The effects of vacancies and their mobility on the dynamic heterogeneity in 1,3-dimethylimidazolium hexafluorophosphate organic ionic plastic crystals.

Abstract

Organic ionic plastic crystals (OIPCs) are the crystals of electrolytes with a long-range translational order. The rotational modes of ions in OIPCs are, however, activated even in solid phases such that the diffusion of dopants such as lithium ions may be facilitated. OIPCs have been, therefore, considered as good candidates for solid electrolytes. Recent experiments and theoretical studies have suggested that both the translational and the rotational diffusion of ions are quite heterogeneous: the diffusion of some ions are quite fast while other ions of the same kind hardly diffuse, either rotationally or translationally. Such dynamic heterogeneity would be a key to the transport mechanism of dopants in solid state electrolytes. In this work, we investigate the effects of defects on the dynamic heterogeneity of OIPCs. We perform atomistic molecular dynamics simulation of 1,3-dimethylimidazolium hexafluorophosphate ([MMIM][PF6]) with a pair of cation and anion vacancies. At low temperature, vacancies undergo hopping motions toward each other and form a charge-neutral cluster. At high temperature, two vacancies act like a loosely bonded molecule and diffuse together via hopping motions. We find that the translational diffusion of ions is correlated strongly with the vacancy diffusion and becomes heterogeneous when the vacancies hop. The rotation of ions also becomes active when the ions are close to vacancies such that the rotational dynamic heterogeneity strengthens.