Theoretical study of first-row transition metal oxide cations

Abstract

The equilibrium geometries, dissociation energies, and electronic structures of the ground and low-lying excited states for the first-row transition metal oxide cations, MO+ (M=Sc to Zn), have been studied using the multireference singles and doubles configuration interaction (MR–SDCI) and the multireference second-order Møller–Plesset methods. To investigate the applicability of the density functional theory (DFT) to an electronic structure system with a multiconfigurational character, the Becke exchange functional with the Lee–Yang–Parr correlation functional, the Becke exchange functional with the one-parameter progressive correlation functional (BOP), and the Becke three-parameter hybrid exchange functional with the Lee–Yang–Parr correlation functional (B3LYP) methods have also been applied. The DFT predicts the ground state M–O bond lengths in good agreement with the multireference-based methods except for MnO+ and CuO+, which have a multiconfigurational electronic structure. With respect to the dissociation energies, the B3LYP results are in good agreement with the multireference-based methods, while the DFT with pure functionals overestimates the energetics by about 20 kcal/mol compared to the MR–SDCI method.