604 C.

11 Mixed Valence and Heavy Fermions

Hubbard centers.

11.2.1 Digression: 'alence Skipping

If electrons are added to a U > 0 system, the valence states follow each other
in an orderly fashion: fo -+ f' -+ f 2 + .... However, the story becomes
entirely different if we assume that the Hubbard U is negative: U = -1UI. Let
us reconsider the reasoning which gave us Fig. 11.2. Though putting the first
electron to a site8 costs the energy c f , putting a second electron to the same
site costs merely E/ - IUI. Hence we conclude that as soon as the chemical
potential reaches the value p = ef - ICrl/2, we start creating f 2 sites. In a
range of the overall electron concentration n, we find fo - f 2 valence mixing.
At the upper end of this range, the filling-up of the band continues and all
sites remain f2. The valence f' is skipped.
Though the assumption of negative4 Hubbard centres may sound un-
founded, it is interesting to observe that there are about fifteen elements which
rather consistently skip certain valence states [426]. For instance, Sb and Bi
are tri- or pentavalent but tetravalence is essentially missing. Pt likes to be
Pt2+ or Pt4+ but apparently shuns Pt3+. Though such observations are often
conveniently interpreted with the empirical rule of preference for (hdf)filled
shellsg, it is tempting to try to give an explanation in terms of an effective
U < 0. It would not be simple to justify that the effective U is negative:
clearly, it should result from the full treatment of a problem in which the shell
electrons in question interact with the lattice displacements of the surround-
ing complex, and with other electronic subsystems. However, we may accept
it that experiments tell us that such a justification should be possible.
To take an example, the average valence state of Bi in the perovskite
BaBiO3 is Bi4+, i.e., 6s' (apart from closed shells). Based on the picture of a
half-filled 6s band, we expect a paramagnetic metal but we find a diamagnetic
insulator. What are the 6s electrons doing in BaBiOs?
Let us model the 6s band with a half-filled negative4 Hubbard model and
assume that ( U (is sufficiently large. The Bi sublattice of BaBiOs is bipartite,
thus we may use the transformation (4.86) (see p. 193) to establish the corre-
spondence with the half-filled -U > 0 Hubbard model. The single-site basis
states are mapped (apart from an alternating sign factor) according to

'Since it is just a formal argument, we do not bother to the change notation, and
go on to speak about "local f-shells". As it turns out, the physical situation arises
for s-,p ,or d-electrons.
'For example, Bi" is [Xe]4f'45d'0, while Bi3+ is [Xe14fl45d"6s2.