Photochemistry of the pyruvate anion produces CO2, CO, CH3–, CH3, and a low energy electron

Clarke, Connor J.; Gibbard, Jemma A.; Hutton, Lewis; Verlet, Jan R.R.; Curchod, Basile F.E.

Abstract

The photochemistry of pyruvic acid has attracted much scientific interest because it is believed to play critical roles in atmospheric chemistry. However, under most atmospherically relevant conditions, pyruvic acid deprotonates to form its conjugate base, the photochemistry of which is essentially unknown. Here, we present a detailed study of the photochemistry of the isolated pyruvate anion and uncover that it is extremely rich. Using photoelectron imaging and computational chemistry, we show that photoexcitation by UVA light leads to the formation of CO2, CO, and CH3−. The observation of the unusual methide anion formation and its subsequent decomposition into methyl radical and a free electron may hold important consequences for atmospheric chemistry. From a mechanistic perspective, the initial decarboxylation of pyruvate necessarily differs from that in pyruvic acid, due to the missing proton in the anion.

Citation

Clarke, C. J., Gibbard, J. A., Hutton, L., Verlet, J. R., & Curchod, B. F. (2022). Photochemistry of the pyruvate anion produces CO2, CO, CH3–, CH3, and a low energy electron. Nature Communications, 13(1), Article 937. https://doi.org/10.1038/s41467-022-28582-4

• Journal Article Type: Article
• Acceptance Date: Feb 1, 2022
• Online Publication Date: Feb 17, 2022
• Publication Date: 2022
• Deposit Date: Mar 15, 2022
• Publicly Available Date: Mar 16, 2022
• Journal: Nature Communications
• Electronic ISSN: 2041-1723
• Publisher: Nature Research
• Peer Reviewed: Peer Reviewed
• Volume: 13
• Issue: 1
• Article Number: 937
• DOI: https://doi.org/10.1038/s41467-022-28582-4
• Public URL: https://durham-repository.worktribe.com/output/1211287