The Origin of the Reactivity of the Criegee Intermediate: Implications for Atmospheric Particle Growth

Journal Article · Fri Dec 04 00:00:00 EST 2015 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201509685· OSTI ID:1401169

Miliordos, Evangelos  ^[1]; Xantheas, Sotiris S. ^[1]

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1. Physical Sciences Division Pacific Northwest National Laboratory 902 Battelle Boulevard, P.O. Box 999, MS K1-83 Richland WA 99352 USA

Abstract The electronic structure of the simplest Criegee intermediate, H ₂ COO, is practically that of a closed shell. On the biradical scale ( β ), where 0 corresponds to the pure closed shell and 1 to a pure biradical, its β  value is only 0.10, suggesting that its ground electronic state is best described as a H ₂ C=O ^δ+ −O ^δ− zwitterion. However, this picture of a nearly inert closed shell contradicts its rich reactivity in the atmosphere. It is shown that the mixing of its ground state with the first triplet excited state, which is a pure biradical state of the type H ₂ C ^. −O−O ^. , is responsible for the formation of strongly bound products during reactions inducing atmospheric particle growth.

• Sponsoring Organization: USDOE
• Grant/Contract Number: AC02-05CH11231
• OSTI ID: 1401169
• Journal Information: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Vol. 55 Journal Issue: 3; ISSN 1433-7851
• Publisher: Wiley Blackwell (John Wiley & Sons)
• Country of Publication: Germany
• Language: English