Derivation of the Hamiltonian in terms of

Unitary Group Generators

C. David Sherrill
Center for Computational Quantum Chemistry
University of Georgia
March 1994

We begin with the second-quantized form of the one- and two-electron operators (see Szabo
and Ostlund [1], p. 95),
O1 =

2K
X

hi|h|jiai aj

(1)

ij

2K
1X
hij|kliai aj al ak
2 ijkl

O2 =

(2)

where the sums run over all spin orbitals {i }. Thus the Hamiltonian is
=
H

2K
X

ap aq [p|h|q] +

pq

2K
1X
a a as aq [pq|rs]
2 pqrs p r

(3)

Now integrate over spin, assuming that spatial orbitals are constrained to be identical for
and spins. A sum over all 2K spin orbitals can be split up into two sums, one over K orbitals
with spin, and one over K orbitals with spin. Symbolically, this is
2K
X
a

K
X
a

K
X

(4)

The one-electron part of the Hamiltonian becomes

one =
H

K
X

[p|h|q]ap aq + [p|h|
q ]ap aq + [
p|h|q]ap aq + [
p|h|
q ]ap aq

(5)

pq

After integrating over spin, this becomes

one =
H

K
X

(p|h|q){ap aq + ap aq }

(6)

pq

The two-electron term can be expanded similarly to give

K
1X

(pq|rs){ap ar as aq + ap ar as aq + ap ar as aq + ap ar as aq }
Htwo =
2 pqrs

(7)

Now we make use of the anticommutation relation

{aj , ai } = aj ai + ai aj = 0

(8)

and we swap the order of as and aq , introducing a minus sign. This yields
K
X

two = 1
H
(pq|rs){ap ar aq as + ap ar aq as + ap ar aq as + ap ar aq as }
2 pqrs

(9)

Now we use the anticommutation relation between a creation and an annihilation operator, which
is
{ai , aj } = ai aj + aj ai = ij
(10)
This relation allows us to swap the aq and ar in each term, to give
K
h
X
two = 1
(pq|rs) ap aq ar as q,r ap as + ap aq ar as q,r ap as
H
2 pqrs

+ ap aq ar as q,r ap as + ap aq ar as q,r ap as

(11)

Now we observe that q,r and q,r can both be written qr , and also that q,r and q,r are
both 0. This simplifies our equation to
K
h
1X

Htwo =
(pq|rs) ap aq ar as + ap aq ar as + ap aq ar as + ap aq ar as
2 pqrs

qr ap as qr ap as

(12)

Now we introduce the unitary group generators, which we write as [2]

Eij = ai aj + ai aj

(13)

and the Hamiltonian becomes

=
H

K
X

1X

(p|h|q)Epq +
(pq|rs) Epq Ers qr Eps
2 pqrs
pq

(14)

This is the Hamiltonian in terms of the unitary group generators [3].

References
[1] A. Szabo and N. S. Ostlund, Modern Quantum Chemistry: Introduction to Advanced Electronic
Structure Theory. McGraw-Hill, New York, 1989.
[2] J. Paldus, J. Chem. Phys. 61, 5321 (1974).
[3] I. Shavitt, Int. J. Quantum Chem. Symp. 12, 5 (1978).
2