The accurate prediction of physicochemical properties of condensed systems is a longstanding goal of theoretical (quantum) chemistry. Ionic liquids comprising entirely of ions provide a unique challenge in this respect due to the diverse chemical nature of available ions and the complex interplay of intermolecular interactions among them, thus resulting in the wide variability of physicochemical properties, such as thermodynamic, transport, and spectroscopic properties. It is well understood that intermolecular forces are directly linked to physicochemical properties of condensed systems, and therefore, an understanding of this relationship would greatly aid in the design and synthesis of functionalized materials with tailored properties for an application at hand. This review aims to give an overview of how electronic structure properties obtained from quantum chemical methods such as interaction/binding energy and its fundamental components, dipole moment, polarizability, and orbital energies, can help shed light on the energetic, physical, and spectroscopic properties of semi-Coulomb systems such as ionic liquids. Particular emphasis is given to the prediction of their thermodynamic, transport, spectroscopic, and solubilizing properties.

Applications of higher correlated levels of ab initio theory to condensed systems require a significant amount of computational resources. The recent development of the fragment molecular orbital (FMO) approach alleviates this issue by splitting the system into individual fragments and achieves the accuracy of the method by accounting for all possible two-body and three-body interactions. In this work a comprehensive application of the FMO approach in combination with a second order of Møller-Plesset perturbation theory method, MP2, is presented for multiscale clusters of ionic liquids such as [Cmim]X, [Cmpyr]X, [Cpy]X, and [NMe]X, where X = chloride and tetrafluoroborates, BF, with the clusters varying in size from 4, 8, 16, to 32 ion pairs. Reliable cutoff criteria for the inclusion of two-body and three-body interactions are identified for both HF energy and MP2 correlation energy to achieve the desired accuracy of 1 kJ mol. The importance of two-body and three-body interactions in ionic liquids is also discussed.

The prediction of physicochemical properties of ionic liquids such as conductivity and melting point would substantially aid the targeted design of ionic liquids for specific applications ranging from solvents for extraction of valuable chemicals to biowaste to electrolytes in alternative energy devices. The previously published study connecting the interaction energies of single ion pairs (1 IP) of ionic liquids to their thermodynamic and transport properties has been extended to larger systems consisting of two ion pairs (2 IPs), in which many-body and same-ion interactions are included. Routinely used cations, of the imidazolium and pyrrolidinium families, were selected in the study coupled with chloride, tetrafluoroborate, and dicyanamide. Their two ion pair clusters were subjected to extensive configuration screening to establish most stable structures. Interaction energies of these clusters were calculated at the spin-ratio scaled MP2 (SRS-MP2) level for the correlation interaction energy, and a newly developed scaled Hartree-Fock method for the rest of energetic contributions to interaction energy. A full geometry screening for each cation-anion combination resulted in 192 unique structures, whose stability was assessed using two criteria-widely used interaction energy and total electronic energy. Furthermore, the ratio of interaction energy to its dispersion component was correlated with experimentally observed melting points in 64 energetically favourable structures. These systems were also used to test the correlation of the dispersion contribution to interaction energy with measured conductivity.

Experimental EPR and quantum chemical analyses show that ionic liquid solvents can stabilise radical through intermolecular interactions.

Clusters of two ion pairs of imidazolium-based ionic liquids were optimized with 43 different levels of theory, including DFT functionals and MP2-based methods combined with varying Dunning's basis sets, and added dispersion corrections. Better preforming DFT functionals were then applied to clusters consisting of four ion pairs. Excellent performance of some DFT functionals for the two ion pair clusters did not always match that of the four ion-paired clusters despite interionic distances remaining constant between the optimized two and four ion-paired clusters of the same ionic liquid. Combinations of DFT functional and basis set such as ωB97X-D/cc-pVDZ, M06-2X/aug-cc-pVDZ, B3LYP-D3/cc-pVTZ, and TPSS-D3/cc-pVTZ gave excellent results for geometry optimization of two ion-paired clusters of imidazolium ionic liquids but gave larger deviations when applied to the four ion-paired clusters of varying ionic liquids. Empirical dispersion corrections were seen to be crucial in correctly capturing correlation effects in the studied ionic liquid clusters, becoming more important in larger clusters. Dunning's double-ζ basis set, cc-pVDZ, is associated with the smallest root mean squared deviations for geometries; however, it also produces the largest deviations in total electronic energies. ωB97X-D and M06-2X produced the best performance with the augmented version of this basis set. The triple-ζ basis set, cc-pVTZ, leads to the best performance of most of the DFT functionals (especially the dispersion-corrected ones) used, whereas its augmented version, aug-cc-pVTZ, was not seen to improve results. The combinations of functional and basis set that gave the best geometry and energetics in both two and four ion-paired clusters were PBE-D3/cc-pVTZ, ωB97X-D/aug-cc-pVDZ, and BLYP-D3/cc-pVTZ. All three combinations are recommended for geometry optimizations of larger clusters of ionic liquids. PBE-D3/cc-pVTZ performed the best with an average deviation of 2.3 kJ mol −1 and a standard deviation of 3.4 kJ mol −1 for total electronic energy when applied to four ion-paired clusters. Geometries optimized with FMO2-SRS-MP2/cc-pVTZ produced total energy within 2.0 kJ mol −1 off the benchmark in two ion-paired clusters, with the cc-pVDZ basis set performing unsurprisingly poorly with the same method. The error increased to 4.8 kJ mol −1 on average in four ionpaired clusters, with the smallest RMSD deviations in geometries when compared to the benchmark ones. This study is the first report that investigated the performance of DFT functionals for two and four ion-paired clusters of a wide range of ionic liquids consisting of commonly used cations such as pyrrolidinium, imidazolium, pyridinium, and ammonium. It also identified the importance of assessing the performance of quantum chemical methods for ionic liquids on a variety of cation-anion combinations.