Chapter 3

Crystal Field Theory

3.1 Incomplete Shells in an Anisotropic

Environment: Crystal Fields
As shown in Fig. 2.1, the formulae (2.76) and (2.89)-(2.93) which de-
scribe the combined response of orbital and spin momenta to external
fields, are spectacularly successful in describing the paramagnetic sus-
ceptibilities of rare earth systems. The high-temperature susceptibilities
of insulating transition metal compounds are described by similar for-
mulae; however, as we can see from Fig. 2.2, the magnetic moment
seems to arise almost solely from the spins of the 3d ions. The orbital
contribution is completely (or in any case, largely) missing.
The reason for the discrepancy is that the above-cited formulae were
derived using free ion eigenstates, while the d-shells in question belong
to ions embedded in a solid. It is intuitively clear that even in an
insulator, the motion of the electrons must be influenced by the crys-
talline environment. Lattice effects are certainly even larger in metals,
so much, that we may be wondering whether the concept of ionic-like d-
or f-electrons has any use at all. There are, however, important classes
of systems where this is the case'.
'Electrons occupying the compact 4f-shell can remain localized even in metals.
Furthermore, the high-temperature susceptibility of transition metals or their alloys
often contains a Curie-like (or Curie-Weiss) component. We will understand in later
chapters why d- and f-electrons can show localized behaviour in solids; here we
assume that they can do so, and explore the consequences.

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