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Title: Deep tunneling in the unimolecular decay of CH3CHOO Criegee intermediates to OH radical products

Abstract

Unimolecular decay of Criegee intermediates produced in alkene ozonolysis is known to be a significant source of OH radicals in the troposphere. In this work, unimolecular decay of the methyl-substituted Criegee intermediate, syn-CH3CHOO, to OH products is shown to occur at energies significantly below the transition state barrier for a 1,4 hydrogen transfer that leads to these products. The rate of appearance of OH products arising from tunneling through the barrier is obtained through direct time-domain measurements following the vibrational activation of syn-CH3CHOO. IR excitation of syn-CH3CHOO at energies nearly 2000 cm-1 below the barrier is achieved through combination bands involving CH stretch and another lower frequency mode, and the resultant OH products are detected by UV laser-induced fluorescence. The observed syn-CH3CHOO combination bands in the 4100–4350 cm-1 region are identified by comparison with the computed IR absorption spectrum. The experimental decay rates are found to be ca. 106 s-1 in this deep tunneling regime, which is approximately 100-times slower than that in the vicinity of the barrier.The experimental results are consistent with statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical decay rates with tunneling through the barrier, and notable deviations may originate from the sparsity in the density of statesmore » for syn-CH3CHOO at lower energies. Finally, thermal unimolecular decay of syn-CH3CHOO is predicted to have significant contribution from microcanonical rates at energies that are much below the barrier.« less

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [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
  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:
1373744
Alternate Identifier(s):
OSTI ID: 1336837
Grant/Contract Number:  
AC02-06CH11357; CHE-1362835; CHE-1619660
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 23; 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; ab initio kinetics; creigee intermediate; tunneling; unimolecular decay

Citation Formats

Fang, Yi, Liu, Fang, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., and Lester, Marsha I. Deep tunneling in the unimolecular decay of CH3CHOO Criegee intermediates to OH radical products. United States: N. p., 2016. Web. doi:10.1063/1.4972015.
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Fang, Yi, Liu, Fang, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., & Lester, Marsha I. Deep tunneling in the unimolecular decay of CH3CHOO Criegee intermediates to OH radical products. United States. https://doi.org/10.1063/1.4972015
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Fang, Yi, Liu, Fang, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., and Lester, Marsha I. Mon . "Deep tunneling in the unimolecular decay of CH3CHOO Criegee intermediates to OH radical products". United States. https://doi.org/10.1063/1.4972015. https://www.osti.gov/servlets/purl/1373744.
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@article{osti_1373744,
title = {Deep tunneling in the unimolecular decay of CH3CHOO 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 = {Unimolecular decay of Criegee intermediates produced in alkene ozonolysis is known to be a significant source of OH radicals in the troposphere. In this work, unimolecular decay of the methyl-substituted Criegee intermediate, syn-CH3CHOO, to OH products is shown to occur at energies significantly below the transition state barrier for a 1,4 hydrogen transfer that leads to these products. The rate of appearance of OH products arising from tunneling through the barrier is obtained through direct time-domain measurements following the vibrational activation of syn-CH3CHOO. IR excitation of syn-CH3CHOO at energies nearly 2000 cm-1 below the barrier is achieved through combination bands involving CH stretch and another lower frequency mode, and the resultant OH products are detected by UV laser-induced fluorescence. The observed syn-CH3CHOO combination bands in the 4100–4350 cm-1 region are identified by comparison with the computed IR absorption spectrum. The experimental decay rates are found to be ca. 106 s-1 in this deep tunneling regime, which is approximately 100-times slower than that in the vicinity of the barrier.The experimental results are consistent with statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical decay rates with tunneling through the barrier, and notable deviations may originate from the sparsity in the density of states for syn-CH3CHOO at lower energies. Finally, thermal unimolecular decay of syn-CH3CHOO is predicted to have significant contribution from microcanonical rates at energies that are much below the barrier.},
doi = {10.1063/1.4972015},
journal = {Journal of Chemical Physics},
number = 23,
volume = 145,
place = {United States},
year = {Mon Dec 19 00:00:00 EST 2016},
month = {Mon Dec 19 00:00:00 EST 2016}
}
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