To represent the different basins characterizing the system, we opt for a two-dimensional free energy surface (FES). As shown in Figure , expanding the exploration of the conformational space in two dimensions permits the separation of different basins otherwise convoluted in the one-dimensional profile, allowing the characterization of both new and previously identified structures like C4, C5 and B6, and their assignment to well-defined basins of the FES. The majority of these structures retains the rhomboidal Li 2 Cl 2 subunit, which is recognized as the fundamental unit of numerous LiX clusters. A second frequently encountered arrangement is a hexagonal ring of alternating Li and Cl, as also observed in some solid-state structures. The low solvation region is characterized by the two cubic structures C4 and C5, arising from the cleavage of one Li-Cl bond in C4, in analogy to the findings from the AIMD study. As the lithium solvation increases, the LiCl cubic cluster further degrades by cleaving a second Li-Cl bond into two possible species: a cyclic R6 structure (if breaking non-adjacent edges of adjacent faces), and a cis boat-type structure B6 (if breaking opposite edges of the same face). No trans conformer of B6 type is detected, suggesting a preference for the cis isomer.