title: Collective translational motions and cage relaxations in molecular ionic liquids.
abstract: In this computational study, the collective translational motions of 1-ethyl-3-methylimidazolium triflate, characterized by its current correlation function and its collective dipolar displacement, are interpreted in terms of an ion cage around a central ion. Thereby, a coincidence of the relevant time constants is observed. Furthermore, the ion cage is long living and its composition is rather heterogeneous. Besides high numbers of counter ions, several ions of like charge populate the first shell around a central ion. In contrast to the strong influence of the local environment on the collective translational motion, rotations are strictly collective. In other words, a local picture falls short of describing the overall antiparallel alignment of ionic dipoles. A further issue of this work is the interpretation of the initial region of the collective dipolar displacement. It can be related to all collective translational processes showing up in the computational dielectric spectrum. In particular, slow translational processes which are invisible in the current correlation function can be detected. The inclusion of these slow processes allow for an excellent computational reconstruction of the experimental spectrum of the generalized dielectric constant.
authors.affiliation: University of Vienna, Department of Computational Biological Chemistry, A-1090 Austria. christian@mdy.univie.ac.at
authors.forename: Christian
authors.initials: C
authors.lastname: Schröder
mesh_terms: D003198:Computer Simulation; D004553:Electric Conductivity; D007093:Imidazoles / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular
chemical_list: D007093:Imidazoles; D052578:Ionic Liquids; C518739:1-ethyl-3-methylimidazolium