5.

2 Superexchange 217

by the atoms squeezing past each other in the space allotted for them, thus
even the nominally pair exchange process must proceed by the nuclei moving
in a loop. For this reason, the exchange coefficient must be rather smaller than
what we would expect from the naively defined exchange charge. - Expressed
in terms of the atomic basis functions 9, q(x-1,r2) would be a sum of many
Slater determinants: we would be dealing with a configuration interaction
problem. This is the reason why this possibility could not be discussed within
the restricted Hilbert space used in Sec. 2.2.
In Hubbard-like lattice fermion models, we meet a similar difficulty when
discussing kinetic exchange in the limit U + 00. The pair term t 2 / U cer-
N

tainly vanishes but the possibility of ring exchange processes via intermediate
empty sites remains. We will describe such a case in detail in the solution to
Problem 7.T (see p. 437 and p. 488). In another interesting case, the interven-
ing sites are anion sites in a transition metal compound. We will see shortly
that the superexchange coupling contains contributions in which the Hubbard
U for the cation orbitals does not appear.

5.2 Superexchange
We declare ourselves basically satisfied with the kinetic exchange mech-
anism of antiferromagnetism we learned about in Sec. 5.1.5, accepting
that it suffices for the qualitative understanding of the majority of the
large number of insulating antiferromagnets. There is, however, a stum-
bling block: our previous argument worked for the singleorbital Hub-
bard model where the source of kinetic exchange is that electrons can
hop from site to site, restrained only by Coulomb repulsion. But most
antiferromagnetic insulators are transition metal compounds, in which
the &electron-bearing cations are separated by large anions (a typical
situation is shown in Fig. 5.1). Direct hopping between d-orbitals seems
rather unlikely.
Anderson [20, 251 has shown that the concept of kinetic exchange
can be extended to such situations and it is even enhanced by the cova-
lent mixing between cation and anion orbitals, thereby explaining the
large ordering temperatures of many compounds. To understand how it
works, let us consider the rather idealized situation shown in Fig. 5.1.
Say, the two cations can be thought of as Ti3+ ions with one d-electron
each, and the intervening anion is an 02-ion, as in LaTiO3. Zeroth-