Molecular Dynamics Investigation of the Vibrational Spectroscopy of Isolated Water in an Ionic Liquid

Experimental studies examining the structure and dynamics of water in ionic liquids (ILs) have revealed local ion rearrangements that occur an order of magnitude faster than complete randomization of the liquid structure. Simulations of an isolated water molecule embedded in 1-butyl-3-methyl imidazolium hexafluorophosphate, [bmim][PF6], were performed to shed insight into the nature of these coupled water-ion dynamics. The theoretical calculations of the spectral diffusion dynamics and the infrared absorption spectra of the OD stretch of isolated HOD in [bmim][PF6] agree well with experiment. The infrared absorption line shape of the OD stretch is narrower and blue-shifted in the IL compared to those in aqueous solution. Decomposition of the OD frequency time correlation function revealed that translational motions of the anions dominate the spectral diffusion dynamics.