On the oxidation state of titanium in titanium dioxide

Abstract

The oxidation state of titanium in titanium dioxide is commonly assumed to be +4. This assumption is used ubiquitously to rationalize phenomena observed with TiO2. 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 suggests a lower oxidation state (+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. The commonly assumed picture may therefore have to be revised.