The experimentally observed absolute bond lengths and the expected slight shortening of Li-X bond distances upon opening the pseudo-cubane seen experimentally for X = Cl are satisfactorily reproduced. The Li-Cl distance in Li 2 Cl 2 (THF) 4 was reported to be 2.308(3) and 2.342(3) Å. In the pseudo-cubane structure, the Li-Cl bond distance was also estimated to be between 2.357(10) and 2.441(12) Å. This agrees well with calculated Li-Cl distances of 2.3(2) and 2.4(2) Å for the dimer and tetramer, respectively. The Li-Br bond distance was found to be around 2.53 Å in the broken cube polymer [(LiBr)(THF)]n, and was mentioned to be slightly longer in different tetrameric species, fitting well a value of 2.6(4) Å in our simulations. In the dimeric form, the computed distances of 2.5(2) Å are consistent with reported 2.51(2)-2.55(2) Å. 113 For Li-I, distances of 2.741(7) Å in the monomer and between 2.787(7) and 2.825(7) Å in the cubane are also in good agreement with our data (2.7(2) and 2.8(2) Å, respectively). The calculations reported here suggest that lithium halides are present in solution in a wide number of species. Their shape and relative abundances are strongly determined by the solvent, even if the nature of X tends to direct the systems towards compact species (X = Cl) or small and open species (X = I). Other solvents, like diethyl ether, are likely to yield similar global energy patterns, but different in their quantitative details. Adding other salts can also have drastic effects, as indicated in our early finding that MgCl 2 dismantles a pseudo-cubane Li 4 Cl 4 into a globally open structure. Thus, these lithium salts have geometrical features that are almost entirely determined by their environment.