10 Ch.

1 Introduction

inadmissible because it leads to a S = 3/2 low-spin state8 of the Fe3+

ion. The physical reason for the exclusion of such processes is of the
same nature as the valence restriction formulated in (1.2): it would lead
from a low-energy subspace to a high-energy subspace. We will learn
later both the reason for the energetical separation of subspaces, and
the formal way of enforcing such constraints.
In our particular case, there is an additional factor which helps to
give a simple form to both constraints, meaning Eq. (1.2), and the re-

-
striction to high-spin states. Magnetite is ferrimagnetic, with the order-
ing temperature TN 858K. If we restrict ourselves to temperatures,
say, T < 200 K, it should be an acceptable approximation to think of
the electrons as moving on the background of a frozen pattern of spin
order.
We recall the basic features of ferrimagnetic order in the inverse
spinel structure of magnetite [209]. There are two sublattices of crystal-
lographically inequivalent lattice sites. Below T N ,the spins on the two
sublattices are oppositely polarized. From the chemical unit of three
iron ions, the sublattice A of tetrahedrally coordinated sites has one
Fe3+ ion, and the sublattice B of sites with octahedral local coordi-
nation, has one Fe3+ ion, and one Fe2+ ion. The spins of Fe3+ ions
thus compensate each other; the residual ferrimagnetic moment of mag-
netite can be ascribed to the Fe2+ ions which are distributed over the
octahedral sublattice B.
Thus at sufficiently low temperatures, where magnetic order is nearly
perfect, the only allowed hopping is that of the minority-spin electrons,
transmuting Fe2+ and Fe3+ sites:
s=5/2 s=2 s = 2 s=5/2

Fe3+ Fe2+ Fe2+ Fe3+

Having fixed the spin order means that, concentrating our attention
to the mobile electrons, the spin degree of freedom can be forgotten,
'It is called low-spin in comparison to S = 5/2 which is the largest possible value
of the spin for this ion.