Oxygen vacancies on TiO2 (110) from first principles calculations

We have carried out a systematic study of oxygen vacancy formation on the TiO₂ (110) surface by means of plane-wave pseudopotential density-functional theory calculations. We have used models with the mean number of vacancies per surface unit cell being θ=0.25 and θ=0.5. The study comprises several kind of vacancies within the outermost layers of the surface. The use of a suitable set of technical parameter is often essential in order to get accurate results. We find that the presence of bridging vacancies is energetically favored in accordance to experimental data, although the formation of sub-bridging vacancies might be possible at moderate temperatures. Surprisingly, the spin state of the vacancy has little influence on the results. Atomic displacements are also analyzed and found to be strongly dependent on the particular arrangement of vacancies.