3.

1 Crystal Fields 79

called K2NiF4 structure [84]which differs from the perovskite structure

by having two A 0 planes (rather than one A 0 plane) in between two
consecutive BO2 planes. The CuOz plane of LaZCu04 (shown in the
right panel of Fig. 3.1) is a famous object because it is thought to be
the relevant structural unit of the high-?’, cuprates, Thus the local
environment of the Cu ions is approximately octahedral as in Fig. 3.1.
Identifying the valence states as LgsCu2+Oi-, we immediately see that
the only “interesting” ion (i.e., one with a partially filled shell) is Cu2+
which has the configuration 3 8 . Since 3d1’ would be a completely filled
shell, it is justified to consider Cu2+ as having one d-hole. The problem
of the electronic structure of Cu2+ is thus the mirror image of that of
the structure of Ti3+: there we were interested in the only d-state which
is occupied; here in the only state which is unoccupied.
Crystal field effects will also give an explanation of the missing or-
bital contribution to the susceptibility of transition metal ions. This
raises, however, another question: why have crystal fields seemingly no
effect on .Qf-electrons? In fact they do have an effect, only a much
weaker one than on 3d-electrons. The reason is that the 4f orbitals
are lying so deep within the ion core that other occupied shells of the
same ion largely screen out the potential of the surrounding ions. 4f
electrons indeed hardly notice whether they are in an ion embedded in
a crystal, or in a free ion. The 4f electrons in rare-earth-based solids
give an example of a weak crystal field satisfying
exchange splittings > spin-orbit coupling > crystal fields
Because of this order of the relevant coupling strengths, even Hund’s
third rule takes precedence over lattice effects. Crystal field effects (and
quite subtle ones at that!) act only within a given J-manifold.
Transition metal ions (particularly 3d-ions) belong to the category
of intermediate crystal field strengths
exchange splittings > crystal fields > spin-orbit coupling
Since crystal fields now dominate over the spin-orbit coupling, Hund’s
third rule ceases to apply. This means that though L and S remain valid
quantum numbers, and their values are still given by Hund’s first and
second rule, J is no longer a good quantum number. An intermediate
crystal field mixes states within a given ( L ,S) term.