The intrinsic structure of the water surface

Abstract

An operational procedure to obtain the intrinsic structure of liquid surfaces is applied here to a molecular dynamics simulation of water, with a model of point charges for the molecular interactions. The method, which had been recently proposed and used for simple fluids, is successfully extended to a molecular liquid with the complex bond structure of water. The elimination of the capillary wave fluctuations, in the intrinsic density and orientation profiles, gives a new overall view of the water surface, at the sharpest molecular level, and without the size-dependent broadening observed in the mean profiles. The molecules belonging to the outer liquid layer are clearly identified, and we find that only these molecules exhibit a clear preferential orientation to lie flat on the surface. Moreover, there is a strong correlation between the dipolar structure and the local curvatures of the intrinsic surface, so that at the extrusions of the intrinsic surface the molecular dipoles point preferentially toward the vapor side of the interface. Finally, we have found an intrinsic density layering structure, although the inner structure is strongly damped beyond the second layer.