Ionic liquids are a subset of molten salts, distinguished by having melting points below 100°C. This reduction in melting point is brought about by weakening electrostatic interactions be-tween the ions and hindering crystal lattice packing, typically by making at least one of the ions large, unsymmetrical and organic. Whilst conventional molecular liquids are structurally homogeneous, ILs are nanostructured. This nanostructure arises from cohesive interactions be-tween the different parts of the ions, and consists of distinct polar and non-polar domains.
In this work we present a novel computational method that combines a stochastic search algorithm and accurate molecular simulations for studying nanostructure in protic ionic liquids . These simulations accurately reproduce experimentally observed nanostructure of bulk protic ionic liquids , and in combination with atomic force microscopy, reveal how this nanostructure changes in the vicinity of a smooth solid surface. Our simulations also demonstrate the dynamic nature of the hydrogen bond network that underpins protic ionic liquid nanostructure, and raise questions regarding previous arguments used to explain anomalous stabilities in ionic liquid clus-ters [3,4].
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