Quantitative Understanding of Liquid Dynamics at Interfaces from a Free-Energy Landscape Perspective

On the basis of molecular dynamics simulations of water and ethanol in nanopores, we devise a methodology to determine the free-energy landscape (FEL) imposed by an interface on an adjoining liquid directly from the particle trajectories. The methodology merely uses the statistical mechanical relation between occupancy and energy and, hence, is particularly suitable in complex situations, e.g., for disordered or rough atomistic interfaces and molecular liquids, as encountered in many biological, geological, and technological situations. Moreover, we show that the thus-obtained FEL enables a quantitative understanding of interface effects on liquid dynamics. Specifically, by determining the local minima and barriers of the FEL and using an Arrhenius-like relation, we reproduce the very strong spatial variation of the structural relaxation time of water and ethanol across nanopores over a broad temperature range. We anticipate that the proposed FEL approach is transferable to various other liquids and interfaces.