AbstractAlkali atoms have unusually low ionization energies because their electronic structures have an excess electron beyond that of a filled electronic shell. Quantum states in metallic clusters are grouped into shells similar to those in atoms, and clusters with an excess electron beyond a closed electronic may also exhibit alkali character. This approach based on shell-filling is the way alkali species are formed as explained by the periodic table. We demonstrate that the ionization energy of metallic clusters with both filled and unfilled electronic shells can be substantially lowered by attaching ligands. The ligands form charge transfer complexes where the electronic spectrum is lifted via crystal field like effect. We demonstrate that the effect works for the weakly bound ligand, N-ethyl-2-pyrrolidone (EP = C₆H₁₁NO), and that the effect leads to a dramatic lowering of the ionization energy independent of the shell occupancy of the cluster.