5.

5 Correlated Insulators 249

non-conductor, but also an extra spin into an ordered magnet. Namely,

a phole amounts to leaving one of the plobes of an oxygen ion with
aa uncompensated spin. This spin is sorrounded by Cu-site spins, and
p-d hybridization gives rise to an antiferromagnetic Cu2+-O- exchange
interaction which consists of contributions t i d / g and
N t:d/(Ud -
N

ep). Actually, it is best to start by considering the four oxygen sites

surrounding a central copper site, and let the phole spread out to the
four sites occupying an orbital which has the same symmetry as the spin-
carrying d-orbital at the central Cu site. This pstate binds optimally
to the central d-spin, forming a Bang-Rice singlet [468]. Low-level Sr
doping of La2CuO4 can be envisaged as giving rise to a dilute gas of
Zhang-Rice singlets which, though they are fairly complex, spread-out
objectsao, still can propagate21.
The cwe of electron doping is different in the sense that it does
not distinguish between the two classes of insulators: in either case,
added electrons go into the upper Hubbard subband". This means that
electron doping and hole doping play asymmetric roles in charge transfer
insulators: for instance, electron-type LazCuO4-like superconductors (of
which Nd2-,CeZCu04 provides an example) we very different from the
hole-type ones. In contrast, for a Mott insulator, the effects of electron-
doping and holedoping can be interpreted in a unified scheme.
Doping is often not intentional at all. Apart from the unavoidable
impurities, transition metal oxides just do not want to grow stoichiomet-
rically: it is not unusual to find several per cent deviation of the oxygen
content from its nominal integer value23. This is a serious problem:

20Lookingfrom far away, we see three charges missing from the immediate envi-
ronment of a Cu atom, so we may think it is the low-spin state of Cu3+. At a closer
look, into resolves into an ordinary CuZf bound to a surrounding phole complex. It
is a not unfrequent experience that unwmmonly looking higher oxidation states of
metal ions had better be envisaged as the ion in a lower oxidation state, bound by
exchange interaction to a surrounding ligand hole.
21Hawever,consideration of the long-range Coulomb force may lead to the conclu-
sion that they localize into thin domain walls. See p. 568.
22Wemight have thought that sometimes they go into the 43 band. However, this
case does not seem to be realized.
231n spite of this fact, COO or magnetite are not metallic. The reason is that,
because of the narrowness of the 3d-band, polaronic effects come into play. Small
polaton8 are heavy quasi-particles which are readiiy localized by the random potentid