32 Ch.

2 Atoms, lons, and Molecules

the same point is not forbidden by the Pauli principle. Therefore elec-
trons in the singlet state feel more of the mutual Coulomb repulsion:
this pushes the singlet energy up.
Since the orbital part of the wave function is rigid, the states can be
labelled by their spin component. We use the basis IS, S”),where S is
the total spin, and S” its z-component. Three eigenstates form a triplet

The fourth eigenstate is a singlet

1
1090) = -($2 - $3) ’ (2.55)
Ji
The action of ‘Id can be expressed in terms of spin operators. Let us
+
note that (Sl S2)2 gives 0 for a singlet and 2 for a triplet. Hence

2s1s2 + -12 = (S1+ s2)2- 1=

1
-1
for a triplet
for a singlet.
(2.56)

Using this identity, (2.52) and (2.53) can be conveniently combined into
a single expression

= constant - 2JabS1 S2. . (2.57)

Within the 4-element subspace, the electron-electron interaction can be

described as an exchange Hamiltonian. The possibility of this appealing
reformulation was first noticed by Dirac.
As we are going to see, a similar result is found in a variety of cases:
Let us assume that some further reasoning’ tells us that the orbital
component of a many-electron wave function can be considered rigid.
Build a subspace of the Hilbert space by keeping the orbital component
fixed, and choosing the spins in all possible ways. Within this subspace,

‘Usually stating that the electrons are Mott-localized.