96 Ch.

3 Crystal Field Theory

Let us return to the case of a cubic field, assuming that the sequence
of levels is as shown in Fig. 3.4.a and that Hund’s first rule applies,
and survey what happens to the orbital momentum for each of the
configurations d”. For d1 and 8, the T2 level is partially filled and for
the reasons described above, we expect that the quenching of the orbital
momentum is only partial. For d3, all the three T2 states are occupied,
and the total Lz must be zero. At d4, the configuration must be t:,e;,
the angular momentum is quenched. d5 with five parallel spins has no
orbital angular momentum at all. For d6 and d7, the filling of the Tz
level begins again, and the quenching is expected to be partial. On the
other hand, the quenching is complete for d8 and 8.

3.5.2 Partial Restoration of Orbital Momentum

by Spin-Orbit Coupling
One of our standard examples, the Cuss ion has the configuration
3 8 . From the above discussion it would follow that even in the high-
symmetry cubic environment, this ion has a spin-only magnetic moment
corresponding to S = 1/2. It should be stressed that this is true only
if we neglect the spin-orbit coupling. The spin-orbit coupling has two
important effects. First, it acts to restore some of the orbital angular
momentum. Second, by tying the spin to the orbital motion which is
influenced by the crystal fields, it provides a mechanism whereby the
spin can “feel” the orientation of the crystal axes. This is the way how
the phenomenon of magnetic anisotropy arises.
A well-studied case is that of the ionic insulator CuS04.5H20, where
the Cu++ ions are sitting in a tetragonal crystal field [465]. As one
can learn by solving Problem 3.1, superimposing a small tetragonal
component on a large cubic field splits the twofold degenerate E level
into two non-degenerate levels (page 135). The single d-hole occupies
the d . 9 4 level. The wave function is real and there could be no doubt
about the complete quenching of the orbital momentum if it were not
for the spin-orbit coupling. Relegating the details of the derivation to
the solution of Problem 3.4 (see page 137), we quote the final result:
switching on a magnetic field H , the Zeeman energies are