Hydration of MgO, CaO, SrO, and BaO (001) Surfaces from First Principles

Abstract In this work we present a computational study of alkaline earth oxides (001) surfaces interfaced with water by means of density functional theory (DFT) in conjunction with ab initio molecular dynamics (AIMD) calculations. We studied the nature of MgO, CaO, SrO, and BaO (001) surfaces in contact with water. Results show that water dissociation is promoted as the alkaline earth metal becomes heavier. Similarly, the coordination number of the cation atoms with water molecules follows the same trend, indicating a more favorable interaction. The combined analysis of rumpling and pair distribution functions allows to provide a correspondence between reactivity of atoms on the surface and capability to coordinate water molecules. Except for MgO, the remaining surfaces display strong structural changes upon hydration, a relevant message when modelling hydrated surfaces. We also investigated the effect of the water thickness by adsorbing a water monolayer and bilayer to the surface. The findings of the study and the adopted approach could be of help for future studies of more complex systems or to provide fundamental rationalizations.