Liquid−Vapor Oscillations of Water Nanoconfined between Hydrophobic Disks: Thermodynamics and Kinetics

Abstract

We use extensive molecular dynamics simulations with the monatomic model of water (mW) to characterize the thermodynamics and kinetics of the liquid-vapor (wetting-drying) equilibrium of water confined between nanoscopic hydrophobic plates. The transition in confined water is first-order-like, with two well-defined states (wet and dry) separated by a free energy barrier. Different from its bulk counterpart, the confined system oscillates between liquid and vapor: the two phases coexist in time but not in space. Also different from the phase behavior in bulk, there is a finite range of the thermodynamic variables (e.g., temperature or separation between the plates) for which the liquid and vapor state coexist in dynamical equilibrium. We determine the range of temperatures and plate separations for which reversible oscillations can be observed between a stable and metastable phase, compute the time scales of the phase transition along the equilibrium coexistence line, and investigate the pathway for drying along simple collective coordinates that describe the opening of a vapor bubble. The results of the simulations are compared with a simple capillary model for the thermodynamics and transition state theory for the kinetics of phase oscillations.