Molecular structures and vibrations of neutral and anionic CuOx (x=1-3,6) clusters -: art. no. 023201

We report equilibrium geometric structures of CuO2, CuO3, CuO6, and CuO6-1 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 C-s symmetry is found to be the lowest-energy structure for CuO2, while a Y-shaped structure with C-2v symmetry is the most stable structure for CuO3. For the larger CuO6 and CuO6-1 clusters, several competitive structures exist with structures containing ozonide units being higher in energy than those with O-2 units. The infrared and Raman spectra are calculated for the stable optimal geometries.