Chemistry Dissolved in Ionic Liquids. A Theoretical Perspective

Abstract

The theoretical treatment of ionic liquids must focus now on more realistic models while at the same time keeping an accurate methodology when following recent ionic liquids research trends or allowing predictability to come to the foreground. In this Perspective, we summarize in three cases of advanced ionic liquid research what methodological progress has been made and point out difficulties that need to be overcome. As particular examples to discuss we choose reactions, chirality, and radicals in ionic liquids. All these topics have in common that an explicit or accurate treatment of the electronic structure and/or intermolecular interactions is required (accurate methodology), while at the same time system size and complexity as well as simulation time (realistic model) play an important role and must be covered as well.

Reactions of noble-metal oxides in ionic liquids near room temperature

“…4 Key features of ionic liquids, in this regard, relate to the high thermal and chemical stability and the weakly coordinating properties. 1,5…”

“…Until now, the synthesis of metastable compounds in ionic liquids was mainly focused on metal halides, metal selenides/tellurides or metal clusters. 1–5 The synthesis of new metal oxides and compounds using metal oxides as starting materials, in contrast, was barely addressed, which can be attributed to the high lattice energy of many metal oxides and their low solubility in ionic liquids. Several studies, however, have successfully shown options to dissolve metal oxides in ionic liquids.…”

Comparison between Ab Initio Molecular Dynamics and OPLS-Based Force Fields for Ionic Liquid Solvent Organization

“… − Delocalization of charge over several atoms and asymmetry in either the size or shape of the cation or anion are essential in the construction of these materials. The physical and chemical properties of ILs are fundamentally related to their solvent structure. , Due to their extensive potential to alter physical and chemical behavior through functionalization, considerable effort has been put forth by the IL community to better understand the nature of these intermolecular interactions. − …”

Error quantification of phase transition quantities from cluster weighting calculations

“…In spite of these efforts, realistic applications from sustainable chemistry often require complex or involved models of the underlying chemistry and large computing time. Examples are the inclusion of liquids or solvents, for example ionic liquids, [11][12][13][14] but also the appropriate description of interfaces 15,16 or systems from energy devices. [17][18][19] When using such approximate methods, the assessment of the errors included is of high importance.…”