DFT study of electronic structure and geometry of anionic copper clusters

Abstract

Calculations of equilibrium geometry, vertical detachment energies (VDE) and transition energies ( T e) from the electronic ground state to excited states of Cu n − clusters ( n=2–10) 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 Cu 2–10 − clusters, the difference between calculated and experimental values of VDE and T e for the most stable isomers does not exceed 0.21 eV. The assignment of previously unknown Cu 6 −, Cu 8 −, Cu 9 − and Cu 10 − 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.