Ab initio investigation of the ground and excited states of RuO+,0,− and their reaction with water

Abstract

High-level quantum chemical calculations on RuO^0,± elucidate the electronic structure of their low-lying electronic states. For thirty-two states, we report the electronic configurations, bond lengths, vibrational frequencies, spin–orbit splittings, and excitation energies. The electronic states of RuO can be generated from those of RuO⁺ by adding one electron to the σ non-bonding orbital closely resembling the 5s atomic orbital of Ru. The ground states for RuO and RuO⁻ are clearly identified as ⁵Δ and ⁴Δ, but the two states (⁴Δ and ²Π) compete for RuO⁺. The difficulty of calculations is revealed by our small binding energies compared to the experimental values. In addition, we studied the reaction of the three species with water in their ground and selected low-lying electronic states. We found a consistent decrease of the activation energy barriers and higher exothermicity as we add electrons to the system. RuO⁻ is found to facilitate the reaction for both kinetic and thermodynamic reasons.