An atomistically informed multiscale approach to the intrusion and extrusion of water in hydrophobic nanopores

Abstract

Understanding intrusion and extrusion in nanoporous materials is a challenging multiscale problem of utmost importance for applications ranging from energy storage and dissipation to water desalination and hydrophobic gating in ion channels. Including atomistic details in simulations is required to predict the overall behavior of such systems, because the statics and dynamics of these processes depend sensitively on microscopic features of the pore such as the surface hydrophobicity, geometry, and charge distribution and on the composition of the liquid. On the other hand, the transitions between the filled (intruded) and empty (extruded) states are rare events which often require long simulation times difficult to achieve with standard atomistic simulations. In this work, we explored the intrusion and extrusion processes by a multiscale approach in which the atomistic details of the system, extracted from molecular dynamics simulations, inform a simple Langevin model of water intrusion/extrusion in the pore. We then used the Langevin simulations to compute the transition times at different pressures, validating our coarse-grained model by comparing it with nonequilibrium molecular dynamics simulations. The proposed approach reproduces experimentally relevant features such as the time and temperature dependence of the intrusion/extrusion cycles, as well as specific details about the shape of the cycle. This approach also drastically increases the timescales that can be simulated allowing to reduce the gap between simulations and experiments and showing promise for more complex systems.