Long, B, Xia, Y, Bao, JL et al. (6 more authors) (2022) Reaction of SO3 with HONO2 and Implications for Sulfur Partitioning in the Atmosphere. Journal of the American Chemical Society, 144 (20). pp. 9172-9177. ISSN 0002-7863
Abstract
Sulfur trioxide is a critical intermediate for the sulfur cycle and the formation of sulfuric acid in the atmosphere. The traditional view is that sulfur trioxide is removed by water vapor in the troposphere. However, the concentration of water vapor decreases significantly with increasing altitude, leading to longer atmospheric lifetimes of sulfur trioxide. Here, we utilize a dual-level strategy that combines transition state theory calculated at the W2X//DF-CCSD(T)-F12b/jun′-cc-pVDZ level, with variational transition state theory with small-curvature tunneling from direct dynamics calculations at the M08-HX/MG3S level. We also report the pressure-dependent rate constants calculated using the system-specific quantum Rice–Ramsperger–Kassel (SS-QRRK) theory. The present findings show that falloff effects in the SO3 + HONO2 reaction are pronounced below 1 bar. The SO3 + HONO2 reaction can be a potential removal reaction for SO3 in the stratosphere and for HONO2 in the troposphere, because the reaction can potentially compete well with the SO3 + 2H2O reaction between 25 and 35 km, as well as the OH + HONO2 reaction. The present findings also suggest an unexpected new product from the SO3 + HONO2 reaction, which, although very short-lived, would have broad implications for understanding the partitioning of sulfur in the stratosphere and the potential for the SO3 reaction with organic acids to generate organosulfates without the need for heterogeneous chemistry.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2022 American Chemical Society. This is an author produced version of an article published in the Journal of the American Chemical Society. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 23 May 2022 06:28 |
Last Modified: | 16 May 2023 00:13 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/jacs.2c03499 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:187102 |