Solvent-Induced Proton Hopping at a Water−Oxide Interface

ABSTRACT: Despite widespread interest, a detailed understanding of the dynamics of proton transfer at interfaces is lacking. Here, we use ab initio molecular dynamics to unravel the connection between interfacial water structure and proton transfer for the widely studied and experimentally well-characterized water−ZnO(101̅0) interface. We find that upon going from a single layer of adsorbed water to a liquid multilayer, changes in the structure are accompanied by a dramatic increase in the proton-transfer rate at the surface. We show how hydrogen bonding and rather specific hydrogen-bond fluctuations at the interface are responsible for the change in the structure and proton-transfer dynamics. The implications of this for the chemical reactivity and for the modeling of complex wet oxide interfaces in general are also discussed. SECTION: Surfaces, Interfaces, Porous Materials, and Catalysis Proton transfer in water is a process of central importance toa number of fields in science and technology. Consider, for example, proton conduction across polymeric membranes used in fuel cells1 or through protein channels in cells.2 Proton