82 Ch.

3 Crystal Field Theory

If all symmetry operators commute with each other then according

to (3.4) we can seek a complete set of common eigenstates of 3t, and
of all the 9 operators. Within a common eigensubspace of the P’s,
the matrix elements of 3t will be, in general, non-vanishing, and all the
eigenenergies are different. In other words: if the symmetry group is
Abelian (commutative) then the energy levels are expected to be non-
degenerate. If we still find a degeneracy then it is not symmetry-related
and is therefore called accidental.
It is often found that not all symmetry operators commute: such is
the case with rotations about different axes, or rotations and transla-
tions. Now symmetry operations have an immediate usefulness because
they permit us to generate new eigenstates. Namely, we must be able
to find an energy eigenstate $n for which P $ n is linearly independent
of $n. Then what about P$n? We apply (3.3) to find

74 * @$n = P * 3t$n = En * P+n. (3.6)

If $n is an eigenstate with eigenvalue En, then $$n is also an eigenstate
with the same eigenvalue. Once we have found an eigenstate &, we can
apply the symmetry operations to generate further eigenstates. The
degeneracy of the eigenstates P $ n is symmetry-related. However, it
does not follow that all the states P $ n should be independent; the
dimensionality of the eigensubspace {P$nI .f) E G} is usually much
smaller than the number N of the group elements (Nis called the
order of the group). The question arises whether group theory allows
us to make general statements about the degree of degeneracy. Such is
indeed the case: The dimensionalities of the irreducible representations
of G give the possible degeneracies.

3.2.1 Irreducible Representations

It should be stressed again that it is not our purpose here to give a
systematic development of group representations. We just want to recall
those results which permit us to proceed straight to the treatment of
the crystal field splittings of ionic levels.
Starting from an eigenstate +n of 3c, let us apply to it all the sym-
metry operators 9. The resulting set of functions forms a d-dimensional
subspace of degenerate eigenstates with the property that applying any