Hydrogen Bond Topology Reveals Layering of LDL-like and HDL-like Water at its Liquid/Vapor Interface

The discovery of high-density liquid (HDL) and low-density liquid (LDL) water has been a major success of molecular simulations, yet extending this analysis to interfacial water is challenging due to conventional order parameters assuming local homogeneity. This limitation previously prevented resolving the composition of the surface layer of the liquid/vapour interface. Here, we apply a recently introduced topological order parameter [R. Foffi and F. Sciortino, J. Phys. Chem. B 127, 378-386 (2022)] to analyze the composition of the water/vapor interface across a broad temperature range. Our results reveal that LDL-like water dominates the outermost region at all temperatures, while HDL-like water accumulates beneath it, presenting a clear layering roughly below the temperature of maximum density. This structured stratification, previously inaccessible, highlights the power of the topological order parameter in resolving interfacial molecular heterogeneity and provides new insights into the structural properties of water at interfaces.