The stabilizing effect of alkali and alkaline-earth metal ions on the oxygen donors of four- and six-membered faujausite-like rings has been calculated in terms of Kohn-Sham core-level (O1s) energy shifts with respect to these same complexes without cations. The results confirm and complement earlier investigations by Vayssilov and co-workers where Na+ and K+ were the only complexing cations. The oxygen donor centers in six-membered rings are stabilized by -3.6 +/- 04, -3.9 +/- 0.5, -7.3 +/- 0.1, and -7.6 +/- 0.2 eV by K+, Na+, Ca2+, and Mg2+ adions, respectively. The energy shifts are even greater for four-membered rings where the stabilization effects attain -3.7 +/- 0.1, -4.1 +/- 0.1, -8.1 +/- 0.1, and -9.0 +/- 0.1 eV, respectively. These effects are also observed on the low-lying a-bonding and antibonding molecular orbitals (MOs) of the oxygen framework, but in a less systematic fashion. Clear relationships with the core level shifts are found when the effects of alkali metal complexation are evaluated through electron localization/delocalization indices, which are defined in terms of the whole wave function and not just of the individual orbitals. Complexation with cations not only involves a small but significant electron sharing of the cation with the oxygen atoms in the ring but also enhances electron exchange among oxygen atoms while reducing that between the O atoms and the Si or Al atoms bonded to them. Such changes slightly increase from Na to K and from Mg to Ca, whereas they are significantly enhanced for alkaline-earth metals relative to alkali metals. With respect to Al-free complexes, Si/Al substitution and cation charge compensation generally enhance electron delocalization among the O atoms, except between those that are linked through an Al atom, and cause either an increased or a decreased Si-O ionicity (smaller/higher electron exchange) depending on the position of O in the chain relative to the Al. atom(s). The generally increased electron delocalization among O atoms in the ring is induced by significant electron transfer from the adsorbed metal to the atoms in the ring. This same transfer establishes an electric field that leads to a noticeable change in the ring-atom core-level energies. The observed shifts are larger for the oxygen atoms because, being negatively charged, they are more easily polarizable than Al and Si. The enhanced electron delocalization among O atoms upon cation complexation is, also manifest in Pauling's double-bond nature of the bent sigma-bonding MO between nonadjacent oxygen centers in O-based ring structures.