Pjd. Lindan et al., FIRST-PRINCIPLES SPIN-POLARIZED CALCULATIONS ON THE REDUCED AND RECONSTRUCTED TIO2(110) SURFACE, Physical review. B, Condensed matter, 55(23), 1997, pp. 15919-15927
We have performed plane-wave pseudopotential density-functional theory
calculations on the stoichiometric and reduced TiO2 (110) surface, th
e 2 x 1 and 1 x 2 reconstructions of the surface formed by the removal
of bridging-oxygen atoms, and on the oxygen vacancy in the bulk. The
effect of including spin polarization is investigated, and it is found
to give a qualitatively different electronic structure compared with
a spin-paired description. In the spin-polarized solutions, the excess
electrons generated by oxygen reduction occupy localized band-gap sta
tes formed from Ti (3d) orbitals, in agreement with experimental findi
ngs. In addition, the inclusion of spin polarization substantially low
ers the energy of all the systems studied, when compared with spin-pai
red solutions. However, spin-polarization does not change the relative
stability of the two reconstructions, which remain energetically equi
valent.