Exploring Rutile (110) and Anatase (101) TiO₂ Water Interfaces by Reactive Force-Field Simulations

Abstract

We have investigated static/structural as well as dynamical properties of anatase (101) and rutile (110) TiO2 interfaces with liquid bulk water by reactive force fields (ReaxFF). Layered, well-organized structure of water in the interface region was clearly observed within 6.5 Å of the surfaces. The first-hydration layer molecules adsorbed to unsaturated surface Ti atoms undergo spontaneous dissociation leading, rather controversially, to full coverage of O2c/Ob by H+ and partial coverage of Ti5c by OH–. Expected large variations of intrinsic electric field on the interfaces, and drop of electrostatic potential, were detected. Interfacial water was found to be heavily confined with a self-diffusion constant of 2 orders of magnitude lower than 2.28 × 10–9 m2/s measured in the bulk water region. Moreover, the rotational movement of adsorbed water molecules was found to be considerably hindered as well. On the other hand, the calculated hydrogen-bond lifetime on the interface was shorter than in bulk water for both surface types. Finally, the IR spectra obtained from collective-water-dipole variations in the interfacial region revealed stronger effects on stretching vibrations on anatase (101) than on rutile (110); however, description of liquid-water bond-stretching vibrations generally suffers from lack of accuracy in the applied reactive potential.