Single Particle Dynamics at the Free Surface of Imidazolium-Based Ionic Liquids

In this work, we carry out a systematic computer simulation investigation of the single particle dynamics at the free surface of imidazolium-based room temperature ionic liquids by applying intrinsic surface analysis. Besides assessing the effect of the potential model and temperature, we focus in particular on the effect of changing the anion type, and, hence, their shape and size. Further, we also address the role of the length of the cation alkyl chains, known to protrude into the vapor phase, on the surface dynamics of the ions. We observe that the surface dynamics of ionic liquids, being dominated by strong electrostatic interactions, is about 2 orders of magnitude slower than that for common molecular liquids. Furthermore, the free energy driving force for exposing apolar chains to the vapor phase "pins" the cations at the surface layer for much longer than anions, allowing them to perform noticeable lateral diffusion at the liquid surface during their stay there. On the other hand, anions, accumulated in the second layer beneath the liquid surface, stay considerably longer here than in the surface layer. The ratio of the mean surface residence time of the cations and anions depends on the relative size of the two ions: larger size asymmetry typically corresponds to larger values of this ratio. We also find, in a clear contrast with the bulk liquid phase behavior, that anions typically diffuse faster at the liquid surface than cations. Finally, our results show that the surface dynamics of the ions is largely determined by the apolar layer of the cation alkyl chains at the liquid surface, as in the absence of such a layer, cations and anions are found to behave similarly with respect to their single particle dynamics.