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PCD 100 SCF
PCD 100 SCF
lecture course given at the DST-SERC School at the Birla Institute of Technology, Pilani, January 9-28, 2011.
ABSTRACT
The analytical solutions to the Schrodinger equation for the non-relativistic
Hydrogen atom are well known to an under-graduate. As one considers an atom
or ion with more than one electron, one encounters formidable challenges, since
exact analytical solutions cannot be obtained for a system of many-electrons.
The electron-electron term makes the solution inseparable in single-particle
coordinates, except in only an approximate manner. The Hartree-Fock Self
Consistent Field approximation (HF SCF) provides an excellent starting point to
deal with a many-electron system and even if further improvements on this are
available and often employed, the HF SCF scheme itself serves a very large
number of applications. The methodology is applicable not only to atoms/ions,
but is readily extended to study other many-body systems, including molecules,
clusters, solids etc. An introduction to the basic principles employed in the HF
SCF scheme is provided in this article.
I.
INTRODUCTION
It is well-known that the first model of the electronic structure of atoms based on
the idea of quantization of the angular momentum was proposed by Niels Bohr
in the year 1913. Bohrs model was based on the planetary model of Kepler, but
the Bohr-Kepler orbits are indefensible since an orbit requires a simultaneous
description of position and momentum of the electron which correspond to
mutually incompatible observables. The Bohr-model thus had to give way to
formal quantum theory based on the Schrodinger equation and the Heisenbergs
principle of uncertainty.
The Schrodinger equation for the Hydrogen atom has exact analytical solution,
but an atom consisting of two or more electrons poses a formidable challenge.
As pointed out by Professor G. E. Brown, if one is looking for exact solutions,
having no body at all is already too many; even the analysis of the vacuum
state requires approximations! Quantum elementary particles such as in a manyelectron system are fundamentally identical, and one cannot track the temporal
dynamics of each electron separately when it is in the company of another. The
f ( ri ) v ri rj
i
i j
(1)
H1 H 2 .
can be defined only in terms of the electron charge densities that generate the
electron-electron interactions, but the charge densities themselves must be
expressed only in terms of the electron wavefunctions, which are to be obtained
from the solution to the N-electron Schrodinger equation - but that requires the
Hamiltonian to be set up in the first place!
It was D. R. Hartree (1897-1958) who came up with the first idea of getting Self
Consistent Field (SCF) solutions to a many-electron problem as a strategy to
break the Catch-22 state. D. R. Hartree was helped by his father, William
Hartree, in solving the numerical problems involved in solving the SCF problem
[3,4]. It is no wonder that with his numerical skills, D. R. Hartree designed a
large differential analyzer, in 1935, prototype for which was a small-scale
machine built from pieces of children's Meccano - which actually solved useful
equations concerned with atomic theory in 1934! When John Eckert set up the
ENIAC, Hartree was asked to go to the USA to advice on its use. Hartree
showed how to use ENIAC to calculate trajectories of projectiles. Hartree
predicted at Cambridge in 1946 that: It may well be that the high-speed digital
computer will have as great an influence on civilization as the advent of nuclear
power. How truthful Hartrees vision has turned out to be!
Hartrees original method made use of the IPA in which the N-electron
wavefunction was written as a product of one-electron wavefunctions. It was the
extension of this idea that has come to be known as the Hartree-Fock method in
which the Paulis exclusion principle got formally incorporated. It accounts for
the fundamental identity of the electrons that makes a many-electron
wavefunction anti-symmetric. This description of the many-electron system is in
accordance with the Fermi-Dirac (FD) statistics.
The spin of the electron plays an essential role in determining the fermion
character of the electron. The spin is an intrinsic property, just like mass and
charge, of the electron; it corresponds to the electrons intrinsic angular
momentum. It has no classical analogue. The rule that particles with halfintegral spin observe Fermi-Dirac statistics (and those with integral spins
observe the Bose-Einstein statistics) is well-known, but it is based on very deep
and difficult principles. With reference to it, Feynman remarks [5]: It appears to
be one of the few places in physics where there is a rule which can be stated very
simply, but for which no one has found a simple and easy explanation. The
explanation is down deep in relativistic quantum mechanics... The electron
spin emerges naturally from the relativistic (Dirac) equation, but it is included in
the N-electron non-relativistic Schrodinger equation on an ad-hoc basis in the
HF SCF method.
The one-electron spin-orbital u (q) for an electron is a function of four
coordinates represented collectively by q r , wherein r is the electrons
position vector made up of the three space coordinates, and represents its spin
coordinate. The atomic electrons spin-orbital is described by the central field
quantum numbers n, l , ml , ms . The spin-orbital is expressed as the product,
ui (q j ) ni ,li , ml (r j ) ms ( j ) , of the orbital part with the spin part. The
i
( N ) (q1 , q2 ......qN )
u1 (q1 ) u1 (q2 )
......
u1 (qN )
u2 (q1 ) u2 (q2 )
......
u2 (q N )
.
:
ui (q j )
:
N! :
u N (q1 ) u N (q2 ) ...... u N (qN )
(2)
The SD explicitly manifests the Pauli Exclusion Principle, since the determinant
would vanish if any two rows were to be equal. It is also manifestly antisymmetric, since the determinant would change its sign every time the parity of
the permutations of the N identical electrons is odd.
II.
The SCF strategy consists of using some guess wavefunctions to construct the
Hamiltonian, and then solve the Schrodinger equation for this Hamiltonian:
H ( N ) (q1 ,., qN ) ( N ) (q1 ,., qN ) E ( N ) ( N ) (q1 ,., qN ).
(3)
One then inquires if the solutions to the Schrodinger equation yield the same
wavefunctions that one had guessed [1,2]. Comparison of the two sets of
wavefunctions is then tested to lie within a desired numerical convergence
criterion. If the convergence fails, the trial functions are varied and the process
iterated upon till self-consistency is attained to yield numerical solutions. The
basic methodology of the HF SCF scheme is very well described in a number of
text books, such as [1,2].
Now, a variation of the one-electron spin-orbitals is required to attain the SCF,
but the variation is subject to the constraints of (i) normalization of the spinorbitals ui u j 1 for j i , and (ii) the orthogonality ui u j 0 for j i ; i
and j stand respectively for the collective complete set of good quantum
th
th
( N ) | H ( N ) | ( N ) 0 .
(4)
(5)
It is clear from Eq. 1 and Eq.4 that we need for our analysis
| | , with
H1 and
H 2 . It may be noted here that the Slater
determinantal wavefunction can be conveniently written as
(1)
N!
(N )
P 1
(6)
dVu (r ) f (r )u (r )
*
i 1
*
*
dV1dV2 u i (r1 )u j (r 2 ) r ui (r1 )u j (r 2 )
1
12
+
1
2 i j
*
*
(msi , ms j ) dV1dV2 u i (r 2 )u j (r1 ) r ui (r1 )u j (r 2 )
12
(7a)
in which the operators f ( r ) and
1
v ri rj have been introduced in Eq.1.
rij
This result can be written in a compact form using the Dirac notation:
N
( N ) | H | ( N ) i | f | i
i 1
1 N N
ij | g | ij ij | g | ji
2 j 1 i 1
(7b)
The first of the two-center integrals in Eq.7a is called as the Coulomb integral,
and the second is the Exchange integral.
Using Lagranges method of variational multipliers [6] ij , the condition (Eq.4)
of the extremum, subject to the constraints described by Eq.5, is then expressed
by the following relation:
(N )
|H |
(N )
ii
(8a)
dV ui* r ui r
i 1
(msi ,ms j )
ij
dV ui* r u j r
ji
dV u *j r ui r
i j
Within the frozen orbital approximation, allowing for a variation in only the k th
orbital and in none other, Eq.8a gives:
u
(
r
)
u
(
r
)
1
2
u j (r 2 ) k
dV u * (r1 )
j
1
k
dV
(
m
,
m
)
u
(
r
)
u
(
r
)
j
2
1
12
sk
sj
k
j
*
0 dV1 uk (r1 )
*
*
(8b)
The necessary and sufficient condition that Eq.8b is satisfied within the frozen
orbital approximation turns out to be:
f (r1)u (r )
k 1
u* j (r 2 ) uk (r1)u j (r 2 )
(9)
dV2
r
j
12 (msk , ms j )uk (r 2 )u j (r1)
( ms ,ms ) u j r
1
j kj
k
j
f (r1)u (r )
i
u* (r 2) ui (r1)u j (r 2)
dV
r
(m , m
2
12
s s )ui (r 2)u j (r1)
j
i
j
u r1
i i
(10)
where
i ii .
(11)
Eq.10 is referred to as the HF equation in the diagonal form. There are N such
coupled integro-differential equations and these are amenable to numerical
solutions.
Within the framework of the frozen orbital approximation, it can be shown that
k | f | k kj | g | kj kj | g | jk = k
(12)
and
E ( N ) E N 1
( nk 0)
k kk ,
where, E ( N ) ( N ) H ( N ) ( N )
(13)
(14)
and
E ( N 1)
nk 0
( N 1) nk 0 H ( N 1) ( N 1) nk 0 .
(15)
Eq.14, except for the fact that the k orbital uk is now considered to be
unoccupied. The result expressed in Eq.13 is a consequence of the frozen orbital
approximation. It lends a direct physical interpretation to the Lagranges
variational multipliers kk k , since the left hand side of Eq.13 can be
directly interpreted as the ionization energy required to produce a hole in the
k th one-electron state, within the framework of the approximation that other
orbitals, and their associated charge densities, are considered frozen. The result
expressed in Eq.13 is known as an extremely famous theorem, known as the
Koopmans theorem [7]. It provides an immediate connection of the HF
methodology with experimentally measurable ionization energies.
III.
The correlation that is built into this framework is the one that stems from the
identity of the electrons: an exchange of one electron with other results in a
configuration that is indistinguishable from the former, but it must result in a
wavefunction for the pair whose sign is -1 times that of the former. This
statement is an expression of the anti-symmetry of the electron wavefunctions,
10
IV. CONCLUSIONS
Hartree-Fock method has central importance in atomic and molecular physics,
quantum chemistry, and in all studies of electron structure studies in condensed
matter physics, including band structure calculations. It is an approximate
method derived through variational approach; its solutions provide the basic
frame work for systematic improvement of accuracy through enlarging the
variational space by considering linear combination of determinants:
Configuration interaction (CI) methods, Multi-configuration Self Consistent
Field (MCSCF) methods. Through the Koopmans theorem, the Lagranges
variational parameters introduced in the scheme attain significant physical
measurable attributes which connect the HF methodology to experimental
observables. It is superfluous to add that all collision dynamics involving matterprobe interactions require an accurate description of the target, no matter what
APPENDIX A
A few useful mathematical expressions are provided in this Appendix which will
be useful in filling in the steps that have been omitted in the formulation of the
HF SCF method described in the main text of this article.
A.1
For every operator which is symmetric with respect to identical
electrons,
( N ) | | ( N )
N!
1
P (1) p ... dq1..dqN P 1 * ( q1 ,.., qN ) {u1 ( q1 )...u N ( q N )}
N ! P1
N!
1
dVu *i (r ) f (r )ui (r ) | i * | i
i 1
N
i 1
i 1
i | f | i i | f | i ,
since
| |
| | i 1.
12
dq dq u (q )u (q ) r
ui (q1 )u j (q2 )
dV1dV2u *i (r 1 )u * j (r 2 )
1
u (r 1 )u j (r 2 )
r12 i
12
| msi * 2 | ms j * 1 | msi 2 | ms j
dV1dV2u *i (r 1 )u * j (r 2 )
1
u (r 1 )u j (r 2 )
r12 i
dq dq u (q )u (q ) r
*
ui (qi )u j (q j )
ij
1
u (q1 )u j (q2 )
r12 i
1
u (r1 )u j (r 2 )
r12 i
2 |msi * 1 | ms j * 1 | msi 2 | ms j
1
1
u (r1 )u j (r 2 ) (msi , ms j )
r12 i
1
{u1 (q1 )..u N (qN )}
ij
j 1, j i i 1
*
*
dqi dq j u i (qi )u j (q j ) r ui (qi )u j (q j )
ij
1
1
2 j 1, j i i1
*
*
dq
dq
u
(
q
)
u
(
q
)
u
(
q
)
u
(
q
)
i j i j j i
i
i
j
j
r
ij
1 N N
ij | v | ij ij | v | ji
2 j 1 i1
*
*
dV
dV
u
(
r
)
u
(
r
)
u
(
r
)
u
(
r
)
1
2
1
2
1
2
k
j
k
j
r12
1
j
*
*
(
m
,
m
)
dV
dV
u
(
r
)
u
(
r
)
u
(
r
)
u
(
r
)
2
1
1
2
sk
sj
1
2
k
j
k
j
r12
*
*
dV
dV
u
(
r
u
(
r
u
(
r
1 )u j ( r 2 )
1)
2)
1
2
k
k
j
r12
1
*
*
j
uk (r 1 ) u j (r 2 )
( msk , ms j ) dV1dV2u k (r 2 )u j (r 1 ) r
12
( N ) | H | ( N )
dV u * (r1 )
1
k
uk (r1 )u j (r 2 )
u
(
r
)
2
dV2 j
*
dV1 uk (r1 )
uk r 1
uk r 1
f r1 uk* r1
References
[1]
[2]
[3]
[4]
[5]
[6]
14
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]