Polymorphism of Water in Two Dimensions

The structure of interfacial water is governed by a delicate interplay between water–substrate and water–water interactions. In order to identify the structure-determining factors of ordered two-dimensional water, first calculations of free-standing water layers have been performed. We demonstrate that square bilayers, rhombic bilayers, truncated-square bilayers, and secondary-prism bilayers are energetically more favorable than the traditionally considered hexagonal bilayer. These two-dimensional water structures are stabilized by a combination of high coordination and optimum tetrahedral bonding geometry. The identified structure-determining factors responsible for the polymorphism of water in two dimensions will be operative in any confined water structure. Graphene influence on the stability of water sheets is for the first time explicitly treated using first-principles electronic structure calculations, and changes in some ordered water structures due to non-negligible graphene–water interaction are described.