11.

2 Valence: Integral, Mixed, Nearly Integral 603

Let us discuss the relationship between the overall electron concen-

tration n, the chemical potential p , and the 4f count n f . The situation
is depicted in Fig. 11.2. Assuming that ~f is lying above the bottom
of the band, increasing n from zero, p rises gradually while the band is
filling up, and the 4f-shells remain empty, i.e., the ionic configuration
is 4f0. However, when p reaches ef at some n = n c l , the electrons
begin to populate the 4f shells. In the range n,l < n < n,l + 1, the
chemical potential is pinned at E f , and a fraction of the f-sites is in the
valence state 4f1, while the remaining sites are empty. This is the case
of 4fo-4f1 valence mixing. To put it differently, the average valence is
intermediate: 0 < nf = n - n,l < 1. We see, however, that the term
“intermediate” has to be interpreted carefully: because of the strong
Coulomb interaction between 4f-electrons, the non-integral value of nf
arises from the mixture of the two neighbouring valence states 4f0 and
4f1 - and nothing else. This should be contrasted with the situation
for uncorrelated electrons, where the contribution of all valence states
is significant. Mixed valent systems are unique in the sense that the
allowed values of the valence are restricted to just two values. The phe-
nomenon of mixed valence offers us the most clear-cut realization of the
principle of minimum polarity.
Ftaising p further, the filling of band states begins again, and ev-
ery site is in the 4f1 state. This integral valent situation is apparently
stable over a wide range of band filling. Then, after the electron con-
centration has reached nc2,further added electrons go into the f-shells,
turning some of the sites into 4f2. In the regime of 4f1-4f2 valence
mixing, p remains pinned to ~j + U until every f-shell has taken up
a second electron. The alternation of integral valent and mixed valent
(generally 4fn-4 f n+l) behaviour continues like this until the f-shells
get completely filled with Af = 14 electrons each.
Allowing for a weak quantum-mechanical mixing (hybridization) be-
tween f and c states, the sharp corners of the p-n plot shown in Fig. 11.2
become rounded, but plateaus with approximately constant p are still
recognizable. However, the bondary between integer and mixed valence
regimes is no longer sharply defined but becomes replaced by a transi-
tion regime of nearly integral valence. We resume this discussion after
a short Digression about valence states in a system with negative4