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https://doi.org/10.5194/egusphere-2025-1364
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/egusphere-2025-1364
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
Preprints
24 Apr 2025
 | 24 Apr 2025
Status: this preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).

Criegee + HONO reaction: the dominant sink of Criegee, and the missing non-photolytic source of OH•

Pradeep Kumar, Vishva Jeet Anand, and Philips Kumar Rai

Abstract. One of the most important puzzles in atmospheric chemistry is a mismatch between observed and modeled concentrations of OH•/HO•2 in the presence of high concentrations of volatile organic compounds. It is now well established that to fulfill this gap, one needs a reaction that is not only capable of producing OH• but also able to act as a sink of HO•2. In the present work, we are proposing the Criegee + HONO reaction as a possible solution of this puzzle. Our quantum chemical and kinetic calculations clearly suggest that this reaction can not only be an important source of OH radicals but can also act as a sink of HO2 radicals. Our study also suggests that HONO has the potential to become the most dominant sink of CI surpasses SO2 and water dimer, even in highly humid conditions.

How to cite. Kumar, P., Anand, V. J., and Rai, P. K.: Criegee + HONO reaction: the dominant sink of Criegee, and the missing non-photolytic source of OH•, EGUsphere [preprint], https://doi.org/10.5194/egusphere-2025-1364, 2025.
Received: 22 Mar 2025 – Discussion started: 24 Apr 2025
Publisher's note: Copernicus Publications remains neutral with regard to jurisdictional claims made in the text, published maps, institutional affiliations, or any other geographical representation in this preprint. The responsibility to include appropriate place names lies with the authors.
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Pradeep Kumar, Vishva Jeet Anand, and Philips Kumar Rai

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Pradeep Kumar, Vishva Jeet Anand, and Philips Kumar Rai

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Pradeep Kumar, Vishva Jeet Anand, and Philips Kumar Rai

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Short summary
In this work, we studied the reaction of simple and dimethyl-substituted Criegee with HONO. By comparing it with other known sinks of CI, we have shown that this reaction can serve as a major sink for Criegee intermediates, even in the presence of high humidity and SO2. The reaction can be a key nocturnal source of OH•, capable of HO•2 ↔ OH• recycling. Consequently, this reaction can be key in fulfilling the gap between the observed and modeled concentration of OH radicals.
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