5.

2 Superexchange 219

(5.56)

If the &electron spin configuration is J,?, the 4-spinpelectron can extend

to the B cation
IPZlY -
I P d + bldsd
d r n
(5.57)

and the total pelectron energy contribution is estimated as

El? - I
~ZlI'(PZtl~lP~t)~J=
P ,2%
~)'
2b2
+ iq&p- E d ) * (5.58)

The exchange splitting is approximately

fU - &lT - 2b4(Ed- e p ) - (1) .
J~~ (5.59)
The parallel configuration costs more energy, thus the effective exchange
is antiferromagnetic. The anion-mediated exchange described here is
known as superexchange.
In terms of perturbation theory, arises from a fourth-order pro-
cess, with two electrons jumping away from the central anion, and
two coming back. There is another fourth-order process which also
contributes to superexchange. Namely, covalent mixing changes the
character of the d-states as well, giving new d-like states of the kind
l d ~ ) 'N l d ~ -
) blp,), etc. Thus even if the original d-orbitals were

-
strictly non-overlapping, the new d-orbitals strongly overlap at the an-
ion site, the overlap being essentially b2(ed - c p ) . The same can be
our estimate for an effective hopping amplitude between the two d-like
orbitals t i B b2(rd - eP). Thus we can envisage the process of a &-spin
N

electron jumping from cation A to the anion, from there to the cation
B , and an ?-spin electron coming back the opposite way. This is quite
literally an exchange of spins, with the coupling

(5.60)