Activation of CO₂ in Photoirradiated CO₂-H₂O Clusters: Direct Ab Initio Molecular Dynamics (MD) Study

Carbon dioxide (CO₂) is one of the stable and inactive molecules that contribute to greenhouse gases. The development of new reactions of CO₂ activation, chemical fixation, and conversion is a very important issue. In this report, the reactions of CO₂-H₂O binary clusters were investigated using a direct ab initio molecular dynamics (AIMD) method to find a new reaction of CO₂ activation. Clusters composed of carbon dioxide and water molecules, CO₂(H₂O) _n ( n = 2-5), were utilized as a model of the binary cluster. The reaction dynamics of [CO₂(H₂O) _n]⁺ following the ionization of parent neutral clusters were also investigated. Two electronic states of [CO₂(H₂O) _n]⁺ were examined for direct AIMD surfaces: CO₂[(H₂O) _n]⁺ (ground state) and (CO₂)⁺(H₂O) _n (excited charge transfer (CT) state). After the ionization of the clusters, a proton-transfer (PT) reaction occurred within the (H₂O) _n⁺ moiety at the ground state, whereas the reactive HCO₃ radical was formed at the CT state for OH addition to CO₂⁺: CO₂⁺(H₂O) _n → HCO₃ + H⁺(H₂O) _n-1. The mechanisms of the PT process and the HCO₃ radical formation were discussed based on the theoretical results.