From this perspective, it is necessary to understand why such a multitude of species exists. Despite the considerable body of work on X-ray diffraction studies, there has been a paucity of investigations into the structural features of the species in solution, which represents the natural operating environment of these compounds. Furthermore, the results of these studies often differ. Lithium NMR spectroscopy experiments suggest that LiCl in tetrahydrofuran (THF) primarily exists as dimeric species, which can be deaggregated to monomeric entities by excess hexamethylphosphoramide. In contrast, LiBr would predominantly exist as a monomer, while LiI would form a contact ion pair, as well as a mixture of monomers and dimers. Another NMR study, also conducted in THF, proposed that LiX were to exist as ion-separated species regardless of the nature of the halide (X = Cl, Br, I). Finally, LiBr was reported to be a cubic tetramer in toluene. These studies were often conducted under low concentration and temperature conditions to minimize signal broadening due to dynamic exchange. Therefore, even from solution studies, the available information is often contradictory and does not reflect the conditions that these species experience under operando conditions. The aforementioned experimental challenges, coupled with the lack of information on high concentra- tion, room temperature data, prompted our recent preliminary study of the structure of LiCl in THF with ab initio molecular dynamics (AIMD). This study underscored the existence of LiCl as a set of chemically distinct structures of high plasticity, in agreement with structures detected in experimental studies. The coexistence of species of different nature reflects stabilization effects from the solvation of the Li atoms, with ethereal solvent oxygens entering the coordination shell of lithium in competition with the halide. This is analogous to our precedent study on Grignard reagents, where solvent fluctuations were reported to be the driving force for the dimerization and disproportion dynamics, producing the different species involved in the Schlenk equilibrium. Our investigation also evidenced how the LiCl structure is prone to perturbation by Lewis acid/base interactions with organometallic species like Grignard derivatives. In particular, basic MgCl 2 is capable of disintegrating the tetrameric pseudo-cubane Li 4 Cl 4 cluster and forming species made of connected LiCl and Li 2 Cl 2 with appropriate increased solvent coordination. This initial study thus established the existence of a vast conformational landscape dependent on the solvation state of the Li atoms. However, due to the high computational cost associated with AIMD simulations, a more complete characterization of the chemical space was unattainable, even when coupled with enhanced sampling approaches.