Density functional theory calculations of dense TiO2 polymorphs: implication for visible-light-responsive photocatalysts.

Structural parameters and electronic band gaps of dense TiO(2) polymorphs, i.e., alpha-PbO(2), baddeleyite, fluorite, and cotunnite types of structures, were calculated using a first-principles density functional method with local-density approximation. The ambient phases, i.e., rutile and anatase, with known theoretical and experimental data were used to ensure the validity of the calculations. The fluorite-type TiO(2) turned out to have the narrowest band gap, 1.08 or 2.18 eV after applying a very approximate band gap correction, due to highly symmetrical TiO(8) polyhedra with Ti(3d) and O(2p) orbitals in the most mixed state. Ti with eight coordinated oxygens, as feasible under high pressure or residual stress, may have potential applications as a visible-light-responsive photocatalyst.