Molecular dynamics study of the dynamical behavior in ionic liquids through interionic interactions

Abstract We have focused on the interionic dynamics of an IL, 1-butyl-3-methylimidazolium cation with the anion, [PF 6 ] − , [BMIm][PF 6 ], and have investigated the interionic interaction in the IL and the polarization effects on the system. Molecular dynamics simulations have been carried out to pursue the understanding of interionic properties in ILs at molecular level. The analyses of velocity cross-correlation functions have been performed to study the interionic interactions. We have computed the momentum correlation functions between ionic species. From simulation results, it is suggested that, at the short time region up to 1 ps, the velocity cross-correlation is predominantly governed by the longitudinal contribution. It is found out that, compared with the longitudinal correlation in the nonpolarizable model, the longitudinal motions are further influenced in the polarizable model. It is indicated that the behavior of mean-squared displacement of the cation at a long-time region is not influenced by polarization effects, while the anion shows important difference. Also, it is concluded that the cage effect in ILs could be reduced by many-body polarization effects.