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Distribution of Ti3+ Surface Sites in Reduced TiO2
Abstract
We describe a DFT + U study of the (110) rutile surface with oxygen vacancies (O v 's). Oxygen vacancies leave behind two excess unpaired electrons per O v, leading formally to the formation of two Ti 3+ ions. We investigate the location of the Ti 3+ ions within the first three surface layers. In total, we obtained 49 unique solutions of possible Ti 3+ 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 O v 's are unstable. Analysis of our results shows that the two Ti 3+ 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 Ti 3+ sites from the surface into the bulk and find the surface locations to be preferred by ∼0.5 eV relative to the bulk. Our systematic results provide a comprehensive picture of excess electrons that indicates that they are not trapped or localized at specific sites but are distributed across several sites due to nearly degenerate Ti 3+ states.
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Metadata
- Authors
- Deskins, N. A., Rousseau, R., & Dupuis, M.
- Venue
- The Journal of Physical Chemistry C
- Publisher
- American Chemical Society (ACS)
- Published
- 2011-03-25
- Volume
- 115
- Issue
- 15
- Pages
- 7562-7572
- ISSN
- 1932-7447 (ISSN-L)
- 1932-7455
- OpenAlex
- W161208503
- Cited by
- 267
- References
- 52
- FWCI
- 8.14
- Type
- journal article
- Language
- en
- Open access
- closed
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