Proton-Transfer Mechanisms at the Water-ZnO Interface: The Role of Presolvation

The dissociation of water is an important step in many chemical processes at solid surfaces. In particular, water often spontaneously dissociates near metal oxide surfaces, resulting in a mixture of H₂O, H⁺, and OH^- at the interface. Ubiquitous proton-transfer (PT) reactions cause these species to dynamically interconvert, but the underlying mechanisms are poorly understood. Here, we develop and use a reactive high-dimensional neural-network potential based on density functional theory data to elucidate the structural and dynamical properties of the interfacial species at the liquid-water-metal-oxide interface, using the nonpolar ZnO(101̅0) surface as a prototypical case. Molecular dynamics simulations reveal that water dissociation and recombination proceed via two types of PT reactions: (i) to and from surface oxide and hydroxide anions ("surface-PT") and (ii) to and from neighboring adsorbed hydroxide ions and water molecules ("adlayer-PT"). We find that the adlayer-PT rate is significantly higher than the surface-PT rate. Water dissociation is, for both types of PT, governed by a predominant presolvation mechanism, i.e., thermal fluctuations that cause the adsorbed water molecules to occasionally accept a hydrogen bond, resulting in a decreased PT barrier and an increased dissociation rate as compared to when no hydrogen bond is present. Consequently, we are able to show that hydrogen bond fluctuations govern PT events at the water-metal-oxide interface in a way similar to that in acidic and basic aqueous bulk solutions.