618 C.

11 Mixed Valence and Heavy Fermions

taking this too literally, we should remember that we considered the

orbitally non-degenerate PAM, and we might worry about whether in
a real system a gap can be opened for all the relevant angular momen-
tum channels, or there is hybridization only in some channels, while
the others give rise to flat bands in the middle of the gap. It seems to
be difficult to decide this by a general argument but the experimental
fact is that mixed valent semiconductors (with an even number of elec-
trons per unit cell) exist, and their behaviour is - roughly speaking - in
accordance with our simple argument [436].
We cite the example of YbBl2 in which the Yb2+ and Yb3+ valence
states are mixed. With 52 valence electrons per formula unit, Lut-
tinger's theorem allows the system to be an insulator, and that is what
it appears to be21. The temperature dependence of the resistivity can
be fitted with an Arrhenius law (Fig. 11.9), which allows the deduction
of the activation energy 5.2meV. In the physics of ordinary semi-
N

conductors, such a small activation energy would be associated with an

impurity level, but we have no qualms about ascribing it to intrinsic
behaviour in the present case. Even for non-interacting electrons, as-
suming w = 0(0.1)eV, and W and ef of 0 ( 1 ) e V , (11.6) readily gives a
gap 5-20meV. Strong interactions cause this value to be divided by 2-5
(see (1 1.16)), yielding values typical for mixed valent semiconductors.
Gaps of order 1-10 meV get washed out at temperatures of order of
100K, or maybe below. First of all, this means that a huge number of
carriers can be produced thermally. As for YbB12, Hall effect measure-
ments show that the carrier concentration is 7.10-6 per formula unit at
T = 1.7K, while it is 120000 times as high at room temperature [436].
Furthermore, thermal agitation destroys the intersite quantum coher-
ence (sustained by an energy gain Qw2/W)which gave rise to the
N

hybridization gap in the first place, and the system can be thought of
as an assembly of independent f-shells, immersed into a light electron
gas of c-electrons. As T is increased from 0 to T,,,,, we pass from a
"We have chosen YbBlz because SmBs which for decades had been thought of
as the canonical mixed valent semiconductor, shows bewildering behaviour. Recent

behaviour with an apparent gap of -

studies on good quality samples indicate that though the resistivity follows activated
4meV at intermediate T , it saturates at low
T ,as if the system were metallic with a very low concentration of carriers. If this is
indeed intrinsic behaviour, it is one for which we can offer no explanation.