Many-body contributions to polymorphism and polyhexaticity in a water monolayer

Nanoconfined water plays a crucial role in nanofluidics, biology, and cutting-edge technologies. The process of melting water monolayers and quasi-two-dimensional confined water involves, as an intermediate stage, the hexatic phase–a state that lies between solid and liquid and is characterized by quasi-long-range orientational order and short-range translational order. However, the influence of hydrogen bond (HB) cooperativity in this process has not been thoroughly investigated. This gap hampers our understanding of the phase behavior of confined water and limits the accuracy of our models. To address this, we extend the water model developed by Franzese and Stanley, which explicitly includes many-body interactions (MBIs) of HBs. We distinguish the contributions of three-body and five-body HB-MBIs. Our Monte Carlo calculations in the isobaric-isothermal ensemble produces a detailed pressure-temperature phase diagram, revealing polymorphism and polyhexaticity: low-density square ice and high-density triangular ice are separated from the liquid phase by distinct hexatic phases. Three-body interactions notably promote crystallization and can destabilize the low-density hexatic phase, while cooperative five-body interactions help restore it, thus modifying the thermodynamic landscape. These findings demonstrate that HB-MBIs are key in determining the phase behavior of confined water, influencing phenomena such as the non-monotonic specific heat, maximum density lines, and the accessibility of the liquid-liquid critical point. Beyond advancing theoretical understanding, these results have wide-ranging implications for nanofluidics, interfacial science, and applications in biology, food technology, and pharmaceutics, where controlling water under confinement is essential.

💡 Research Summary

The authors address a long‑standing gap in the theoretical description of water confined to a quasi‑two‑dimensional monolayer by explicitly incorporating many‑body interactions (MBIs) of hydrogen bonds (HBs) into a lattice‑free version of the Franzese‑Stanley (FS) model. While the original FS model includes a two‑body HB term (energy scale J) and a single many‑body term (Jσ) that treats all cooperative effects identically, the present work separates three‑body and five‑body contributions. A new coupling constant Jθ governs three‑body angular interactions that favor square‑like arrangements (θ = 0°, 90°, 180°) through a smooth function Δ(θ)=½