A first-principles atomic orbital-based electronic structure method is
used to investigate the low index surfaces of rutile titanium dioxide
(TiO2). The method is relatively cheap in computational terms, making
it attractive for the study of oxide surfaces, many of which undergo
large reconstructions, and may be governed by the presence of oxygen v
acancy defects. Calculated surface charge densities are presented for
low-index surfaces of TiO,, and the relation of these results to exper
imental scanning tunnelling microscopy images is discussed. Atomic res
olution images at these surfaces tend to be produced at positive bias,
probing states which largely consist of unoccupied Ti 3d bands, with
a small contribution from O 2p. These experiments are particularly int
eresting since the O atoms tend to sit up to 1 Angstrom above the Ti a
toms, so providing a play-off between electronic and geometric structu
re in image formation.