Exploring s-d, s-f, and d-f Electron Interactions in Ag n Ce + and Ag n Sm + by Chemical Reaction toward O 2 .

We investigate gas-phase reactions of free Ag n Ce + and Ag n Sm + clusters with oxygen molecules to explore s-d, s-f, and d-f electron interactions in the finite size regime; a Ce atom has a 5d electron as well as a 4f electron, whereas a Sm atom has six 4f electrons without 5d electrons. In the reaction of Ag n Ce + ( n = 3-20), the Ce atom located on the cluster surface provides an active site except for n = 15 and 16, as inferred from the composition of the reaction products with oxygen bound to the Ce atom as well as from their relatively high reactivity. The extremely low reactivity for n = 15 and 16 is due to encapsulation of the Ce atom by Ag atoms. The minimum reactivity observed at n = 16 suggests that a closed electronic shell with 18 valence electrons is formed with a delocalized Ce 5d electron, while the localized Ce 4f electron does not contribute to the shell closure. As for Ag n Sm + ( n = 1-18), encapsulation of the Sm atom was observed for n ≥ 15. The lower reactivity at n = 17 than at n = 16 and 18 implies that an 18-valence-electron shell closure is formed with s electrons from Ag and Sm atoms; Sm 4f electrons are not involved in the shell closure as in the case of Ag n Ce + . The present results suggest that the 4f electrons tend to localize on the lanthanoid atom, whereas the 5d electron delocalizes to contribute to the electron shell closure.