title: Relaxation of Voronoi shells in hydrated molecular ionic liquids.
abstract: The relaxation of solvation shells is studied following a twofold strategy based on a direct analysis of simulated data as well as on a solution of a Markovian master equation. In both cases solvation shells are constructed by Voronoi decomposition or equivalent Delaunay tessellation. The theoretical framework is applied to two types of hydrated molecular ionic liquids, 1-butyl-3-methyl-imidazolium tetrafluoroborate and 1-ethyl-3-methyl-imidazolium trifluoromethylsulfonate, both mixed with water. Molecular dynamics simulations of both systems were performed at various mole fractions of water. A linear relationship between the mean residence time and the system's viscosity is found from the direct analysis independent of the system's type. The complex time behavior of shell relaxation can be modeled by a Kohlrausch-Williams-Watts function with an almost universal stretching parameter of 1/2 indicative of a square root time law. The probabilistic model enables an intuitive interpretation of essential motional parameters otherwise not accessible by direct analysis. Even more, incorporating the square root time law into the probabilistic model enables a quantitative prediction of shell relaxation from very short simulation studies. In particular, the viscosity of the respective systems can be predicted.
authors.affiliation: Department of Computational Biological Chemistry, University of Vienna, Wien A-1090, Austria.
authors.forename: G
authors.initials: G
authors.lastname: Neumayr
authors.forename: C
authors.initials: C
authors.lastname: Schröder
authors.forename: O
authors.initials: O
authors.lastname: Steinhauser
mesh_terms: D052578:Ionic Liquids / Q000737:chemistry*; D008390:Markov Chains; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D009038:Motion; D013997:Time Factors; D014867:Water / Q000737:chemistry*
chemical_list: D052578:Ionic Liquids; D014867:Water