Applying Computational Spectroscopy Methods to Raman Spectra of Dicationic, Imidazolium-Based, Ionic Liquids

Studying ionic liquids (ILs) through computational methods is one of the ways to accelerate progress in the design of novel and potentially green materials optimized for task-specific applications. Therefore, it is essential to develop simple and cost-effective computational procedures that are able to replicate and predict experimental data. Among these, spectroscopic measurements are of particular relevance since they are often implicated in structure–property relationships, especially in the infrared spectral region, where characteristic absorption and scattering processes due to molecular vibrations are ultimately influenced by the surrounding environment in the condensed phase. In this frame, we validate, vis-à-vis experimental data, an efficient theoretical method to compute the Raman spectra in the liquid phase of four especially synthesized dicationic ionic liquids and to assess the conformational cation/anion contributions to the experimental bands. The computational procedure is based on the assessment of the most probable conformations as evaluated by a computational protocol involving both molecular dynamics and ab initio methods.