Toward a Unified Picture of the Water Self-Ions at the Air–Water Interface: A Density Functional Theory Perspective

The propensities of the water self-ions, H3O+ and OH–, for the air–water interface have implications for interfacial acid–base chemistry. Despite numerous experimental and computational studies, no consensus has been reached on the question of whether or not H3O+ and/or OH– prefer to be at the water surface or in the bulk. Here we report a molecular dynamics simulation study of the bulk vs interfacial behavior of H3O+ and OH– that employs forces derived from density functional theory with a generalized gradient approximation exchange-correlation functional (specifically, BLYP) and empirical dispersion corrections. We computed the potential of mean force (PMF) for H3O+ as a function of the position of the ion in the vicinity of an air–water interface. The PMF suggests that H3O+ has equal propensity for the interface and the bulk. We compare the PMF for H3O+ to our previously computed PMF for OH– adsorption, which contains a shallow minimum at the interface, and we explore how differences in solvation of each ion at the interface vs in the bulk are connected with interfacial propensity. We find that the solvation shell of H3O+ is only slightly dependent on its position in the water slab, while OH– partially desolvates as it approaches the interface, and we examine how this difference in solvation behavior is manifested in the electronic structure and chemistry of the two ions.