Effect of Anions on Static Orientational Correlations, Hydrogen Bonds, and Dynamics in Ionic Liquids:  A Simulational Study

Abstract

Three different ionic liquids are investigated via atomistic molecular dynamics simulations using the force field of Lopes and PAdua (J. Phys. Chem. B 2006, 110, 19586). In particular, the 1-ethyl-3-methylimidazolium cation EMIM+ is studied in the presence of three different anions, namely, chloride Cl-, tetrafluoroborate BF(4)(-), and bis((trifluoromethyl)sulfonyly)imide TF2N-. In the focus of the present study are the static distributions of anions and cations around a cation as a function of anion size. It is found that the preferred positions of the anions change from being close to the imidazolium hydrogens to being above and below the imidazolium rings. Lifetimes of hydrogen bonds are calculated and found to be of the same order of magnitude as those of pure liquid water and of some small primary alcohols. Three kinds of short-range cation-cation orderings are studied, among which the offset stacking dominates in all of the investigated ionic liquids. The offset stacking becomes weaker from [EMIM][Cl] to [EMIM][BF4] to [EMIM][TF2N]. Further investigation of the dynamical behavior reveals that cations in [EMIM][TF2N] have a slower tumbling motion compared with those in [EMIM][Cl] and [EMIM][BF4] and that pure diffusive behavior can be observed after 1.5 ns for all three systems at temperatures 90 K above the corresponding melting temperatures.