Molecular structures and vibrations of neutral and anionic CuOx (x = 1-3,6) clusters

Abstract

We report equilibrium geometric structures of CuO2, CuO3, CuO6, and CuO clusters obtained by an all-electron linear combination of atomic orbitals scheme within the density-functional theory with generalized gradient approximation to describe the exchange-correlation effects. The vibrational stability of all clusters is examined on the basis of the vibrational frequencies. A structure with Cs symmetry is found to be the lowest-energy structure for CuO2, while a -shaped structure with C2v symmetry is the most stable structure for CuO3. For the larger CuO6 and CuO clusters, several competitive structures exist with structures containing ozonide units being higher in energy than those with O2 units. The infrared and Raman spectra are calculated for the stable optimal geometries. ~