236 Ch.

5 Mott Insulators

be qualitatively understood on the basis of the simple picture developed

in Ch. 4. Afterwards, we discuss some complications.
V203 has the secalled corundum structure. For our purposes, it
suffices to think of the structure as the sequence of puckered honey-
comb lattices of vanadium sites. We will call these the ub planes, and
the orthogonal direction the c-axis. The local environment is such that
the d-level splits13 into a non-degenerate ulg level and two twofold de-
generate eg levels. Correspondingly, we envisage a tight binding band
structure consisting of non-degenerate a l g and twofold degenerate eg
bands.
The band structure of a complicated material like this is subject
to recurring revisions, thus we rather prefer to take clues from experi-
ments. Ti203 is another interesting transition metal oxide, and it also
has the corundum structure. At low temperatures, it is a non-magnetic
insulator. People often use a real-space picture, in which each Ti ion
donates its 3d electron to form a singlet bond with its nearest neighbour
along the c-direction. This also implies a doubling of the unit cell along
the c-axis. In band language, the nature of the ground state can be
understood to arise from the filling of a non-degenerate ulg band. We
assume that the sequence of the bands is the same in V2O3, thus the
lowest-lying ulg band is filled. The electrical and magnetic properties
are then ascribed to the remaining one electron per V site which be-
come Mott-localized. This would suggest that though a free V3+ ion
has S = 1, in V2O3 the localized moments belong rather to S = 1/2,
possibly augmented by some orbital contribution^'^.

-
Nominally pure and stoichiometric V203 is an antiferromagnetic in-
sulator below T~-160K. The ordered moment is 1 . 2 ~ It~ is
what larger than the spin-only value for S = 1/2.
. some-

The antiferromagnetic-paramagnetictransition at the N6el temper-

ature TNis at the same time an insulator-to-metal transition of strongly
first-order character (Fig. 5.4, left): the resistivity drops by about six
orders of magnitude [115, 2551. We identify this transition from an anti-
~

I3The six oxygen ions surrounding the V site form approximately an octahedron.
The insulating phase shows a marked trigonal distortion, and this gives rise to the
olg-e9 splitting.
l4NNMR measurements [388]canfirm the presence of an orbital contribution.