Mechanism of Aqueous Carbon Dioxide Reduction by the Solvated Electron

Aqueous solvated electron, e_aq, a key species in radiation and plasma chemistry, can effciently reduce CO₂ in a potential green chemistry application. Here, the mechanism of this reaction is unravelled by condensed-phase Born-Oppenheimer molecular dynamics based on the correlated wave function and accurate DFT approximation. We introduce and apply the holistic protocol for solvated electron's reactions encompassing all relevant reaction stages starting from diffusion. The carbon dioxide reduction proceeds via a cavity intermediate, which is separated from the product, CO2^-, by an energy barrier due to the bending of CO₂ and the corresponding solvent reorganization energy. The formation of the intermediate is caused by solvated electron's diffusion, whereas the intermediate transformation to CO₂^- is triggered by solvent fluctuations. This picture of activation-controlled e_aq reaction is very different from both rapid barrierless electron transfer, and proton-coupled electron transfer, where key transformations are caused by proton migration.