4.

1 Metals and Insulators 149

On the other hand, with an odd number of electrons per unit cell we
necessarily have a partially filled band, so p ( e ~ #
) 0, and consequently
the material must be a metal.
This basic prediction of band theory spectacularly fails in a number
of cases [5, 293, 3301. One of the oldest-known, and clearest, examples
is provided by the transition metal oxide COO. The material has a
(slightly distorted) rocksalt structure so the unit cell contains one Co
atom, and one 0 atom. Remembering that the outer shells of Co have
the configuration 3d74s2,and for oxygen we can take 2s22p4,the number
of electrons3 per unit cell is 9+6=15, an odd number. According to
band theory, COO should be a metal. In fact, it is one of the toughest
insulators known. Band theory has failed.
Unfortunately, the argument cannot be kept as simple as this, nei-
ther so transparent. Independent electron theory in principle allows
that the symmetry of the mean field be lower than the symmetry of the
crystal lattice. In our particular case, this is realized by the “different
orbitals for different spins” scheme4. We take the sublattice of Co ions
and subdivide it further into magnetic sublattices so that ?-spins set-
tle predominantly on one sublattice, and $-spins on another5. Having
done this, we find an even number of electrons per magnetic supercell
and thus the independent electron description has, in principle at least,
an escape route to avoid contradiction with experiment. It is a quite
different question whether the band structure calculation based on the
assumption of a magnetic superstructure is then able to come up with
the right size of the gap to show COO to be as insulating as it actually
is. Without wishing to enter the argument, we note that it is at least
doubtful that it can [306].
So much for the ground state. At sufficiently high temperatures,
the antiferromagnetic order sustaining the magnetic supercell vanishes,
so we are back at the chemical unit cell with an odd number of elec-
3Electrons in deeper-lying closed shells could be included in the count without
affecting the argument.
4Also called the unrestricted Hartree-Fock method. A particular version of it will
be described in detail in Sec. 7.6.
‘From our present point of view, it is just a cumbersome detail that this subdi-
vision is not easy. The Co sublattice is the close-packed fcc lattice so it cannot be
divided into two alternate sublattices; at the very least, it must be divided into four.
It is sufficient to know that the number of magnetic sublattices is even.