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Title: Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products

Abstract

The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH3CH2CHOO, following vibrational activation under collision-free conditions. Furthermore, complementary statistical Rice-Ramsperger-Kassel-Marcus calculations of the microcanonical unimolecular decay rate for CH3CH2CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantly to the decay rate. Infrared transitions of CH3CH2CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH3CH2CHOO of ca. 107 s-1, which are slower than those obtained for syn-CH3CHOO or (CH3)(2)COO reported previously at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH3CH2CHOO under atmospheric conditions, giving a rate of 279 s-1 at 298 K.

Authors:
 [1]; ORCiD logo [1];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1350088
Alternate Identifier(s):
OSTI ID: 1273668
Grant/Contract Number:  
AC02-06CH11357; CHE-1362835
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; RRKM theory; creigee intermediate; photodissociation

Citation Formats

Fang, Yi, Liu, Fang, Klippenstein, Stephen J., and Lester, Marsha I. Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products. United States: N. p., 2016. Web. doi:10.1063/1.4958992.
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Fang, Yi, Liu, Fang, Klippenstein, Stephen J., & Lester, Marsha I. Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products. United States. https://doi.org/10.1063/1.4958992
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Fang, Yi, Liu, Fang, Klippenstein, Stephen J., and Lester, Marsha I. Wed . "Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products". United States. https://doi.org/10.1063/1.4958992. https://www.osti.gov/servlets/purl/1350088.
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@article{osti_1350088,
title = {Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products},
author = {Fang, Yi and Liu, Fang and Klippenstein, Stephen J. and Lester, Marsha I.},
abstractNote = {The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH3CH2CHOO, following vibrational activation under collision-free conditions. Furthermore, complementary statistical Rice-Ramsperger-Kassel-Marcus calculations of the microcanonical unimolecular decay rate for CH3CH2CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantly to the decay rate. Infrared transitions of CH3CH2CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH3CH2CHOO of ca. 107 s-1, which are slower than those obtained for syn-CH3CHOO or (CH3)(2)COO reported previously at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH3CH2CHOO under atmospheric conditions, giving a rate of 279 s-1 at 298 K.},
doi = {10.1063/1.4958992},
journal = {Journal of Chemical Physics},
number = 4,
volume = 145,
place = {United States},
year = {2016},
month = {7}
}
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https://doi.org/10.1063/1.4958992
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    Works referencing / citing this record:

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