Understanding the Properties of Ionic Liquids: Electrostatics, Structure Factors, and Their Sum Rules

Abstract

The properties of room-temperature ionic liquids (ILs) may be viewed as resulting from a balance of electrostatic interactions that can be tuned at short range but constrained to satisfy universal, asymptotic screening conditions. Short-range interactions and ion packing provide ample opportunity for chemical tunability, while asymptotic sum rules dictate that the long-range structure and charge oscillation be similar to those of molten alkali halide salts. In this work, we study the structure factors and long-range electrostatic interactions in six ILs. The cation in all cases is 1-butyl-3-methylimidazolium (BMIM⁺), and we study six anions, namely, tetrafluoroborate (BF₄^-), hexafluorophosphate (PF₆^-), nitrate (NO₃^-), triflate (CF₃SO₃^-), bisfluorosulfonylimide [(FSO₂)₂N^-], and bistriflimide [(CF₃SO₂)₂N^-]. To gain insight, we perform similar computer simulations of a primitive molten salt model with and without electronic polarization. We emphasize universal similarities among ionic liquids and molten salts in the long-range ion ordering and the influence of electronic polarization on the screening conditions while also characterizing important differences in the short-range electrostatic interactions. We show that polarization systematically reduces charge oscillations by as much as ∼0.5-1 ion per radial shell, which we argue is general to all room-temperature ILs as well as molten salts. We suggest that a fundamentally important distinction among BMIM-based ionic liquids (with different anions) is the nature of the midrange, ∼1 Å^-1 peak in the charge-correlation structure factor; while this correlation is straightforward to analyze in computer simulations, it may often be hidden in X-ray and/or neutron scattering structure factors.