Electronic structure of small copper clusters. II. Localized d hole in excited states and ionized states of Cu2 and Cu3

Abstract

The electronic structure of Cu2 and Cu3 clusters is investigated by ab initio SCF calculations. The geometry optimization is performed. Because of the Jahn–Teller effects the obtuse and acute isosceles triangle configurations of Cu3 are energetically lower than the regular triangle one. The ‘‘localized’’ orbital which is located at the top or center atom is commonly found through the obtuse, regular, acute, and linear triangle Cu3’s. The excited and ionized states where the localized d electron participates are energetically close to those of (s → s or s*) and (s → ∞) states, which suggests that the electronic structure of Cu3’s is similar to that of bulk. The calculated excitation energies and ionization potentials for these states agree with experiment within error of 1.0 eV. The localized d hole excited states and the ionized states are found in Cu2 as well. The effect of the basis set superposition on Cu2 and Cu3 and the band structure of larger Cu clusters are also discussed.