84 Ch.

3 Crystal Field Theory

null matrix. - In this case, we call the representation I' reducible: it

has been decomposed into the representations rl and I'2.
What has happened is that instead of the original basis $1,. . , ,$d we
(1) , . . . , $dl
managed to find new basis states $1 (1) , and 41
(2) , . . . , $$I,
so that
j ).
the states cPj(1) are mixed only among themselves (and similarly for $ (2)
Clearly, the symmetry does not require a d-fold degeneracy; it may
require a dl-fold (and a &-fold) degeneracy - unless the representations
I'l and I'2 are themselves reducible.
If it is impossible to find a transformation U with the property (3.11),
we call the representation irreducible. The degeneracy of an eigenvalue
of 3t should thus be the dimensionality of one of the irreducible repre-
sentations of the symmetry group6.
We are frequently faced with the following problem: we have iden-
tified a (perhaps rather small) number of basis states which span the
physically relevant subspace of the Hilbert space. We find, however,
that these form the basis of a reducible representation. Quite often, it
is not so much the detailed solution of the actual eigenvalue problem
that we are interested in but rather in predicting how many different en-
ergy levels are expected, with which degeneracies. We want a machinery
for the decomposition of reducible representations.
Returning to (3.11): for the characters,

(3.12)

holds. This suggests that the decomposition of a representation can be

found by looking for a corresponding decomposition of its character. In
this, we are helped by the following orthogonality theorem

where h/ is the order of the group.

'These are the degeneracies which we can explain as following from the symmetry.
It is possible that additional degeneracies are found; these should be considered
(and are called) accidental, resulting from a special choice of the parameters of the
Hamiltonian. It may happen, however, that a seemingly inexplicable degeneracy can
be explained as the consequence of a previously unrecognized greater symmetry of
the problem. The degeneracy of the different l-levels in the non-relativistic hydrogen
atom problem is a case in point.