Interfacial Organization of Acetonitrile: Simulation and Experiment

Molecular dynamics simulations and vibrational SUM frequency generation (VSFG) experiments in the methyl-stretching spectral region have been used to study acetonitrile at the silica/liquid, silica/vapor, and liquid/ vapor interfaces. Our simulations show that, at the silica/liquid interlace. acetonitrile takes on a considerably different structure than in the bulk liquid. The interfacial structure is reminiscent of a lipid bilayer. and this type of ordering persists for tens of Angstroms into the bulk liquid. This result has important implications for processes involving solid/acetonitrile interfaces, such as heterogeneous catalysis and chromatographic separations. Fitting of VSFG data that have an extremely low nonresommt background contribution provides strong evidence for interfacial populations pointing in opposite directions at these interfaces, in agreement with our simulations. The picture developed from our simulations and experiments reconciles conflicting interpretations of data front previous experimental studies of interfacial acelonitrile.