DFT study of electronic structure and geometry of anionic copper clusters

Calculations of equilibrium geometry, vertical detachment energies (VDE) and transition energies <f>(Te)</f> from the electronic ground state to excited states of Cu<f>n</f>- clusters <f>(n=2–10)</f> have been carried out within DFT model with the new functional developed recently [J. Mol. Struct. (Theochem) 664–665 (2003) 291]. The results of calculations have been compared with observed photoelectron spectra (PHES). The method provides a good agreement between calculations and experiment. For anionic Cu2–10- clusters, the difference between calculated and experimental values of VDE and <f>Te</f> for the most stable isomers does not exceed 0.21 eV. The assignment of previously unknown Cu6-, Cu8-, Cu9- and Cu10- structures has been made by both total energy calculations and comparison of experimental and calculated PHES. The electronic sructure, geometry and energetic characteristics of low-lying isomers have been studied. [Copyright &y& Elsevier]