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Title: UV Photodissociation Dynamics of the CH3CHOO Criegee Intermediate: Action Spectroscopy and Velocity Map Imaging of O-Atom Products

Abstract

We report that UV excitation of jet-cooled CH3CHOO on the B1A'–X1A' transition results in dissociation to two spin-allowed product channels: CH3CHO X1A' + O 1D and CH3CHO a3A" + O 3P. The O 1D and O 3P products are detected using 2 + 1 REMPI at 205 and 226 nm, respectively, for action spectroscopy and velocity map imaging studies. The O 1D action spectrum closely follows the previously reported UV absorption spectrum for jet-cooled CH3CHOO [Beames et al. J. Chem. Phys. 2013, 138, 244307]. Velocity map images of the O 1D products following excitation of CH3CHOO at 305, 320, and 350 nm exhibit anisotropic angular distributions indicative of rapid (ps) dissociation, along with broad and unstructured total kinetic energy (TKER) distributions that reflect the internal energy distribution of the CH3CHO X1A' coproducts. The O 3P action spectrum turns on near the peak of the UV absorption spectrum (ca. 324 nm) and extends to higher energy with steadily increasing O 3P yield. Excitation of CH3CHOO at 305 nm, attributed to absorption of the more stable syn-conformer, also results in an anisotropic angular distribution of O 3P products arising from rapid (ps) dissociation, but a narrower TKER distribution since less energy ismore » available to the CH3CHO a3A" + O 3P products. The threshold for the higher energy CH3CHO a3A" + O 3P product channel is determined to be ca. 88.4 kcal mol–1 from the termination of the TKER distribution and the onset of the O 3P action spectrum. This threshold is combined with the singlet-triplet spacings of O atoms and acetaldehyde to establish the dissociation energy for syn-CH3HOO X1A' to the lowest spin-allowed product channel, CH3CHO X1A' + O 1D, of ≤55.9 ± 0.4 kcal mol–1. Lastly, a harmonic normal-mode analysis is utilized to identify the vibrational modes of CH3CHO likely to be excited upon dissociation into the two product channels.« less

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1598535
Grant/Contract Number:  
FG02-87ER13792
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 119; Journal Issue: 30; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Hongwei, Fang, Yi, Kidwell, Nathanael M., Beames, Joseph M., and Lester, Marsha I. UV Photodissociation Dynamics of the CH3CHOO Criegee Intermediate: Action Spectroscopy and Velocity Map Imaging of O-Atom Products. United States: N. p., 2015. Web. doi:10.1021/acs.jpca.5b05352.
Li, Hongwei, Fang, Yi, Kidwell, Nathanael M., Beames, Joseph M., & Lester, Marsha I. UV Photodissociation Dynamics of the CH3CHOO Criegee Intermediate: Action Spectroscopy and Velocity Map Imaging of O-Atom Products. United States. https://doi.org/10.1021/acs.jpca.5b05352
Li, Hongwei, Fang, Yi, Kidwell, Nathanael M., Beames, Joseph M., and Lester, Marsha I. Mon . "UV Photodissociation Dynamics of the CH3CHOO Criegee Intermediate: Action Spectroscopy and Velocity Map Imaging of O-Atom Products". United States. https://doi.org/10.1021/acs.jpca.5b05352. https://www.osti.gov/servlets/purl/1598535.
@article{osti_1598535,
title = {UV Photodissociation Dynamics of the CH3CHOO Criegee Intermediate: Action Spectroscopy and Velocity Map Imaging of O-Atom Products},
author = {Li, Hongwei and Fang, Yi and Kidwell, Nathanael M. and Beames, Joseph M. and Lester, Marsha I.},
abstractNote = {We report that UV excitation of jet-cooled CH3CHOO on the B1A'–X1A' transition results in dissociation to two spin-allowed product channels: CH3CHO X1A' + O 1D and CH3CHO a3A" + O 3P. The O 1D and O 3P products are detected using 2 + 1 REMPI at 205 and 226 nm, respectively, for action spectroscopy and velocity map imaging studies. The O 1D action spectrum closely follows the previously reported UV absorption spectrum for jet-cooled CH3CHOO [Beames et al. J. Chem. Phys. 2013, 138, 244307]. Velocity map images of the O 1D products following excitation of CH3CHOO at 305, 320, and 350 nm exhibit anisotropic angular distributions indicative of rapid (ps) dissociation, along with broad and unstructured total kinetic energy (TKER) distributions that reflect the internal energy distribution of the CH3CHO X1A' coproducts. The O 3P action spectrum turns on near the peak of the UV absorption spectrum (ca. 324 nm) and extends to higher energy with steadily increasing O 3P yield. Excitation of CH3CHOO at 305 nm, attributed to absorption of the more stable syn-conformer, also results in an anisotropic angular distribution of O 3P products arising from rapid (ps) dissociation, but a narrower TKER distribution since less energy is available to the CH3CHO a3A" + O 3P products. The threshold for the higher energy CH3CHO a3A" + O 3P product channel is determined to be ca. 88.4 kcal mol–1 from the termination of the TKER distribution and the onset of the O 3P action spectrum. This threshold is combined with the singlet-triplet spacings of O atoms and acetaldehyde to establish the dissociation energy for syn-CH3HOO X1A' to the lowest spin-allowed product channel, CH3CHO X1A' + O 1D, of ≤55.9 ± 0.4 kcal mol–1. Lastly, a harmonic normal-mode analysis is utilized to identify the vibrational modes of CH3CHO likely to be excited upon dissociation into the two product channels.},
doi = {10.1021/acs.jpca.5b05352},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 30,
volume = 119,
place = {United States},
year = {Mon Jul 20 00:00:00 EDT 2015},
month = {Mon Jul 20 00:00:00 EDT 2015}
}

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