Two Liquid-Liquid Phase Transitions in Confined Water Nanofilms

The stories behind supercooled bulk and confined water can be different. Bulk water has a metastable liquid-liquid phase transition at deeply supercooled conditions, but the existence of such a phenomenon in confined water is in question. Herein we show simulation results of first-order phase transitions between high- and low-density liquid (HDL and LDL) in confined water in both positive and negative pressures. A mid-density state between these two local states appears, which lets the transition show the hysteresis loop with transiently stable intermediate states. On the basis of Landau theory that we have adapted for mixing of moieties with high- and low-density states, we explain the phase transitions with the order parameter-dependent free energy change which is governed by second- to higher-order interactions among those moieties.