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© 2022. This work is published under https://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.

Abstract

Reaction with ozone is an important atmospheric removal process for alkenes. The ozonolysis reaction produces carbonyls and carbonyl oxides (Criegee intermediates, CI), which can rapidly decompose to yield a range of closed shell and radical products, including OH radicals. Consequently, it is essential to accurately represent the complex chemistry of Criegee intermediates in atmospheric models in order to fully understand the impact of alkene ozonolysis on atmospheric composition. A mechanism construction protocol is presented which is suitable for use in automatic mechanism generation. The protocol defines the critical parameters for describing the chemistry following the initial reaction, namely the primary carbonyl/CI yields from the primary ozonide fragmentation, the amount of stabilisation of the excited CI, the unimolecular decomposition pathways, rates and products of the CI, and the bimolecular rates and products of atmospherically important reactions of the stabilised CI (SCI). This analysis implicitly predicts the yield of OH from the alkene–ozone reaction. A comprehensive database of experimental OH, SCI and carbonyl yields has been collated using reported values in the literature and used to assess the reliability of the protocol. The protocol provides estimates of OH, SCI and carbonyl yields with root mean square errors of 0.13 and 0.12 and 0.14, respectively. Areas where new experimental and theoretical data would improve the protocol and its assessment are identified and discussed.

Details

Title
Estimation of mechanistic parameters in the gas-phase reactions of ozone with alkenes for use in automated mechanism construction
Author
Newland, Mike J 1 ; Mouchel-Vallon, Camille 2   VIAFID ORCID Logo  ; Valorso, Richard 3 ; Aumont, Bernard 3   VIAFID ORCID Logo  ; Vereecken, Luc 4   VIAFID ORCID Logo  ; Jenkin, Michael E 5   VIAFID ORCID Logo  ; Rickard, Andrew R 6   VIAFID ORCID Logo 

 Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, UK; now at: ICARE-CNRS, 1 C Av. de la Recherche Scientifique, 45071 Orléans CEDEX 2, France 
 Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, UK; now at: Laboratoire d'Aérologie, Université de Toulouse, CNRS, UPS, Toulouse, France 
 Univ Paris Est Creteil and Université de Paris, CNRS, LISA, 94010 Créteil, France 
 Forschungszentrum Jülich GmbH, Institute for Energy and Climate, IEK-8 Troposphere, 52428 Jülich, Germany 
 Atmospheric Chemistry Services, Okehampton, Devon, EX20 4QB, UK 
 Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, UK; National Centre for Atmospheric Science, Wolfson Atmospheric Chemistry Laboratories, University of York, York, UK 
Pages
6167-6195
Publication year
2022
Publication date
2022
Publisher
Copernicus GmbH
ISSN
16807316
e-ISSN
16807324
Source type
Scholarly Journal
Language of publication
English
ProQuest document ID
2661774121
Copyright
© 2022. This work is published under https://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.