1.

3 Getting Acquainted: Magnetite 13

and we get essentially a half-filled band, with a little suppression of the

simultaneous occupancy of nearest-neighbour sites. On the other hand,
if we set t = 0, for half as many particles as sites the term

<ij>

will want to set up a superstructure in which only every other site is

occupied:

Fe3+ Fe2+ Fe3+ Fe2$

Such an electron crystal'can be considered as a large-amplitude

charge density wave. The Verwey transition in magnetite has been
considered as a candidate for the long-sought phenomenon of Wigner
crystallization, the formation of an electron crystal. In our particular
case, it also means that the two different valence states tend to form a
superstructure: this can be referred to as heterogeneous mixed valence.
The phenomenon is widespread in transition metal oxides.
The Wigner crystal is a prime example for strongly correlated states.
Here it is clear what strong correlation means: the electrons do their
utmost to avoid each other in direct space. It is easy to accept that the
electron crystal is insulating (in contrast, the ground state of Xhop would
be a conducting electron fluid). Another interesting point is that the
charge-ordered ground state shown above does not have the full trans-
lational invariance of the underlying lattice: it is symmetry-breaking.
Quite generally, one of the most important effects of electron-electron
interaction is the appearance of symmetry-breaking ground states, Le.,
of ground states whose symmetry is lower than that of the Hamiltonian.
Returning now to the real, three-dimensional magnetite, let us ac-
cept that the first-order transition manifested in the spectacular jump

' -
in conductivity is a charge ordering transition of the kind we have been
discussing. Below the Verwey temperature T 122K,a superstruc-
ture of different valence states should be seen. Once it was thought
that it can be envisaged as a simple alternation of Fe2+ and Fe3+ sites
when looking down along certain rows of atoms [18]. However, we would