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Mechanism of Aqueous Carbon Dioxide Reduction by the Solvated Electron

preprint
submitted on 20.07.2020 and posted on 21.07.2020 by Vladimir Rybkin
Aqueous solvated electron, eaq, 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 eaq reaction is very different from both rapid barrierless electron transfer, and proton-coupled electron transfer, where key transformations are caused by proton migration.

Funding

Swiss National Science Foundation PZ00P2_174227

History

Email Address of Submitting Author

vladimir.rybkin@chem.uzh.ch

Institution

University of Zurich

Country

Switzerland

ORCID For Submitting Author

0000-0001-5136-6035

Declaration of Conflict of Interest

No conflicts of interest

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