Molecular transport across fluid interfaces: Coupling between solute dynamics and interface fluctuations

Abstract

We investigate the transport mechanism of a small hydrophobic solute molecule across two types of fluid interfaces, (i) an interface between two immiscible liquids and (ii) a surfactant-covered liquid-liquid interface. These systems are modeled by coarse-grained molecular dynamics simulations. It is demonstrated that the dynamics of the solute molecule near the interface significantly deviates from Markovian Brownian motion. Specifically, the correlation time of the random force acting on the solute strongly depends on the distance between the solute and the interface and increases by two orders of magnitude within a very narrow (less than 1 nm wide) region near the interface. The slow fluctuations of the random force in this narrow region are caused by capillary waves. The region location and width are determined by interface protrusions caused by attraction between the solute and the hydrophobic phase. We use results of molecular dynamics simulations to develop a stochastic model for the coupled solute-interface dynamics and estimate the rate of the solute transport across the interface. The observed phenomenon appears to be a general feature of mass transport across fluid or flexible membranes. The coupling between the solute transport and the interface fluctuations is the strongest in areas corresponding to a large free energy gradient or near a free energy barrier for the solute transport. This suggests a strong influence of the coupled solute-interface dynamics on the rate of mass transfer across interfaces.