A water structure indicator suitable for generic contexts: two-liquid behavior at hydration and nanoconfinement conditions and a molecular approach to hydrophobicity and wetting

In a recent work we have briefly introduced a new structural index for water that, unlike previous indicators, was devised specifically for generic contexts beyond bulk conditions, making it suitable for hydration and nanoconfinement settings. In this work we shall study this metric in detail, demonstrating its ability to reveal the existence of a fine-tuned interplay between local structure and energetics in liquid water. This molecular principle enables the establishment of an extended hydrogen bond network, while simultaneously allowing for the existence of network defects by compensating for uncoordinated sites. By studying different water models and different temperatures encompassing both the normal liquid and the supercooled regime, this molecular mechanism will be shown to underlie the two-state behavior of bulk water. Additionally, by studying functionalized self-assembled monolayers and diverse graphene-like surfaces, we shall show that this principle is also operative at hydration and nanoconfinement conditions, thus generalizing the validity of the two-liquids scenario of water to these contexts. This approach will allow us to define conditions for wettability, providing an accurate measure of hydrophobicity and a reliable predictor of filling and drying transitions. Hence, it might open the possibility of elucidating the active role of water in broad fields of biophysics and materials science. As a preliminary step, we shall study the hydration structure and hydrophilicity of graphene-like systems (parallel graphene sheets and carbon nanotubes) as a function of the confinement dimensionality. FOR A PROGRAMMING CODE TO IMPLEMENT V4s, PLEASE GO TO: https://github.com/nicolas-loubet/V4S