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Title: Unimolecular Decay of Criegee Intermediates to OH Radical Products: Prompt and Thermal Decay Processes

Abstract

Alkene ozonolysis is a primary oxidation pathway for anthropogenic and biogenic alkenes emitted into the troposphere. It is also an important source of atmospheric hydroxyl (OH) radicals, often called the atmosphere's detergent. Alkene ozonolysis takes place through a highly exothermic reaction pathway with multiple intermediates and barriers prior to releasing the OH radical products. Here, this Account focuses on a key reaction intermediate with a carbonyl oxide functional group (-COO), known as the Criegee intermediate, which is formed along with a carbonyl coproduct in alkene ozonolysis reactions. Under atmospheric conditions, the initially energized Criegee intermediates may promptly decay to OH products or be collisionally stabilized prior to thermal decay to OH radicals and other products.

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1461467
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Accounts of Chemical Research
Additional Journal Information:
Journal Volume: 51; Journal Issue: 4; Journal ID: ISSN 0001-4842
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lester, Marsha I., and Klippenstein, Stephen J. Unimolecular Decay of Criegee Intermediates to OH Radical Products: Prompt and Thermal Decay Processes. United States: N. p., 2018. Web. doi:10.1021/acs.accounts.8b00077.
Lester, Marsha I., & Klippenstein, Stephen J. Unimolecular Decay of Criegee Intermediates to OH Radical Products: Prompt and Thermal Decay Processes. United States. doi:10.1021/acs.accounts.8b00077.
Lester, Marsha I., and Klippenstein, Stephen J. Tue . "Unimolecular Decay of Criegee Intermediates to OH Radical Products: Prompt and Thermal Decay Processes". United States. doi:10.1021/acs.accounts.8b00077. https://www.osti.gov/servlets/purl/1461467.
@article{osti_1461467,
title = {Unimolecular Decay of Criegee Intermediates to OH Radical Products: Prompt and Thermal Decay Processes},
author = {Lester, Marsha I. and Klippenstein, Stephen J.},
abstractNote = {Alkene ozonolysis is a primary oxidation pathway for anthropogenic and biogenic alkenes emitted into the troposphere. It is also an important source of atmospheric hydroxyl (OH) radicals, often called the atmosphere's detergent. Alkene ozonolysis takes place through a highly exothermic reaction pathway with multiple intermediates and barriers prior to releasing the OH radical products. Here, this Account focuses on a key reaction intermediate with a carbonyl oxide functional group (-COO), known as the Criegee intermediate, which is formed along with a carbonyl coproduct in alkene ozonolysis reactions. Under atmospheric conditions, the initially energized Criegee intermediates may promptly decay to OH products or be collisionally stabilized prior to thermal decay to OH radicals and other products.},
doi = {10.1021/acs.accounts.8b00077},
journal = {Accounts of Chemical Research},
number = 4,
volume = 51,
place = {United States},
year = {2018},
month = {4}
}

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Works referencing / citing this record:

Formation of Criegee intermediates and peroxy acids: a computational study of gas-phase 1,3-cycloaddition of ozone with catechol
journal, January 2019

  • Deb, Debojit Kumar; Sarkar, Biplab
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 27
  • DOI: 10.1039/c9cp01312a

Threshold photoelectron spectrum of the CH 2 OO Criegee intermediate
journal, January 2019

  • Chicharro, David V.; Poullain, Sonia Marggi; Bañares, Luis
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 24
  • DOI: 10.1039/c9cp02538c

Formation of Criegee intermediates and peroxy acids: a computational study of gas-phase 1,3-cycloaddition of ozone with catechol
journal, January 2019

  • Deb, Debojit Kumar; Sarkar, Biplab
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 27
  • DOI: 10.1039/c9cp01312a

Threshold photoelectron spectrum of the CH 2 OO Criegee intermediate
journal, January 2019

  • Chicharro, David V.; Poullain, Sonia Marggi; Bañares, Luis
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 24
  • DOI: 10.1039/c9cp02538c