11.

2 Valence: Integral, Mixed, Nearly Integral 609

I I I
15 10 5 0-EF
BINDINQ ENERQY (eW

Figure 11.5: XPS data on intermediate valent SmB6 can be fitted by assuming a
40%-60% mixture of Sm2+ and Sm3+ valence states (after [%I, reproduced in [436]).
The 4f6-4fs Hubbard splitting is U4f M 7eV.

with the drive towards particularly stable 4f shell configurations. We

have mentioned that Eu prefers divalency in order to have an exactly
half-filled f-shell; similarly, Yb2+ ions have a completely filled 4f shell.
We find also a value which is remarkably small: one of the points for
Ce. Cerium has two modifications: y-Ce looks trivalent and behaves like
the majority of rare earths but a-Ce appears to be strongly intermediate
valent, say like Ce+3*6,and has a much smaller atomic volume.
An important general lesson is that the valence state of the con-
stituent ions has a large effect on the lattice constant. The relationship
is so marked that (after establishing suitable benchmarks) it can be used
to determine the valence state from lattice constant measurements. Nat-
urally, it is best to take an isostructural series of certain compounds:
e.g., the RE hexaboride series, or the family of RE monosulphides.
A further hybridization effect is that the chemical potential suffers
a shift of the order N V 2 p ( p ) ,and becomes slightly n-dependent. Thus
the plateaus shown in Fig. 11.2 would be no longer perfectly fiat but
gently rising. Still, the picture of the mixed valence regimes remains
essentially valid: there are wide ranges of n where the chemical potential
is pinned within a distance V 2 p ( e f )to one of the f-levels, and the
N

main effect of changing n is the corresponding change in the f”-fnsl

mixing ratio.
The model argument based on Fig. 11.2 may lead us to believe that