Distribution of Ti3+ Surface Sites in Reduced TiO2

TLDR: In this article, a DFT+U study of the (110) rutile surface with oxygen vacancies (Ov's) was performed, and the authors obtained 49 unique solutions of possible Ti3+ pairs, to examine the stability of all Ti types.

Abstract: We describe a DFT + U study of the (110) rutile surface with oxygen vacancies (Ov's). Oxygen vacancies leave behind two excess unpaired electrons per Ov, leading formally to the formation of two Ti3+ ions. We investigate the location of the Ti3+ ions within the first three surface layers. In total, we obtained 49 unique solutions of possible Ti3+ pairs, to examine the stability of all Ti types (e.g., five-coordinated surface Ti, six-coordinated surface Ti, subsurface sites, etc.). Our results show that subsurface sites are preferred but that many configurations are close in energy, within up to 0.3−0.4 eV of each other. In contrast to findings in previous work, we show that sites directly adjacent to the Ov's are unstable. Analysis of our results shows that the two Ti3+ ions within a pair behave independently of each other, as there are little electronic interactions between the excess electrons associated with these sites. We also examined the migration of Ti3+ sites from the surface into the bulk and fi...