Freezing of Confined Water: A Bilayer Ice Phase in Hydrophobic Nanopores

Abstract

Molecular dynamics simulations were performed to study the phase behavior of a thin film of water confined to a slit nanopore with smooth walls. A first-order water-to-ice freezing transition has been observed. The resulting ice, which is a crystal of bilayer consisting of rows of distorted hexagons, does not resemble any ice crystals found so far. The confined water contracts upon freezing when the confinement load is low ( $\sim 0.5\mathrm{kbar}$) and expands when the load is high (10 kbar). The residual entropy of the bilayer ice can be calculated exactly, which is about half of the entropy of the bulk ice.