Strength, number, and kinetics of hydrogen bonds for water confined inside boron nitride nanotubes

Water has shown a myriad of highly interesting properties and behaviors, such as very low friction, phase transition under unexpected conditions, massive property alterations, etc. inside strong nanoconfinements of few-nanometer to sub-nanometer diameters. Water-water hydrogen bonding is one of the most important factors dictating such water behavior and properties inside such strong nanoconfinements. In this paper, we employ Reactive Force Field (ReaxFF) molecular dynamics (MD) simulations for studying multiple facets of such water-water hydrogen bonds (HBs) inside boron-nitride nanotubes (BNNTs) having diameters ranging from a few nanometers to sub-nanometers. First, the strength of the water-water HB interactions, as a function of the HB configuration, is quantified by studying the corresponding PMF (potential of mean force). For water present in extreme confinements (BNNTs with sub-nanometric diameters), we see completely isolated HB basins. On the other hand, for bulk water the HB basin is connected (via a saddle point) to a nearby second PMF well. Therefore, our analysis successfully distinguishes the HB characteristics between the cases of water in extreme confinement and bulk water. Second, we study the kinetics of such water-water HBs: HBs formed by a given pair of water molecules in extreme confinements show a much larger probability of remaining intact once formed or re-forming after they have been broken. Both these results, which shed new light on water-water hydrogen bonding inside strong nanoconfinements, can be explained by the single-file structure formed by the water molecules in extreme BNNT confinements.