Temperature-pressure phase diagram of confined monolayer water/ice at first-principles accuracy with a machine-learning force field

Abstract

Understanding the phase behaviour of nanoconfined water films is of fundamental importance in broad fields of science and engineering. However, the phase behaviour of the thinnest water film – monolayer water – is still incompletely known. Here, we developed a machine-learning force field (MLFF) at first-principles accuracy to determine the phase diagram of monolayer water/ice in nanoconfinement with hydrophobic walls. We observed the spontaneous formation of two previously unreported high-density ices, namely, zigzag quasi-bilayer ice (ZZ-qBI) and branched-zigzag quasi-bilayer ice (bZZ-qBI). Unlike conventional bilayer ices, few inter-layer hydrogen bonds were observed in both quasi-bilayer ices. Notably, the bZZ-qBI entails a unique hydrogen-bonding network that consists of two distinctive types of hydrogen bonds. Moreover, we identified, for the first time, the stable region for the lowest-density 4 ⋅ 8 2 monolayer ice (LD-48MI) at negative pressures (