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Title: Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products

Abstract

In the atmosphere, a dominant loss process for carbonyl oxide intermediates produced from alkene ozonolysis is also an important source of hydroxyl radicals. In this work, the rate of appearance of OH radicals is revealed through direct time-domain measurements following vibrational activation of prototypical methyl-substituted Criegee intermediates under collision-free conditions. Complementary theoretical calculations predict the unimolecular decay rate for the Criegee intermediates in the vicinity of the barrier for 1,4 hydrogen transfer that leads to OH products. Both experiment and theory yield unimolecular decay rates of ca. 108 and 107 s–1 for syn-CH3CHOO and (CH3)2COO, respectively, at energies near the barrier. Tunneling through the barrier, computed from high level electronic structure theory and experimentally validated, makes a significant contribution to the decay rate. Extension to thermally averaged unimolecular decay of stabilized Criegee intermediates under atmospheric conditions yields rates that are six orders of magnitude slower than those evaluated directly in the barrier region.

Authors:
 [1]; ORCiD logo [1];  [1];  [2];  [3];  [1]
+ Show Author Affiliations
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1350086
Alternate Identifier(s):
OSTI ID: 1237774
Grant/Contract Number:  
AC02-06CH11357; CHE-1362835; CHE-1465001; CHE-1213347
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 6; 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; criegee intermediate; theoretical kinetics; unimolecular

Citation Formats

Fang, Yi, Liu, Fang, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., and Lester, Marsha I. Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products. United States: N. p., 2016. Web. doi:10.1063/1.4941768.
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Fang, Yi, Liu, Fang, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., & Lester, Marsha I. Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products. United States. https://doi.org/10.1063/1.4941768
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Fang, Yi, Liu, Fang, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., and Lester, Marsha I. Wed . "Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products". United States. https://doi.org/10.1063/1.4941768. https://www.osti.gov/servlets/purl/1350086.
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@article{osti_1350086,
title = {Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products},
author = {Fang, Yi and Liu, Fang and Barber, Victoria P. and Klippenstein, Stephen J. and McCoy, Anne B. and Lester, Marsha I.},
abstractNote = {In the atmosphere, a dominant loss process for carbonyl oxide intermediates produced from alkene ozonolysis is also an important source of hydroxyl radicals. In this work, the rate of appearance of OH radicals is revealed through direct time-domain measurements following vibrational activation of prototypical methyl-substituted Criegee intermediates under collision-free conditions. Complementary theoretical calculations predict the unimolecular decay rate for the Criegee intermediates in the vicinity of the barrier for 1,4 hydrogen transfer that leads to OH products. Both experiment and theory yield unimolecular decay rates of ca. 108 and 107 s–1 for syn-CH3CHOO and (CH3)2COO, respectively, at energies near the barrier. Tunneling through the barrier, computed from high level electronic structure theory and experimentally validated, makes a significant contribution to the decay rate. Extension to thermally averaged unimolecular decay of stabilized Criegee intermediates under atmospheric conditions yields rates that are six orders of magnitude slower than those evaluated directly in the barrier region.},
doi = {10.1063/1.4941768},
journal = {Journal of Chemical Physics},
number = 6,
volume = 144,
place = {United States},
year = {Wed Feb 10 00:00:00 EST 2016},
month = {Wed Feb 10 00:00:00 EST 2016}
}
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https://doi.org/10.1063/1.4941768
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