76 Ch.

3 Crystal Field Theory

In this Chapter, we will be speaking about systems where the d- or f -

electrons in partially filled shells occupy well-localized, ionic-like states.
In other words, we assume that the d-electron systems we have in mind
are Mott-insulators2. f-electrons are often localized even if the sur-
rounding solid is a metal; this phenomenon, like the Mott-localization of
&electrons, is an electron correlation effect. In either case, the localized
electrons must be affected by the electrostatic field of the surrounding
ions: the crystal fields.
A typical situation is shown in Fig. 3.1. Many interesting com-
pounds with the composition ABO3 (where A and B stand for different
metals) have the well-known perovskite structure (see, e.g., Ch. 14 of
[209]). The ideal perovskite structure is cubic; the actual structure can
often be understood as a slightly distorted perovskite. For a first ori-
entation, it is perfectly alright to pick out a small detail of the ideal
structure: the left panel of Fig. 3.1 shows the typical local environment
“seen” by the metal ion B. If we are paying attention to the B atoms
only (say, because only they carry magnetic moments), we can envisage
the structure as a cubic array of corner-sharing BOG octahedra. The
horizontal planes can be drawn its the BO2 planes shown in the right
panel of the figure. These planes are separated by A 0 planes.
The Mott insulator LaTi03 has attracted considerable interest [401].
Though the material is not really cubic, the gross features can be under-
stood by assuming the ideal perovskite structure, identifying the filled
circles in Fig. 3.1 with Ti ions. When discussing the electronic structure
of a material like this, it is useful to start with the assumption that it
is an ionic compound, and try to guess the ionic charges. La is very
stable as a trivalent ion, and oxygen usually likes to be divalent, so the
nominal valence states can be summarized in the formula La3+Ti3+0i-.
La3+ and 02- have closed shells. A closed-shell ion is non-magnetic3
and more-or-less tightly bound. It means that a finite, often consider-
able energy is needed to excite an electron out of the shell. As far as
the low-temperature, low-energy electrical and magnetic properties are
concerned, all the action is taking place in the incomplete shells (or in
the bands derived from them). In our particular case, the magnetic mo-
ment is carried by the remaining single d-electron of the Ti3+ ion. Now,
‘For a detailed treatment, cf. Ch. 4
31n the sense of having no permanent moment.