A first-principles computational comparison of defect-free and disordered, fluorinated anatase TiO₂ (001) interfaces...

Chemical doping and other surface modifications have been used to engineer the bulk properties of materials, but their influence on the surface structure and consequently the surface chemistry are often unknown. Previous work has been successful in fluorinating anatase TiO₂ with charge balance achieved via the introduction of Ti vacancies rather than the reduction of Ti. Our work here investigates the interface between this fluorinated titanate with cationic vacancies and a monolayer of water via density functional theory based molecular dynamics. We compute the projected density of states for only those atoms at the interface and for those states that fall within 1 eV of the Fermi level for various steps throughout the simulation, and we determine that the variation in this visualization of the density of states serves as a reasonable tool to anticipate where surfaces are most likely to be reactive. In particular, we conclude that water dissociation at the surface is the main mechanism that influences the anatase (001) surface whereas the change in the density of states at the surface of the fluorinated structure is influenced primarily through the adsorption of water molecules.