A Molecular Mechanism for the Water–Hydroxyl Balance during Wetting of TiO₂

Abstract

We show that the formation of the wetting layer and the experimentally observed continuous shift of the H2O–OH balance toward molecular water at increasing coverage on a TiO2(110) surface can be rationalized on a molecular level. The mechanism is based on the initial formation of stable hydroxyl pairs, a repulsive interaction between these pairs, and an attractive interaction with respect to water molecules. The experimental data are obtained by synchrotron radiation photoelectron spectroscopy and interpreted with the aid of density functional theory calculations and Monte Carlo simulations.