80 Ch.

3 Crystal Field Theory

Strong crystal fields are comparable to (or larger than) the exchange
splittings giving rise to Hund’s first and second rule, thus they mix
even states belonging to different terms. It is quite usual to find strong
crystal fields in 4d and 5d transition metal compounds. On the other
hand, there are only rare instances of insulating solids where 3d ions are
subject to such strong crystal fields that even Hund’s first rule is put out
of action. In any case, the description of strong effects of surrounding
anions usually requires going beyond the simple ionic model, and taking
into account the mixing of the d-orbitals of the central cation with the
porbitals of the neighbouring anions. The binding of the substance
becomes partially covalent, and the details of the electronic structure
are rather different from the simple ionic picture we are using. However,
the symmetry analysis of the orbitals remains essentially the same which
we introduce in this Chapter. As a matter of terminology, let us remark
that considering the effects of the mixing between cation- and anion-
orbitals is the subject of ligandfield theory [379], while the term “crystal
field theory” is reserved for the purely ionic description.

3.2 The Role of Symmetry Arguments

in Quantum Mechanics
A detailed account of the theory of representations of symmetry groups,
and their application to solid state physics, would require an entire
course5. Here we assume that the reader is already familiar with the
elements of group theory and recall just the arguments why group theory
is useful in solving the quantum mechanical eigenvalue problem.
Let us assume that there exists a set of geometric transformations
P : r + r’ which leave the Hamiltonian 3t invariant: X({r’}) = %({r}).
(In general, X depends on a number of position vectors r, which are all
transformed by P . {r} stands for the set of all the r vectors. However,
‘In the author’s experience, the typical student will have taken courses in group
theory, which were usually rather more advanced than what we need here, but put
less emphasis on applications to finite groups. The aim of the present text is to
refresh the reader’s memory about group theory, going into details about what we
are going to use, and omitting (as far as the continuity of the argument allows) what
we do not need. For a systematic treatment, see [399] or [195]. Other texts are
quoted elsewhere.