Rapid Hydrogen Shift Scrambling in Hydroperoxy-Substituted Organic Peroxy Radicals
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.
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.Attached Files
Supplemental Material - jp5b06768_si_001.pdf
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Additional details
- Eprint ID
- 63921
- Resolver ID
- CaltechAUTHORS:20160125-090211778
- Danish Council for Independent Research
- NSF
- CHE-1508526
- Created
-
2016-01-25Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field
- Caltech groups
- Division of Geological and Planetary Sciences