Predicting the Stepwise Growth of Lithium Clusters Around Sulfur Species (S and S 2 ) From the Topology of the Electron Localization Function

(n = 1-10), with the aim of elucidating the mechanism governing the stepwise growth of lithium around sulfur centers. The equilibrium geometries of all clusters were first determined using density functional theory (DFT), and their electronic structures were subsequently analyzed through the topology of the electron localization function (ELF). The ELF analysis revealed the presence of two distinct types of topological valence domains: an inner domain fully localized on the sulfur atom and an outer domain delocalized over the lithium framework. We show that the growth of the lithium cluster is governed by the subtle interplay between these two domains. Most importantly, the combined topology of the inner and outer valence domains provides a predictive framework that not only identifies the preferred insertion site for each incoming lithium atom but also explains the progressive emergence of successive coordination shells, thereby leading systematically to the most stable structures throughout the growth process. The present findings open the way to a predictive description of lithium growth around larger sulfur species.