3.

5 Splitting of a d-Level in Cubic Field 93

affair that with a little more effort, it is possible to guess the order of
the levels.
At the level of the atomic (ionic) Hamiltonian, we are free to choose
any five linearly independent states as a basis. (A.g)-(A.ll) (or (A.12)-
(A.14)) give the standard complex form of the 1 = 2 spherical harmonics.
Here, we find it instructive to go over to a basis of real wave functions.
When writing these down, we include the common factor r 2 which de-
scribes a part of the hitherto neglected radial dependence of the actual
3d-states (but we still omit the factor e-'/[ which is uninteresting from
our present point of view). The real basis functions are the so-called
tesseral harmonics [178] of the general form Tmf y-"

Introducing real basis states has immediately led to finding the standard
basis of the T2 and E representations (see Table 3.1).
The charge distribution of one representative of the E-type, and the
T2-type, functions is shown in Fig. 3.3. We see that the E functions
have lobes pointing along the coordinate axes, while the lobes of the T2
basis states point along the (110) directions bisecting the angle between
two coordinate axes. Recalling Fig. 3.1, we readily understand the
reason for the energy difference between the E and T2 levels. The E (or
es) states have electron charge maxima near to the negatively charged
oxygen ions, while the T2 (or t z g ) states manage to avoid these repelling
charges, as much as it is possible for d-states. We conclude that in
an octahedral environment of anions, the T2 level is lying lower than
the E level. On the other hand, if we place anions at the corners of
the cube shown in Fig. 3.2, we find the T2 orbitals getting nearer to
the repulsive charge of the ions, hence the order of the levels must be
reversed (Fig. 3.4).