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Rapid Hydrogen Shift Scrambling in Hydroperoxy-Substituted Organic Peroxy Radicals

Jørgensen, Solvejg and Knap, Hasse C. and Otkjær, Rasmus V. and Jensen, Annesofie M. and Kjeldsen, Mette L. H. and Wennberg, Paul O. and Kjaergaard, Henrik G. (2016) Rapid Hydrogen Shift Scrambling in Hydroperoxy-Substituted Organic Peroxy Radicals. Journal of Physical Chemistry A, 120 (2). pp. 266-275. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20160125-090211778

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Abstract

Using quantum mechanical calculations, we have investigated hydrogen shift (H-shift) reactions in peroxy radicals derived from the atmospheric oxidation of 1-pentene (CH_2═CHCH_2CH_2CH_3) and its monosubstituted derivatives. We investigate the peroxy radicals, HOCH_2CH(OO)CR_1HCH_2CH_3, HOCH_2CH(OO)CH_2CR_1HCH_3, and HOCH_2CH(OO)CH_2CH_2CR_1H_2, where the substituent R_1 is an alcoholic (OH), a hydroperoxy (OOH), or a methoxy (OCH_3) group. For peroxy radicals with an OOH substituent, the H-shift reaction from the hydrogen atom on the OOH group to the OO group is extremely fast. We find that the rate constants of this type of H-shift reactions are greater than 10^3 s^(–1) for both the forward and the reverse reactions. It leads to the formation of two different radical isomers that react through different reaction mechanisms and yield different products. These very fast H-shift reactions are much faster than the reactions with NO and HO_2 under most atmospheric conditions and must be included in the atmospheric modeling of volatile organic compounds where hydroperoxy peroxy radicals are formed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acs.jpca.5b06768DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.jpca.5b06768PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.jpca.5b06768PublisherSupporting Information
ORCID:
AuthorORCID
Otkjær, Rasmus V.0000-0002-6094-1828
Wennberg, Paul O.0000-0002-6126-3854
Kjaergaard, Henrik G.0000-0002-7275-8297
Additional Information:© 2015 American Chemical Society. Received: July 14, 2015; Revised: December 11, 2015; Published: December 15, 2015. We are grateful to Theo Kurtén for helpful discussions and to Kristian H. Møller for running some of the calculations. We thank the Copenhagen Center for Exploitation of Solar Energy for time on their computer. We thank the Danish Council for Independent Research - Natural Sciences and the Danish Center for Scientific Computing (DCSC) for funding. This material is based upon work supported by the National Science Foundation under CHE-1508526. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Danish Council for Independent ResearchUNSPECIFIED
NSFCHE-1508526
Issue or Number:2
Record Number:CaltechAUTHORS:20160125-090211778
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160125-090211778
Official Citation:Rapid Hydrogen Shift Scrambling in Hydroperoxy-Substituted Organic Peroxy Radicals Solvejg Jørgensen, Hasse C. Knap, Rasmus V. Otkjær, Annesofie M. Jensen, Mette L. H. Kjeldsen, Paul O. Wennberg, and Henrik G. Kjaergaard The Journal of Physical Chemistry A 2016 120 (2), 266-275 DOI: 10.1021/acs.jpca.5b06768
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:63921
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:25 Jan 2016 17:15
Last Modified:09 Mar 2020 13:19

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