Collectivity in ionic liquids: a temperature dependent, polarizable molecular dynamics study
András Szabadi1, Philipp Honegger1, Flora Schöfbeck1
1Department of Computational Biological Chemistry, Faculty of Chemistry, University of Vienna, Währingerstr. 17, A-1090 Vienna, Austria. christian.schroeder@univie.ac.at.
Abstract:
We use polarizable molecular dynamics simulations to study the thermal dependence of both structural and dynamic properties of two ionic liquids sharing the same cation (1-ethyl-3-methylimidazolium). The linear temperature trend in the structure is accompanied by an exponential Arrhenius-like behavior of the dynamics. Our parameter-free Voronoi tessellation analysis directly casts doubt on common concepts such as the alternating shells of cations and anions and the ionicity. The latter tries to explain the physico-chemical properties of the ionic liquids based on the association and dissociation of an ion pair. However, cations are in the majority of both ion cages, around cations and around anions. There is no preference of a cation for a single anion. Collectivity is a key factor in the dynamic properties of ionic liquids. Consequently, collective rotation relaxes faster than single-particle rotations, and the activation energies for collective translation and rotation are lower than those of the single molecules.
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