100 Ch.

3 Crystal Field Theory

these mechanisms are capable to drive a low-spin-high-spin phase tran-

sition. Indeed Lac003 shows complicated phase transitions but their
description requires a lot more sophistication [I]than the simple picture
we have been contemplating.
LaMn03 is another highly interesting perovskite. The Mn3+ ion
clearly preserves its S = 2 high-spin state (Fig. 3.5, right), but the
large t29-eg gap is not without consequences: it enables us to distinguish
between the electrons which form essentially stable t:, “cores”, and the
lightly bound eg electrons. This distinction plays an important role in
theories of the magnetism of doped LaMnOs (see Sec. 8.5.3).

3.6 Jahn-Teller Effect

Returning now to the case of a Cu2+ ion in an octahedral environment:
the d-hole is in an e,-state. As long as the environment is truly octahe-
dral, we cannot decide whether the orbital character is (3z2 - r2)-like
or (z2- y2)-like: the ionic ground state is predicted to be orbitally de-
generate. Now, it is just this what is not allowed to happen, as stated
in the celebrated
Jahn-Teller theorem (1938): if the symmetry of the crystal field
is so high that the ground state of an ion is predicted to be orbitally
degenerate then it will be energetically preferable for the crystal to
distort in such a way that the orbital degeneracy is lifted [182]. The
appearance of the distortion is the Jahn-Teller effect13.
For the sake of simplicity, let us assume that the octahedron gets
elongated in the x-direction (Fig. 3.6). Since now the two oxygen ions
on the z-axis are lying farther from the Cu-ion than the oxygen ions in
the z-y-plane, an electron in the (3z2- r2)-orbital is less repelled by
other charges, and thus lying at a lower energy level, than an electron
in the (z2 - y2)-orbital. The twofold degenerate E-level has been split
by the tetragonal distortion into (orbitally) non-degenerate levels (see
Fig. 3.7).
It should be stressed that we were ascribing the Jahn-Teller splitting
to a tetragonal distortion mainly because it is the easiest to envisage,
Any other distortion which splits the eg level, would do equally well.
13See [309] for a recent pedagogical review.