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Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study

The mechanism of the chemical reaction of H(2)O with three stabilized Criegee intermediates (stabCI-OO, stabCI-CH(3)-OO and stabCIx-OO) produced via the limonene ozonolysis reaction has been investigated using ab initio and DFT (Density Functional Theory) methods. It has been shown that the formatio...

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Autores principales: Jiang, Lei, Lan, Ru, Xu, Yi-Sheng, Zhang, Wen-Jie, Yang, Wen
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Molecular Diversity Preservation International (MDPI) 2013
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3634429/
https://www.ncbi.nlm.nih.gov/pubmed/23481640
http://dx.doi.org/10.3390/ijms14035784
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author Jiang, Lei
Lan, Ru
Xu, Yi-Sheng
Zhang, Wen-Jie
Yang, Wen
author_facet Jiang, Lei
Lan, Ru
Xu, Yi-Sheng
Zhang, Wen-Jie
Yang, Wen
author_sort Jiang, Lei
collection PubMed
description The mechanism of the chemical reaction of H(2)O with three stabilized Criegee intermediates (stabCI-OO, stabCI-CH(3)-OO and stabCIx-OO) produced via the limonene ozonolysis reaction has been investigated using ab initio and DFT (Density Functional Theory) methods. It has been shown that the formation of the hydrogen-bonded complexes is followed by two different reaction pathways, leading to the formation of either OH radicals via water-catalyzed H migration or of α-hydroxy hydroperoxide. Both pathways were found to be essential sources of atmospheric OH radical and H(2)O(2) making a significant contribution to the formation of secondary aerosols in the Earth’s atmosphere. The activation energies at the CCSD(T)/6-31G(d) + CF level of theory were found to be in the range of 14.70–21.98 kcal mol(−1). The formation of α-hydroxy hydroperoxide for the reaction of stabCIx-OO and H(2)O with the activation energy of 14.70 kcal mol(−1) is identified as the most favorable pathway.
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spelling pubmed-36344292013-05-02 Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study Jiang, Lei Lan, Ru Xu, Yi-Sheng Zhang, Wen-Jie Yang, Wen Int J Mol Sci Article The mechanism of the chemical reaction of H(2)O with three stabilized Criegee intermediates (stabCI-OO, stabCI-CH(3)-OO and stabCIx-OO) produced via the limonene ozonolysis reaction has been investigated using ab initio and DFT (Density Functional Theory) methods. It has been shown that the formation of the hydrogen-bonded complexes is followed by two different reaction pathways, leading to the formation of either OH radicals via water-catalyzed H migration or of α-hydroxy hydroperoxide. Both pathways were found to be essential sources of atmospheric OH radical and H(2)O(2) making a significant contribution to the formation of secondary aerosols in the Earth’s atmosphere. The activation energies at the CCSD(T)/6-31G(d) + CF level of theory were found to be in the range of 14.70–21.98 kcal mol(−1). The formation of α-hydroxy hydroperoxide for the reaction of stabCIx-OO and H(2)O with the activation energy of 14.70 kcal mol(−1) is identified as the most favorable pathway. Molecular Diversity Preservation International (MDPI) 2013-03-12 /pmc/articles/PMC3634429/ /pubmed/23481640 http://dx.doi.org/10.3390/ijms14035784 Text en © 2013 by the authors; licensee MDPI, Basel, Switzerland. http://creativecommons.org/licenses/by/3.0 This article is an open-access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/3.0/).
spellingShingle Article
Jiang, Lei
Lan, Ru
Xu, Yi-Sheng
Zhang, Wen-Jie
Yang, Wen
Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study
title Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study
title_full Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study
title_fullStr Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study
title_full_unstemmed Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study
title_short Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Water: Ab Initio and DFT Study
title_sort reaction of stabilized criegee intermediates from ozonolysis of limonene with water: ab initio and dft study
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3634429/
https://www.ncbi.nlm.nih.gov/pubmed/23481640
http://dx.doi.org/10.3390/ijms14035784
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