Multiresolution calculation of ionic liquids.
Résumé
Ionic liquids—which are special solvents composed entirely of ions—are difficult albeit interesting to study for several reasons. Owing to the many possible cation and anion combinations that form ionic liquids, common properties are hard to classify for them, which makes the theoretical investigation crucial for ionic liquids. The system size, the amount of possible isomers including cation–anion orientation and coordination, as well as the rotation of the side chain(s) prevent the use of high-level electronic structure methods, and density functional theory is the method of choice. Dispersion forces—although they are small compared to electrostatics—play a major role in ionic liquids; therefore, methods that describe such kind of interplay are preferred. Between the cation and the anion, there is a sizable charge transfer, which has important consequences for molecular dynamics simulations and force field development. Already based on the first generation of force fields important discoveries were made, namely that ionic liquids are nanostructured. Moreover, it was possible to predict that their distillation is possible. Throughout the construction of these force fields, transferability was taken into account which allowed them to describe homologous series. For studying reactions in ionic liquid (IL) media, continuum models were found to improve the results. Ab initio molecular dynamics (AIMD) and quantum mechanics (QM)/molecular mechanics (MM) approaches are well suited for spontaneous events. In case of very large systems, such as cellulose in ionic liquids, coarse-grained methods are providing insight and are applied more frequently. This makes ionic liquids real multiscalar systems.