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Mechanism of Aqueous Carbon Dioxide Reduction by the Solvated Electron


Rybkin, Vladimir V (2020). Mechanism of Aqueous Carbon Dioxide Reduction by the Solvated Electron. Journal of Physical Chemistry B, 124(46):10435-10441.

Abstract

Aqueous solvated electron (eaq–), a key species in radiation and plasma chemistry, can efficiently reduce CO2 in a potential green chemistry application. Here, the mechanism of this reaction is unravelled by condensed-phase molecular dynamics based on the correlated wave function and an accurate density functional theory (DFT) approximation. Here, we design 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 hydrogen bond breaking in the second solvation shell of the solvated electron. This picture of an 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.

Abstract

Aqueous solvated electron (eaq–), a key species in radiation and plasma chemistry, can efficiently reduce CO2 in a potential green chemistry application. Here, the mechanism of this reaction is unravelled by condensed-phase molecular dynamics based on the correlated wave function and an accurate density functional theory (DFT) approximation. Here, we design 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 hydrogen bond breaking in the second solvation shell of the solvated electron. This picture of an 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.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Physical and Theoretical Chemistry
Physical Sciences > Surfaces, Coatings and Films
Physical Sciences > Materials Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, Materials Chemistry, Surfaces, Coatings and Films
Language:English
Date:19 November 2020
Deposited On:01 Feb 2021 15:57
Last Modified:02 Feb 2021 21:00
Publisher:American Chemical Society (ACS)
ISSN:1520-5207
OA Status:Closed
Publisher DOI:https://doi.org/10.1021/acs.jpcb.0c07859
PubMed ID:33170009
Project Information:
  • : FunderSNSF
  • : Grant IDPZ00P2_174227
  • : Project TitleCondensed-Phase Quantum Chemistry via Embedding Theory

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