Ground and low-lying excited states of Na(NH3)n and Na(H2O)n clusters: Formation and localization of solvated electron

The ground and low-lying excited states of Na(NH3)n and Na(H2O)n (n = 1–8) clusters were studied using ab initio molecular orbital methods. The calculated vertical transition energies to the 32P(Na)-type states agree well with the energies of the absorption maxima. The clusters change from a valence state to a two-center state via a diffuse one-center state with increasing n in both the ground and excited states. The localization of an unpaired electron proceeds at a faster rate against n in Na(H2O)n than in Na(NH3)n. The formation of an excited state of the solvated electron is found in Na(H2O)4–8.