Single-Sheeted Double Many-Body Expansion Potential Energy Surface for Ground-State ClO2

A global single-sheeted double many-body expansion potential energy surface is reported for the ground electronic state of ClO2. The potential energy surface is obtained by fitting 3200 energy points that map all atom diatom dissociation channels as well as all relevant stationary points, including the well-known OClO and ClOO structures. The ab initio calculations are obtained at the multireference configuration interaction level of theory, employing the cc-pVXZ (X = D, T) Dunning basis sets, and then extrapolated to the complete basis set limit with the generalized uniform singlet- and triplet-pair protocol. The topographical features of the novel global potential energy surface are examined in detail.