Atom Substitution Effects of [XF6]- in Ionic Liquids. 2. Theoretical Study

Following the preceding spectroscopic study, we further investigate atomic mass effects of [XF6](-) in 1-butyl-3-methylimidazolium cation ([BMIm](+)) based ionic liquids (ILs) on dynamical natures by a computational approach in this study. We carry out the molecular dynamics simulations for 1-butyl-3-methylimidazolium cation based ILs ([BMIm][PF6], [BMIm][AsF6], and [BMIm][SbF6]) with the development of the force fields of [AsF6](-) and [SbF6](-) by an ab initio calculation. We have calculated density of state (DOS) and velocity autocorrelation function (VACF) profiles, polarizability time correlation function (TCF) and Kerr spectra, intermediate scattering functions, and dynamical structure factors. The decomposition analysis has been also carried out to understand the ion species and types of motion. From these computational studies, we find that the contribution of the reorientation of cations and anions mainly governs the Kerr spectrum profile in all three ILs, while the contribution of the collision-induced and cross terms, which are related to translational motions including coupling with librational motion, is not large at higher frequencies than 50 cm(-1). It is suggested that, with the atom substitution effects of anion units on interionic interactions, many properties in ILs are controllable. In addition, it is emphasized in this study that atomic mass effects in ILs are accessible through a complementary approach of both experimental and theoretical approaches.