130 Ch.

3 Crystal Field Theory

(3.83)

The prefactors depend on the geometry of the charges: for instance, for
six point charges q at the positions (*a, O,O), (0, fa,0), ( O , O , Ax),one
finds
(3.84)

If the cubic field arises from eight charges situated at the corners of
a cube (Fig. 1.2) then

(3.85)

It should be noted that the sign of A4 differs for the two configurations.
The formulae (3.82), (3.83) look pleasingly symmetrical but they
are cumbersome to use: it is not quite simple to evaluate the matrix
element of, say, x2z4 between f-states. The situation gets worse if
we have several electrons in the shell and the matrix elements have to
be taken between Slater determinants. Noticing that all the relevant
matrix elements have to be taken between states of a given L- (or for
f-electrons, 2-)manifold, Stevens suggested that V4, etc., should be
replaced by their operator equivalents which are expressed in terms of
total angular momentum operators.
If we have in mind d-electrons, we may neglect the spin-orbit cou-

- - -
pling and express the operator equivalent in terms of the components
of the (total) orbital angular momentum L.The simple recipe is to per-
form the replacements I L,, y L,, z L,, and (I f iy) "v) L*.

-
Furthermore, if we meet an expression like zy, we have to remember
that though x and y commute, L, and L, do not, thus we have to use
the symmetrical replacement zy (L,L, +L,L,)/2. -- The justifica-
tion for introducing operator equivalents comes from the Wigner-Eckart
theorem.
To see an example, let us consider the operator equivalent of V4 in
terms of L,, L,, and L,. It is useful to go back to (3.55) and (3.54).
Omitting the prefactor, the relevant replacement is

+ + 5-[(x
35z4 - 30x2r2 3r4
2
+ 2 ~ + (z - Z Y ) ~ ]
) ~