Chapter 11

Mixed Valence and Heavy

Fermions

Placed into a solid environment, rare earth atoms donate two or three
electrons to wide bands, and are thus left with 4f valence electrons
only. The valence of a rare earth ion in a solid is defined as the number
of electrons donated to the 5d-6s type conduction bands. Rare earth
ions are usually trivalent. Notable exceptions are Eu, and Yb, which
tend to be divalent, and Ce which may loose more than three electrons,
becoming tetravalent.
An alternative way to characterize the valence state of an ion is to
count its f-electrons. Though the energies of the 5d-, 6s-, and 4f-like
states tend to overlap, it turns out that the number of the strongly
interacting 4f electrons which remain at the ion, is often a sharply
defined integer. For instance, Sm3+ is described as a 4f5 ion, and Yb2+
has the closed-shell configuration 4f14.
In many systems, including most elemental rare earths, all 4f sites
have the same integral valence. In addition, there are also systems in
which the valence can have any of two neighbouring integral values;
these are the so-called mixed-valent systems. Quite often, the local va-
lence states are mixed by either the quantum-mechanical motion of the
electrons, or thermally; this gives rise to a non-integral, intermediate va-
lence. Both integral and intermediate valence arise in a natural manner
as a result of strong correlations.

597