On the Charge State of Titanium in Titanium Dioxide.

The oxidation state of titanium in titanium dioxide is commonly assumed to be +4. This assignment is based on the ionic approximation and is used ubiquitously to rationalize phenomena observed with TiO2. It implies a charge state +4 and that no further oxidation of the metal center is possible. We present a comprehensive electronic structure investigation of Ti ions, TiO2 molecules, and TiO2 bulk crystals using different density functional theory and wave function-based approaches, which shows that the charge state of Ti is +3. Specifically, there is evidence of a significant remaining contribution from valence s and d electrons of Ti, including the presence of a nuclear cusp around the Ti core. The charge corresponding to valence s and d states of Ti amounts to 1 e. This suggests the possibility of further oxidation of Ti in TiO2 compounds and challenges the commonly assumed picture of assigning the oxidation state of Ti in titania to +4.