Chapter 6

Self-consistent Field
A way to solve a system of many electrons is to consider each electron under the
electrostatic eld generated by all other electrons. The many-body problem is
thus reduced to the solution of single-electron Schrodinger equations under an
eective potential. The latter is generated by the charge distribution of all other
electrons in a self-consistent way. This idea is formalized in a rigorous way in
the Hartree-Fock method and in Density-Functional theory. In the following
we will see an historical approach of this kind: the Hartree method.
6.1 The Hartree Approximation
The idea of the Hartree method is to try to approximate the wave functions,
solution of the Schrodinger equation for N electrons, as a product of single-
electron wave functions, called atomic orbitals. As we have seen, the best
possible approximation consists in applying the variational principle, by mini-
mizing the expectation value of the energy E = |H| for state |.
The Hamiltonian of an atom having a nucleus with charge Z and N electrons
is
H =

i
h
2
2m
e

2
i

i
Zq
2
e
r
i
+

ij
q
2
e
r
ij
(6.1)
where the sum is over pairs of electrons i and j, i.e. each pair appears only
once. Alternatively:

ij
=
N1

i=1
N

j=i+1
(6.2)
It is convenient to introduce one-electron and two-electrons operators:
f
i

h
2
2m
e

2
i

Zq
2
e
r
i
(6.3)
g
ij

q
2
e
r
ij
(6.4)
With such notation, the Hamiltonian is written as
H =

i
f
i
+

ij
g
ij
(6.5)
46
provided that g act symmetrically on the two electrons (denitely true for the
Coulomb interaction).
6.2 Hartree Equations
Let us assume that the total wave function can be expressed as a product of
single-electron orbitals (assumed to be orthonormal):
(1, 2, . . . , N) =
1
(1)
2
(2) . . .
N
(N) (6.6)
_

i
(1)
j
(1) dv
1
=
ij
. (6.7)
As in previous chapter, variables 1, 2, .., mean position and spin variables
for electrons 1,2,...;
_
dv
i
means integration on coordinates and sum over spin
components. Index
i
labels instead the quantum numbers used to classify a
given single-electron orbitals. All orbitals must be dierent: Paulis exclusion
principle tells us that we cannot build a wave function for many electrons using
twice the same single-electron orbital. In practice, for the case of atoms, the
main quantum number n, orbital angular momentum and its projection m.
The expectation value of the energy is
|H| =
_

1
(1) . . .

N
(N)
_
_

i
f
i
+

ij
g
ij
_
_

1
(1) . . .
N
(N) dv
1
. . . dv
N
=

i
_

i
(i)f
i

i
(i) dv
i
+

ij
_

i
(i)

j
(j)g
ij

i
(i)
j
(j) dv
i
dv
j
=

i
_

i
(1)f
1

i
(1) dv
1
+

ij
_

i
(1)

j
(2)g
12

i
(1)
j
(2) dv
1
dv
2
(6.8)
In the rst step, we made use of orthonormality (6.7); in the second we just
renamed dummy integration variables with the standard choice 1 and 2.
Let us now apply the variational principle to formulation (4.10), with the
constraints that all integrals
I
k
=
_

k
(1)
k
(1) dv
1
(6.9)
are constant, i.e. the normalization of each orbital function is preserved:

_
|H|

k
I
k
_
= 0 (6.10)
where
k
are Lagrange multipliers, to be determined. Let us vary only the
orbital function
k
. We nd
I
k
=
_

k
(1)
k
(1) dv
1
+ c.c. (6.11)
47
(the variations of all other normalization integers will be zero) and, using the
hermiticity of H as in Sec.4.1.1,
|H| =
_

k
(1)f
1

k
(1) dv
1
+ c.c.
+

j=k
_

k
(1)

j
(2)g
12

k
(1)
j
(2) dv
1
dv
2
+ c.c. (6.12)
This result is obtained by noticing that the only involved terms of Eq.(6.8) are
those with i = k or j = k, and that each pair is counted only once. For instance,
for 4 electrons the pairs are 12, 13, 14, 23, 24, 34; if I choose k = 3 the only
contributions come from 13, 23, 34, i.e.

j=k
(since g is a symmetric operator,
the order of indices in a pair is irrelevant)
Thus the variational principle takes the form
_

k
(1)
_
_
f
1

k
(1) +

j=k
_

j
(2)g
12

k
(1)
j
(2) dv
2

k

k
(1)
_
_
dv
1
+ c.c. = 0
i.e. the term between square brackets (and its complex conjugate) must vanish
so that the above equation is satised for any variation:
f
1

k
(1) +

j=k
_

j
(2)g
12

k
(1)
j
(2) dv
2
=
k

k
(1) (6.13)
These are the Hartree equations (k = 1, . . . , N). It is useful to write down
explicitly the operators:

h
2
2m
e

2
1

k
(1)
Zq
2
e
r
1

k
(1) +
_
_

j=k
_

j
(2)
2
r
12

j
(2) dv
2
_
_

k
(1) =
k

k
(1)
(6.14)
We remark that each of them looks like a Schrodinger equation in which in
addition to the Coulomb potential there is a Hartree potential:
V
H
(r
1
) =
_

k
(2)
q
2
e
r
12
dv
2
(6.15)
where we have used

k
(2) =

j=k

j
(2)
j
(2) (6.16)

j
is the charge density due to all electrons diering from the one for which we
are writing the equation.
6.2.1 Eigenvalues and Hartree energy
Let us multiply Hartree equation, Eq(6.13), by

k
(1), integrate and sum over
orbitals: we obtain

k
=

k
_

k
(1)f
1

k
(1)dv
1
+

j=k
_

k
(1)
k
(1)g
12

j
(2)
j
(2)dv
1
dv
2
.
(6.17)
48
Let us compare this expression with the energy for the many-electron system,
Eq.(6.8). The Coulomb repulsion energy is counted twice, since each < jk >
pair is present twice in the sum. The energies thus given by the sum of eigen-
values of the Hartree equation, minus the Coulomb repulsive energy:
E =

k

<jk>
_

k
(1)
k
(1)g
12

j
(2)
j
(2)dv
1
dv
2
. (6.18)
6.3 Self-consistent potential
Eq.(6.15) represents the electrostatic potential at point r
1
generated by a charge
distribution
k
. This fact claries the meaning of the Hartree approximation.
Assuming that is factorizable into a product, we have formally assumed that
the electrons are independent. This is of course not true at all: the electrons
are strongly interacting particles. The approximation is however not so bad if
the Coulomb repulsion between electrons is accounted for under the form of an
average eld V
H
, containing the combined repulsion from all other electrons on
the electron that we are considering. Such eect adds to the Coulomb attraction
exerted by the nucleus, and partially screens it. The electrons behave as if they
were independent, but under a potential Zq
2
e
/r +V
H
(r) instead of Zq
2
e
/r of
the nucleus alone.
V
H
(r) is however not a true potential, since its denition depends upon
the charge density distributions of the electrons, that depend in turn upon the
solutions of our equations. The potential is thus not known a priori, but it is a
function of the solution. This type of equations is known as integro-dierential
equations.
The equations can be solved in an iterative way, after an initial guess of the
orbitals is assumed. The procedure is as follows:
1. calculate the charge density (sum of the square moduli of the orbitals)
2. calculate the Hartree potential generated by such charge density (using
classical electrostatics)
3. solve the equations to get new orbitals.
The solution of the equations can be found using the methods presented in
Ch.2. The electron density is build by lling the orbitals in order of increasing
energy (following Paulis principle) until all electrons are placed.
In general, the nal orbitals will dier from the starting ones. The procedure
is then iterated by using as new starting functions the nal functions, or with
more sophisticated methods until the nal and starting orbitals are the same
(within some suitably dened numerical threshold). The resulting potential V
H
is then consistent with the orbitals that generate it, and it is for this reason
called self-consistent eld.
6.3.1 Self-consistent potential in atoms
For closed-shell atoms, a big simplication can be achieved: V
H
is a central
eld, i.e. it depends only on the distance r
1
between the electron and the
49
nucleus. Even in open-shell atoms, this can be imposed as an approximation,
by spherically averaging
k
. The simplication is considerable, since we know
a priori that the orbitals will be factorized as in Eq.(2.10). The angular part is
given by spherical harmonics, labelled with quantum numbers and m, while
the radial part is characterized by quantum numbers n and . Of course the
accidental degeneracy for dierent is no longer present. It turns out that even
in open-shell atoms, this is an excellent approximation.
Let us consider the case of two-electron atoms. The Hartree equations,
Eq.(6.14), for orbital k = 1 reduces to

h
2
2m
e

2
1

1
(1)
Zq
2
e
r
1

1
(1) +
_
_

2
(2)
q
2
e
r
12

2
(2) dv
2
_

1
(1) =
1

1
(1) (6.19)
For the ground state of He, we can assume that
1
and
2
have the same spher-
ically symmetric coordinate part, (r), and opposite spins:
1
= (r)v
+
(),

2
= (r)v

(). Eq.(6.19) further simplies to:

h
2
2m
e

2
1
(r
1
)
Zq
2
e
r
1
(r
1
) +
_
_
q
2
e
r
12
|(r
2
)|
2
d
3
r
2
_
(r
1
) = (r
1
) (6.20)
6.4 Code: helium hf radial
Code helium hf radial.f90
1
(or helium hf radial.c
2
) solves Hartree equa-
tions for the ground state of He atom. helium hf radial is based on hydrogen radial
and uses the same integration algorithm based on Numerovs method. The new
part is the implementation of the method of self-consistent eld for nding the
orbitals.
The calculation consists in solving the radial part of the Hartree equation
(6.20). The eective potential V
scf
is the sum of the Coulomb potential of the
nucleus, plus the (spherically symmetric) Hartree potential
V
scf
(r) =
Zq
2
e
r
+ V
H
(r), V
H
(r
1
) =
q
2
e
2
_
|R(r
1
)|
2
r
12
d
3
r
2
. (6.21)
We start from an initial estimate for V
H
(r), calculated in routine init pot (
V
(0)
H
(r) = 0, simply). With the ground state R(r) obtained from such potential,
we calculate in routine rho of r the charge density (r) = |R(r)|
2
. Routine
v of rho re-calculated the new Hartree potential V
out
H
(r) by integration, using
the Gauss theorem:

V
out
H
(r) = V
0
+ q
2
e
_
r
rmax
Q(s)
s
2
ds, Q(s) =
_
r<s
(r)4r
2
dr (6.22)
where Q(s) is the charge contained in the sphere of radius s; r
max
is the out-
ermost grid point, such that the potential has already assumed the asymptotic
value V
0
= q
2
e
/r
max
, valid at large r.
1
http://www.sica.uniud.it/%7Egiannozz/Corsi/MQ/Software/F90/helium hf radial.f90
2
http://www.sica.uniud.it/%7Egiannozz/Corsi/MQ/Software/C/helium hf radial.c
50
The Hartree potential is then re-introduced in the calculation not directly
but as a linear combination of the old and the new potential. This is the
simplest technique to ensure that the self-consistent procedure converges. It
is not needed in this case, but in most cases it is: there is no guarantee that
re-inserting the new potential in input will lead to convergence. We can write
V
in,new
H
(r) = V
out
H
(r) + (1 )V
in
H
(r), (6.23)
where 0 < 1. The procedure is iterated (repeated) until convergence is
achieved. The latter is veried on the norm, i.e. the integral of the square, of
V
out
H
(r) V
in
H
(r). square.
In output the code prints the eigenvalue
1
of Eq.6.13, plus various terms of
the energy, with rather obvious meaning except the term Variational correction.
This is
E =
_
(V
in
H
(r) V
out
H
(r))(r)d
3
r (6.24)
and it is useful to correct
3
the value of the energy obtained by summing the
eigenvalues as in Eq.(6.18), so that it is the same as the one obtained using
Eq.(6.8), where eigenvalues are not used. The two values of the energy are
printed side by side. Also noticeable is the virial check: for a Coulomb
potential, the virial theorem states that T = V /2, where the two terms
are respectively the average values of the kinetic and the potential energy.
6.4.1 Laboratory
Observe the behavior of self-consistency, verify that the energy (but not
the single terms of it!) decreases monotonically.
Compare the energy obtained with this and with other methods: per-
turbation theory with hydrogen-like wave functions (E = 5.5 Ry, Sect.
C.1), variational theory with eective Z (E = 5.695 Ry, Sect. C.2),
best numerical Hartree(-Fock) result (E = 5.72336 Ry, as found in the
literature), experimental result (E = 5.8074 Ry).
Make a plot of orbitals (le wfc.out) for dierent n and . Note that
the orbitals and the corresponding eigenvalues become more and more
hydrogen-like for higher n. Can you explain why?
If you do not know how to answer the previous question: make a plot
of V
scf
(le pot.out) and compare its behavior with that of the Zq
2
e
/r
term. What do you notice?
Plot the 1s orbital together with those calculated by hydrogen radial
for Hydrogen (Z = 1), He
+
(Z = 2), and for a Z = 1.6875. See Sect. C.2
if you cannot make sense of the results.
3
Eigenvalues are calculated using the input potential; the other terms are calculated using
output potential
51