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Title: Unimolecular dissociation dynamics of vibrationally activated CH3CHOO Criegee intermediates to OH radical products

Abstract

The hydroxyl radical is a vital atmospheric oxidant, and a significant source of its production occurs through alkene ozonolysis. This takes place via a cycloaddition reaction and subsequent fragmentation to form an energized carbonyl oxide (for example, CH3CHOO), known as a Criegee intermediate, which can then either react with another atmospheric species or decay and, in doing so, produce the hydroxyl radical. In this work, we examine the dissociation dynamics of a prototypical Criegee intermediate by characterizing the translational and internal energy distributions of the OH radical products, which reflect critical configurations along the reaction pathway. Experimentally, the kinetic energy release to OH products is ascertained through velocity map imaging. Theoretically, quasi-classical trajectories are performed on a new full-dimensional, ab initio potential energy surface. Both experiment and theory show that most of the available energy flows into internal excitation of the vinoxy products. The isotropic angular distribution of OH fragments indicates that dissociation occurs in ≥2 ps, in agreement with theory.

Authors:
 [1];  [1];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Emory Univ., Atlanta, GA (United States)
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States); Emory Univ., Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1598279
Grant/Contract Number:  
FG02-87ER13792; FG02-97ER14782
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 8; Journal Issue: 5; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kidwell, Nathanael M., Li, Hongwei, Wang, Xiaohong, Bowman, Joel M., and Lester, Marsha I. Unimolecular dissociation dynamics of vibrationally activated CH3CHOO Criegee intermediates to OH radical products. United States: N. p., 2016. Web. doi:10.1038/nchem.2488.
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Kidwell, Nathanael M., Li, Hongwei, Wang, Xiaohong, Bowman, Joel M., & Lester, Marsha I. Unimolecular dissociation dynamics of vibrationally activated CH3CHOO Criegee intermediates to OH radical products. United States. https://doi.org/10.1038/nchem.2488
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Kidwell, Nathanael M., Li, Hongwei, Wang, Xiaohong, Bowman, Joel M., and Lester, Marsha I. Mon . "Unimolecular dissociation dynamics of vibrationally activated CH3CHOO Criegee intermediates to OH radical products". United States. https://doi.org/10.1038/nchem.2488. https://www.osti.gov/servlets/purl/1598279.
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@article{osti_1598279,
title = {Unimolecular dissociation dynamics of vibrationally activated CH3CHOO Criegee intermediates to OH radical products},
author = {Kidwell, Nathanael M. and Li, Hongwei and Wang, Xiaohong and Bowman, Joel M. and Lester, Marsha I.},
abstractNote = {The hydroxyl radical is a vital atmospheric oxidant, and a significant source of its production occurs through alkene ozonolysis. This takes place via a cycloaddition reaction and subsequent fragmentation to form an energized carbonyl oxide (for example, CH3CHOO), known as a Criegee intermediate, which can then either react with another atmospheric species or decay and, in doing so, produce the hydroxyl radical. In this work, we examine the dissociation dynamics of a prototypical Criegee intermediate by characterizing the translational and internal energy distributions of the OH radical products, which reflect critical configurations along the reaction pathway. Experimentally, the kinetic energy release to OH products is ascertained through velocity map imaging. Theoretically, quasi-classical trajectories are performed on a new full-dimensional, ab initio potential energy surface. Both experiment and theory show that most of the available energy flows into internal excitation of the vinoxy products. The isotropic angular distribution of OH fragments indicates that dissociation occurs in ≥2 ps, in agreement with theory.},
doi = {10.1038/nchem.2488},
journal = {Nature Chemistry},
number = 5,
volume = 8,
place = {United States},
year = {Mon Apr 04 00:00:00 EDT 2016},
month = {Mon Apr 04 00:00:00 EDT 2016}
}
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https://doi.org/10.1038/nchem.2488
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