The joint effect of surface polarity and concentration on the structure and dynamics of acetonitrile solution: a molecular dynamics simulation study

The interfacial properties of the acetonitrile (ACN)-water-silica interface have great implications in both liquid chromatography and heterogeneous catalysis. We have performed molecular dynamics (MD) simulations of ACN and water binary solutions to give a comprehensive study of the collective effect of silica surface polarity and ACN concentration on interfacial structures and dynamics by tuning both surface charges and ACN concentration. MD simulation results indicate that many properties in the liquid-solid interface region undergo a monotonic change as the silica surface is tuned from polar to apolar due to the weakening of hydrogen bonding, while their dependence on ACN concentration is presumably governed by the preferential adsorption of water at the silica surface over ACN. However, at apolar surfaces, the interfacial structures of both water and ACN behave like the liquid-vapor interface, and this resemblance leads to an enrichment of ACN at the interface as well as accelerated dynamics, which is very different from that in the bulk solution. The organization of ACN molecules at both polar and apolar surfaces can be attributed to the amphiphilic nature of ACN, by which the micro-heterogeneity domain formed can persist both in the bulk and at the liquid-solid interface. Moreover, extending diffusion analysis to the second layer of the interface shows that the interfacial transport pathways at polar surfaces are likely very different from that of apolar surfaces. These simulation results give a full spectrum description of the ACN/water liquid-solid interface at the microscopic level and will be helpful for explaining related spectroscopic experiments and understanding the microscopic mechanisms of separation protocols in current chromatography applications.