Self‐Diffusion of Individual Adsorbed Water Molecules at Rutile (110) and Anatase (101) TiO₂ Interfaces from Molecular Dynamics

The distribution of individual water molecules’ self‐diffusivities in adsorbed layers at TiO₂ surfaces anatase (101) and rutile (110) have been determined at 300 K for inner and outer adsorbed layers, via classical molecular‐dynamics methods. The layered‐water structure has been identified and classified in layers making use of local order parameters, which proved to be an equally valid method of “self‐ordering” molecules in layers. Significant distinctness was observed between anatase and rutile in disturbing these molecular distributions, more specifically in the adsorbed outer layer. Anatase (101) presented significantly higher values of self‐diffusivity, presumably due to its “corrugated” structure that allows more hydrogen bonding interaction with adsorbed molecules beyond the first hydration layer. On the contrary, rutile (110) has adsorbed water molecules more securely “trapped” in the region between Ob atoms, resulting in less mobile adsorbed layers.