Abstract
Reduced, stoichiometric and oxidized TiO${}_{2}$(110) surfaces have been compared using valence photoelectron spectroscopy. The results show that the intensity from the band-gap state carries contributions from both oxygen surface vacancies and residual Ti interstitials, present after the sample cleaning procedure. The density of Ti interstitials was found to be 0.05 \ifmmode\pm\else\textpm\fi{} 0.02 monlayers (ML), while the density of oxygen vacancies was estimated to 0.09 \ifmmode\pm\else\textpm\fi{} 0.01 ML. Both these values are in good agreement with previous STM studies. O 1$s$ core-level photoelectron spectra show that oxidation of the interstitials had negligible effect on the OH-H${}_{2}$O balance within the first water layer. The characteristic OH-H${}_{2}$O balance found on a surface free from oxygen vacancies previously reported [Walle et al., Phys. Rev. B 80, 235436 (2009)] is therefore an inherent property of the TiO${}_{2}$(110) surface; that is, the primary mechanism leading to partial dissociation is not related to the presence of residual Ti interstitials.
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