Issue 42, 2012

The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere

Abstract

The reaction of Criegee intermediates (CI) with NO and RO2 radicals is studied for the first time by theoretical methodologies; additionally, the reaction of CI with SO2 molecules is re-examined. The reaction of CI with NO was found to be slow, with a distinct energy barrier. Their reaction with RO2 radicals proceeds by the formation of a pre-reactive complex followed by addition of the RO2 radical on the CI carbon over a submerged barrier, leading to a larger peroxy radical and opening the possibility for oligomer formation in agreement with experiment. The impact of singlet biradicals on the reaction of CI with SO2 is examined, finding a different reaction mechanism compared to earlier work. For larger CI, the reaction with SO2 at atmospheric pressures mainly yields thermalized sulfur-bearing secondary ozonides. The fate of the CI in the atmosphere is examined in detail, based on observed concentration of a multitude of coreactants in the atmosphere, and estimated rate coefficients available from literature data. The impact of SCI on tropospheric chemistry is discussed.

Graphical abstract: The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere

Supplementary files

Article information

Article type
Paper
Submitted
06 Jul 2012
Accepted
05 Sep 2012
First published
05 Sep 2012

Phys. Chem. Chem. Phys., 2012,14, 14682-14695

The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere

L. Vereecken, H. Harder and A. Novelli, Phys. Chem. Chem. Phys., 2012, 14, 14682 DOI: 10.1039/C2CP42300F

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