3.

5 Splitting of a d-Level in Cubic Field 97

where 8 is the angle between the magnetic field and the tetragonal four-
fold axis. The isotropic g-factor seen in (2.38) (and, more particularly,
in (2.39)) became replaced by an anisotropic quantity

(3.29)

(3.30)

where X is the spin-orbit coupling constant, and the crystal field energy
levels carry the indices of the tetragonal point group (see p. 135).
For a spin-only moment, we would expect g = 2. If the level in
question is non-degenerate, the deviation from 2 can be estimated by
first-order perturbation theory, and it is small if X is sufficientlysmaller
than the relevant crystal field splittings. In this case, the magnetic
moment is still mainly a spin moment, and the restoration of the orbital
magnetic moment is a weak effect. (As a matter of fact, for Cuss
in C a 0 4 . 5 H 2 0 the corrections are quite substantial: 911 = 2.4 and
91 = 2.06. In any case, the deviation of g from 2 due to solid-state effects
is expected to be rather larger than the radiative correction shown in
(2.39)).
The above results can be reformulated in a more elegant manner by
introducing the tensor
0 0
g=(? 91 0 ) (3.31)
0 911
0
which allows us to write the coupling to the field as
' H = / J B S * g oH . (3.32)
This is a simple example of single-ion effective spin Hamiltonians. Spin
Hamiltonians are useful for the description of systems like CuS04.5H20:
the aagular momentum is almost quenched by the crystal field, thus
the magnetic field acts on the spin, but the weak spin-orbit coupling
manages to transmit the effect of the anisotropic environment. Doing
calculations like that in Problem 3.4, but for ions with spin S > 1/2,
one finds that the general form of the spin Hamiltonian is 14651
~ = E ( O ) + ~ ~ S g. . H-X~S.A.S-&H.A.H (3.33)