Structure of a Water Monolayer on the Anatase TiO₂(101) Surface

Titanium dioxide (TiO$_2$) plays a central role in the study of artificial photosynthesis, owing to its ability to perform photocatalytic water splitting. Despite over four decades of intense research efforts in this area, there is still some debate over the nature of the first water monolayer on the technologically-relevant anatase TiO$_2$ (101) surface. In this work we use first-principles calculations to reverse-engineer the experimental high-resolution X-ray photoelectron spectra measured for this surface in [Walle et al., J. Phys. Chem. C 115, 9545 (2011)], and find evidence supporting the existence of a mix of dissociated and molecular water in the first monolayer. Using both semilocal and hybrid functional calculations we revise the current understanding of the adsorption energetics by showing that the energetic cost of water dissociation is reduced via the formation of a hydrogen-bonded hydroxyl-water complex. We also show that such a complex can provide an explanation of an unusual superstructure observed in high-resolution scanning tunneling microscopy experiments.