to
the electron anities are often very poor. In fact usually the HF energies of virtual orbitals are positive, which means that
often the anion is predicted to be unstable on the basis of a simple SCF theory. This can be easily understood in terms of
electron correlation. When an electron is added to a system, the electron correlation increases simply due to the increase
in the number of electron-electron interactions. HF lacks of a complete treatment of electron correlation (it is a mean eld
approach) and is therefore unable to provide an accurate description of the electron-attachment process.
The relations above, Eq. (43) and (45) are the formal demonstration of the so colled Koopmans Theorem: in the
frozen-orbital approximation, the orbital energies of occupied levels are the negative of the ionization potentials, IPs, while
orbital energies of virtual orbitals equals the electron anities, AE.
B. The Brillouin theorem
We know that from the self-consistent resolution of the HF equations one obtains a set of hole orbitals, which are
occupied in the HF determinant, which will be denoted with [
0
), and a set of particle orbitals, which are unoccupied in
the HF reference state. We can construct a set of singly excited determinants, denoted with [
r
a
), by promoting single
electron excitations from one occupied HF orbital,
a
, to a virtual orbital,
r
. Likewise we can construct doubly excited
determinants by promoting a pair of electrons from occupied to virtual levels, and so on for higher excitations. Fixing our
notation:
[
0
) = [
i

j
. . .
a
. . .
b
. . .
k
), (46)
[
r
a
) = [
i

j
. . .
r
. . .
b
. . .
k
), (47)
[
rs
ab
) = [
i

j
. . .
r
. . .
s
. . .
k
), (48)
7
and so on. Next we evaluate the matrix element,
0
[

H[
r
a
) by making use of the Slater-Condon rules:

0
[

H[
r
a
) =
a
[

h[
r
) +

b
[[
r

b
)
=
a
[(

h +

b
[

J
b


K
b
])[
r
)
=
a
[

f[
r
)
=
ar
= 0. (49)
The last result is known as the Brillouin Theorem, and simply states that the optimized HF wave function does not mix
with singly excited determinants, or in other words, that the HF wave function is stable with respect to single excitations.
This has important consequencies in Conguration Interaction (CI) theory; in a CI expansion of the exact non relativistic
wave function:
[) = [
0
) +

ar
c
ra
[
r
a
) +

a<b
r<s
c
rasb
[
rs
ab
) +. . . (50)
the singly excited determinants are expected not to contribute that much to the expansion of the exact wave function
and therefore to the ground state energy. This is not completely true since CI matrix elements of the type
r
a
[

H[
rs
ab
) are
dierent from zero and the single excitations contribute trough coupling with the double excitations.
C. The Hartree-Fock Hamiltonian
The HF determinant, i.e. the determinant constructed from the lowest N spin-orbitals is, in general, not an eigenstate
of the true electrostatic Hamiltonian (it would be so if the particles were truly interacting in a mean eld sense, i.e. in the
absence of two-body interaction terms). Therefore we have:

H
e
[
0
) , = E[
0
) (51)
However, the SCF solution is an eigenstate of a one-particle operator, sometimes called Fockian, of the form:

H
0
=
N

i=1

f(i) (52)
as can be easily proven since

H
0
is invariant over permutation of the electron labels [

/,

H
0
] = 0 with

/ the antisym-
metrization operator:

H
0
[
0
) =

H
0

/
i

j
. . .
a
. . .
b
. . .
k

=

/(
N

i=1

f(i))
i

j
. . .
a
. . .
b
. . .
k

= (
N

i=1

i
)[
0
) = E
0
[
0
). (53)
This result will be used in the perturbation analysis of the correlation energy, later in the course.
8
III. CLOSED SHELL HARTREE-FOCK EQUATIONS
In this section we specialize to the simpler but important case of closed-shell molecules, which are by far the more common
in Chemistry. We rst rewrite the Hartree-Fock equations in the special case of a closed-shell system where electrons with
and spin occupy the same spatial orbitals. These HF equations are some times referred with the term restricted. We
then invoke the algebraic approximation, we will introduce a nite basis set for the expansion of the spatial function of the
spin-orbitals, deriving thus the Roothaan-Hall equations, routinely solved by every quantum chemistry package. We will
end the section with some comments on population analysis and the calculation of expectation values.
A. Restricted spin-orbitals
We will consider so called restricted spin-orbitals, for which the radial part of the orbital is the same for and spins.
Fixing our notation:

1
=
1

2
=
1

. . .

2i1
=
i

2i
=
i

. . .

N1
= N
2

N
= N
2
.
In this case, we can derive a set of HF equations involving only the radial part of the spin-orbitals. The HF restricted
determinant for a system of N electrons is then obtained by pairing the electrons (with and spin) in the
N
2
lowest
energy orbitals. We derive the spatial Hartree Fock equations with reference to spin spin-orbitals; the same result is
obtained if we start with spin. Therefore we have:

f
i
(r
1
)() =
i

i
(r
1
)() (54)
and we integrate over the spin, to obtain:

()

f
i
(r
1
)() = [

()

f()]
i
(r
1
)
=

f(r
1
)
i
(r
1
)
=
i

i
(r
1
) (55)
with the obvious notation

f(r
1
) =

()

f().
We now consider the quantity

f(r
1
)
i
(r
1
):
9

f(r
1
)
i
(r
1
) =

h(r
1
)
i
(r
1
) +
N
2

j=1

dd

dr
2

()[

j
(r
2
)

)
1
r
12

j
(r
2
)(

)
+

j
(r
2
)

)
1
r
12

j
(r
2
)(

)]
i
(r
1
)()]

N
2

j=1

dd

dr
2

()[

j
(r
2
)

)
1
r
12

i
(r
2
)(

)
i
(r
1
)()
+

j
(r
2
)

)
1
r
12

i
(r
2
)(

)]
j
(r
1
)()]
= [

h + 2
N
2

j=1

dr
2

j
(r
2
)
1
r
12

j
(r
2
)
N
2

j=1

dr
2

j
(r
2
)
T
12
r
12

j
(r
2
)]
i
(r
1
)
=
i

i
(r
1
), (56)
due to the orthonormality of the spin eigenfunction, or in other words, as a direct consequence of the absence of exchange
interactions between electrons with dierent spins. T
12
in Eq. (56) permutes the electronic coordinates 1 and 2.
We can therefore write the restricted closed-shell Hartree-Fock equations:

f(r)
i
(r) =
i

i
(r) (57)
with

f(r
1
) =

h(r
1
) +
N
2

a=1

dr
2

a
(r
2
)
(2 T
12
)
r
12

a
(r
2
). (58)
B. The Roothaan-Hall Equations
The Hartree-Fock equations can be solved either numerically, as often done for atoms, or by recasting the integro-
dierential equation to the solution of a pseudo eigenvalue problem, via the introduction of a nite basis set. Quite
recently, grid-methods approaches have also been attempted for the resolution of the molecular HF equations, but these
methods, although promising, are still not of standard use. In almost every quantum chemistry code the HF equations are
solved via the introduction of a nite basis set of either Gaussians or Slater type orbitals, which are used to expand the
spatial part of the spin orbitals. Clearly in the limit that the basis set approaches completeness, the HF limit is obtained.
For nite basis set, the resulting SCF solution is an approximation to the HF solution. We nonetheless will refer to HF
solution also for the solution of the HF equations in a nite basis set.
The spatial part of the HF molecular orbitals is written as a linear combination of known K basis functions:

i
(r) =
K

=1

C
i
(59)
and introducing this linear combination in the restricted HF equations, Eq. (57) one obtains:

f(r)

C
i
=
i

C
i
. (60)
We now multiply the above equation on the left by a generic basis function,

, and integrate over the conguration

f[

)C
i
=
i

)C
i
. (61)
10
If we now introduce the following notation for the matrix elements of the Fock operator,

f, and for the overlap between
basis functions:
F

f[

) =

(r)

f(r)

(r)dr
S

) =

(r)

(r)dr (62)
then the solution of the HF equations is recast to an algebraic eigenvalue problem:
FC = SC (63)
where is a diagonal matrix of the eigenvalues, and the expansion coecients of the molecular orbitals in the nite basis
set are arranged into columns:
C =

C
11
C
12
. . . C
1K
. . . . . . . . . . . .
C
1
C
2
. . . C
2K
. . . . . . . . . . . .
C
K1
C
K2
. . . C
KK

, (64)
i.e. the expansion coecients of the rst molecular orbital are arranged in the rst column, and so on. It should be
clear that the dimension of the basis set determines the dimension of the eigenvalue problem. If we use K basis functions
for the expansion of the molecular orbitals, then we obtain, at the end of the SCF procedure, K radial orbitals, and
2K spin-orbitals. Of these, the N spin orbitals with the lowest energy will be occupied in the HF reference state, and
N 2K are the set of virtual orbitals. This set of orbitals is important in CI since electron correlation eects will be
accounted through virtual excitations to these empty states. Note that the HF eigenvalue equation of Eq. (63) is preferably
termed pseudo-eigenvalue since the Fock operator is dened through the molecular orbitals, Eq. (58). We will consider this
issue in the next subsection.
C. Expressions for the Fock matrix
Let us now evaluate the Fock matrix elements over the basis functions:
F

f[

) =

(r)[

h +
N
2

a=1
(2

J
a


K
a
)]

(r)dr (65)
with

J
a

(r
1
) =

a
(r
2
)
1
r
12

a
(r
2
)dr
2

(r
1
)
=

a
C
a

(r
2
)
1
r
12

(r
2
)dr
2

(r
1
) (66)
and

K
a

(r
1
) =

a
(r
2
)
1
r
12

(r
2
)dr
2

a
(r
1
)
=

a
C
a

(r
2
)
1
r
12

(r
2
)dr
2

(r
1
). (67)
Therefore:
11
F

f[

) =

h[

) +
N
2

a=1

a
C
a
[2

(r
1
)

(r
2
)
1
r
12

(r
1
)

(r
2
)dr
1
dr
2

(r
1
)

(r
2
)
1
r
12

(r
1
)

(r
2
)dr
1
dr
2
]. (68)
We now dene the so-called density matrix in the following way:
P

= 2
N
2

a=1
C

a
C
a
(69)
which permits us to rewrite the expression for the Fock matrix elements in the following way:
F

f[

) =

h[

) +

(r
1
)

(r
2
)
1
r
12

(r
1
)

(r
2
)dr
1
dr
2

1
2

(r
1
)

(r
2
)
1
r
12

(r
1
)

(r
2
)dr
1
dr
2
]. (70)
Note that, according to Eq. (70), the Fock matrix is dened once the density matrix is known. Since the knowledge of
the density matrix requires a knowledge of the HF molecular orbitals, it is clear that a solution to the HF equations can
only be found through an iterative procedure. Hence the terminology SCF (Self-Consistent Field) used for the solution of
the HF equations. The SCF cycle must start with a guess to the density matrix. One possible guess would correspond
to a null matrix P = 0 and the rst SCF cycle thus solves the mono-electronic problem. A typical choice would be to
use H uckel orbitals. Note also that we need to calculate the matrix elements of the Hamiltonian over the known basis
functions. These integrals can be subdivided in mono-electronic, i.e. matrix elements over the mono-electronic part of the
electrostatic Hamiltonian (kinetic energy and electron-nuclear repulsion):

h[

) =

(r)[
1
2

K
Z
K
[r R
K
[
]

(r)dr (71)
which are usually computationally inexpensive, and a far larger set of bi-electronic integrals:

) =

(r
1
)

(r
2
)
1
r
12

(r
1
)

(r
2
)dr
1
dr
2
(72)
which are in number of K
4
for K basis functions. Symmetry properties of the integrals can be used to reduce the scaling
to
K
4
8
. Note that in modern quantum chemistry programs, the basis functions (usually GTO or Slater type functions)
are centered on the atomic nuclei. Therefore mono-electronic integrals can at most involve two dierent atomic centers,
while bi-electronic integrals can involve up to four dierent centers. The numerical evaluation of a four-center integral can
be very costly, this is the reason for the wide spread use of GTO functions over STOs. Note also that the evaluation of
the mono-electronic integrals requires in input to the program a molecular structure, dening the positions of the nuclei
(coordinates R
K
). Integrals over basis functions are calculated before the beginning of the SCF cycle and stored on disk
or in memory.
D. The Density Matrix
The electron density operator is a one-electron operator, which, in the coordinate representation takes the following form:
=
N

i=1
(r r
i
). (73)
12
The HF electron density is therefore the expectation value of with the HF wave function:
(r) =
0
[ [
0
)
=
0
[
N

i=1
(r r
i
)[
0
)
= 2
N
2

i=1
[
i
(r)[
2
(74)
where, in Eq. (74),
0
is the restricted HF solution, and
i
are the set of occupied HF spatial orbitals. The factor 2 in
Eq. (74) is due to the spin. The solutions of the restricted HF equations are expressed as a linear combination of the basis
elements:

i
=

C
i
(75)
and after insertion of the linear combination in Eq. (74) one obtains:
(r) = 2
N
2

i=1

i
(r)
i
(r)
= 2

i
C
i
=

. (76)
from which it is clear that the density matrix is simply the matrix representation of the electron density in the one-electron
orbital basis.
The number of electron is given by:

(r)dr =

dr
=

= Tr(PS), (77)
where S

is the overlap matrix.

a=1

a
[h[
a
) +
1
2

ab

b
[[
a

b
)
= 2
N
2

i=1

a
[h[
a
) +
N
2

ab=1
(2J
ab
K
ab
) (78)
where J
ij
and K
ij
are Coulomb and Exchange intregrals respectively:
13
J
ij
=

i
(r
1
)

j
(r
2
)
1
r
12

i
(r
1
)
j
(r
2
)dr
1
dr
2
(79)
and
K
ij
=

i
(r
1
)

j
(r
2
)
1
r
12

j
(r
1
)
i
(r
2
)dr
1
dr
2
. (80)
The orbital energy of an occupied HF spin orbital can be written as:

a
= f
aa
=
a
[

f[
a
)
=
a
[

h +
N
2

b=1
(2

J
b


K
b
)[
a
)
=
a
[

h[
a
) +
N
2

b=1
(2J
ab
K
ab
) (81)
and comparing with the expression for the HF energy we get:
E
HF
=
N
2

a=1
(h
aa
+
a
[

f[
a
)) (82)
If we express the matrix elements in terms of the elements of the density matrix we readily obtain:
E
HF
=
1
2

(h
core

+F

) (83)
which is a convenient expression for the calculation of the HF energy at each SCF iteration by multiplying the elements
of the density matrix with the matrix elements of the Fock operator, F

, and of the one-electron part of the Hamiltonian,

. Note that the one electron matrix elements h

depend only on the molecular geometry and are calculated once

i=1
r
i
+
M

K=1
Z
K
R
K
(84)
where index i runs over the electrons and index K over the nuclei. The quantum mechanical expectation value then
becomes:

0
[ [
0
) =
0
[
N

i=1
r
i
+
M

K=1
Z
K
R
K
[
0
)
=
N
2

a=1

a
[r[
a
) +
M

K=1
Z
K
R
K
(85)
since the integration is over the electronic coordinates. In terms of the density matrix it becomes:

0
[ [
0
) =
N
2

a=1

[r[

) +
M

K=1
Z
K
R
K
(86)
14
and we see that the calculation of the dipole moment is easily accomplished by calculating the dipole matrix elements

[r[

(r)r

(r)dr, usually done at the beginning of the SCF procedure, multiplied by the converged density
matrix elements.
We nish this section with a discussion on population analysis. In most QM programs basis functions are centered on
the atomic nuclei. It is reasonable to calculate the electronic charge on atom A with the following formula:
q
A
= Z
A

A
(PS)

(87)
which is derived from equation Eq. (77). Z
A
is the nuclear charge of atoms A, and the sum is only over the basis
functions centered on that atom. The above formula is at the basis of the Mulliken population analysis. Note that the
denition, Eq. (87) is not unique, since we can write:
Tr(PS) = Tr(SP) = Tr(S

PS
1
). (88)
If we chose =
1
2
we obtain:
q
A
= Z
A

A
(S
1
2
PS
1
2
)

(89)
which is at the basis of the Lodwin population analysis.
Population analysis are of widespread use and principally for qualitative interpretations. In fact, a mapping of the partial
charge on every atom in the molecule could help in predicting the reactivity of the molecule. However, population analysis
are basis-set dependent, and not too much meaning should be attached to the predicted partial charges. In fact, if one
describe water by using a monocentric expansion (all basis functions are centered on a privileged point, for instance the
Oxygen atom) then a population analysis would predict a charge of +1 on both hydrogens, and a charge of 2 on the
Oxygen, i.e. an ionic bond situation, which is not realistic. Furthermore usually population analysis lose of signicance
when the basis set is particularly rich, as it is usually the case for highly correlated electronic structure calculations.
F. Unrestricted Hartree-Fock
In case one wants to describe an open-shell situation, i.e. when the molecular ground-state is not a singlet state, or in
situations where chemical bonds are stretched, i.e. in the dissociation process, a restricted closed shell HF determinant is
not able to describe, even qualitatively, the electronic distribution. There are two possible ways of applying the HF theory.
In one approach, termed Restricted Open-Shell HF, one uses spin-adapted conguration state functions CSFs, i.e. linear
combinations of Slater determinants, but in such a case the HF equations are rather more complicated. In a simpler
approach, called Unrestricted Hartree-Fock, UHF, electrons with and spins are described by dierent spatial functions.
The UHF equations are very similar to the restricted closed-shell HF equations we described above, but now two set of HF
equations must be solved in the SCF procedure, one set for the set of spatial orbitals with spin, and one set for the set of
spatial orbitals with spin. Upon introduction of a nite basis set we obtain the Pople-Nesbet equations. The UHF wave
function is able to qualitatively describe the dissociation of a molecule, although for quantitative agreement one needs to
revert to post-HF methods. One drawback of the UHF approach is the spin-contamination of the wave function, since a
single open-shell Slater determinant is usually not eigenfunction of the spin operator S
2
.
G. Hartree-Fock solutions of the H
2
molecule in a minimal basis set
In the following we will solve the Hartree-Fock equations for the hydrogen molecule in a minimal basis, i.e. we will
use one basis function for each occupied atomic orbital. Since the electron in the hydrogen atom occupies a 1s orbital,
we introduce two normalized basis functions,
1
and
2
as our minimal basis. These are taken to be the two hydrogen
1s orbitals and are centered on the position of the nuclei. Suppose that the two basis functions have an overlap integral
S =
1
[
2
) which depends on the internuclear distance. Orthonormal molecular orbitals of gerade (g) and ungerade (u)
symmetry with respect to the inversion around the mid-bond point can be formed as follows:

1
(r) =
1

2(1 +S)
(
1
(r) +
2
(r)),
15
and

2
(r) =
1

2(1 S)
(
1
(r)
2
(r)),
To derive the above equations we consider two linear combinations of the form:

1
= C
1
(
1
+
2
)

2
= C
2
(
1

2
)
The coecients C
1
and C
2
can be easily found by requiring that
1
and
2
are normalized. For
1
we have:

1
[
1
) = [C
1
[
2

1
+
2
[
1
+
2
) = [C
1
[
2
(2 + 2S)
= 1
from which it follows that C
1
=
1

2(1+S)
. Similarly one obtains that C
2
=
1

2(1S)
.
Obviously
1
transfroms into itself by application of the inversion operator, i.e.

i
1
= +
1
and
1
is of g symmetry.

i
2
=
2
and
2
is of u symmetry.
The above molecular orbitals are the eigenfunctions of the Hartree-Fock (HF) equations in a minimal basis. In fact the
HF hamiltonian commutes with the symmetry operations of the point group of the hydrogen molecule (which includes the
inversion symmetry). Since the two molecular orbitals have dierent parity, the corresponding matrix element of the Fock
matrix,
1
[

f[
2
) is identically zero.
1
is the bonding orbital and is doubly occupied in the ground state of H
2
.
The HF orbital energies
1
and
2
for the two molecular orbitals
1
and
2
respectively, can be expressed in terms of the
following quantities:
h
11
=
1
[

h[
1
)
h
22
=
2
[

h[
2
)
J
11
=
1

1
[
1

1
)
J
22
=
2

2
[
2

2
)
J
12
=
1

2
[
1

2
)
K
12
=
1

2
[
2

1
)
(90)
Note that the molecular orbitals
1
and
2
are real. In order to derive the expressions for the orbital eigenvalues we note
that the restricted Hartree-Fock operator can be written as:

f =

h +
N/2

a=1
(2

J
a


K
a
)
where

h represent the kinetic energy operator and the electron-nuclei attraction, i.e. the core hamiltonian, while

J
a
and

K
a
are the coulomb and exchange operators. N is the number of electrons and a label the occupied states. For the
hydrogen molecule we have
N
2
= 1. Therefore the Fock operator becomes:

f =

h + (2

J
1


K
1
)
where

J
1
=

1
(r
2
)
1
r
12

1
(r
2
)dr
2
and

K
1

j
(r
1
) =

1
(r
2
)
1
r
12

j
(r
2
)dr
2

1
(r
1
) for the exchange operator. We have:

1
=
1
[

f[
1
) =
1
[

h[
1
) + 2
1
[

J
1
[
1
)
1
[

K
1
[
1
)
=

1
(r
1
)

h(r
1
)
1
(r
1
)dr
1
+ 2


1
(r
1
)

1
(r
2
)

1
r
12

1
(r
2
)
1
(r
1
)dr
1
r
2

1
(r
1
)

1
(r
2
)

1
r
12

1
(r
2
)
1
(r
1
)dr
1
r
2
= h
11
+J
11
16
since the wave functions are real. For
2
we similarly obtain:

2
=
2
[

f[
2
) =
2
[

h[
2
) + 2
2
[

J
1
[
2
)
2
[

K
1
[
2
) = h
11
+ 2J
12
K
12
.
Let us now consider the ground state Hartree-Fock solution and discuss its spin properties. Since
1
is doubly occupied
in the ground state, we have [HF) = [
1

1
). Clearly

S
z
[HF) = 0[HF) and M
S
= 0. In order to nd if [HF) is an
eigenstate of the spin operator

S
2
we make use of the identity

S
2
=

S
+

S

S
z
+

S
2
z
or equivalently

S
2
=

S

S
+
+

S
z
+

S
2
z
.
Recall that

S

N
i=1
s

(i) and that:

[) = [)
s
+
[) = [)
s

[) = 0
We therefore have to evaluate the quantity:

S
2
[
1

1
) = (

S
+

S

S
z
+

S
2
z
)[
1

1
)
and note that

S
z
[
1

1
) =

S
2
z
[
1

1
) = 0. By expanding the product

S
+

S

in terms of one-particle operators,

(i) with i = 1, 2 we obtain:

S
+

S

[
1

1
) = ( s
+
(1) + s
+
(2))( s

(1) + s

(2))[
1

1
)
= ( s
+
(1) s

(1) + s
+
(1) s

(2) + s
+
(2) s

(1) + s
+
(2) s

(2))[
1

1
)
= ([
1

1
) + 0 +[
1

1
) + 0) = 0
due to the antisymmetric nature of the wave function. It then follows that

S
2
[HF) = 0[HF) and S = 0. This state is
therefore a singlet state.
Finally, the ground state Hartree-Fock energy can be expressed in terms of the integrals written above. Denoting with
[HF) the Hartree-Fock solution we have that [HF) = [
1

1
):
E
HF
= HF[

H
e
[HF) = HF[

h
1
+

h
2
[HF) +HF[
1
r
12
[HF)
= h
11
+h
11
+
1
2
[
1

1
[[
1

1
)
+
1

1
[[
1

1
) +
1

1
[[
1

1
)
+
1

1
[[
1

1
)]
= 2h
11
+J
11
after the integration over the spin variables and the denition of the [[) symbols in terms of coulomb and exchange
integrals.
17