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Title: Photodissociation of iso-propoxy (i-C3H7O) radical at 248 nm

Abstract

Photodissociation of the i-C3H7O radical is investigated using fast beam photofragment translational spectroscopy. Neutral i-C3H7O radicals are produced through the photodetachment of a fast beam of i-C3H7O- anions and are subsequently dissociated at 248 nm (5.0 eV). Furthermore, the dominant product channels are CH3 + CH3CHO and OH + C3H6 with some contribution from H + C3H6O. The CH3 and H loss channels are attributed to dissociation on the ground electronic state of i-C3H7O, but in a nonstatistical manner because calculated RRKM dissociation rates exceed the rate of energy randomization. Translational energy and angular distributions for OH loss are consistent with ground state dissociation, but the branching ratio for this channel is considerably higher than predicted from RRKM rate calculations. Additionally, i-C3H7O undergoes three-body fragmentation to CH3 + CH3 + HCO and CH3 + CH4 + CO. These three-body channels are attributed to dissociation of i-C3H7O to CH3 + CH3CHO, followed by secondary dissociation of CH3CHO on its ground electronic state.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Institutes of Health (NIH); USDOE
OSTI Identifier:
1782158
Alternate Identifier(s):
OSTI ID: 1644714
Grant/Contract Number:  
AC02-05CH11231; S10OD023532
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 22; Journal Issue: 31; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sullivan, Erin N., Saric, Steven, and Neumark, Daniel M.. Photodissociation of iso-propoxy (i-C3H7O) radical at 248 nm. United States: N. p., 2020. Web. https://doi.org/10.1039/d0cp02493g.
Sullivan, Erin N., Saric, Steven, & Neumark, Daniel M.. Photodissociation of iso-propoxy (i-C3H7O) radical at 248 nm. United States. https://doi.org/10.1039/d0cp02493g
Sullivan, Erin N., Saric, Steven, and Neumark, Daniel M.. Mon . "Photodissociation of iso-propoxy (i-C3H7O) radical at 248 nm". United States. https://doi.org/10.1039/d0cp02493g. https://www.osti.gov/servlets/purl/1782158.
@article{osti_1782158,
title = {Photodissociation of iso-propoxy (i-C3H7O) radical at 248 nm},
author = {Sullivan, Erin N. and Saric, Steven and Neumark, Daniel M.},
abstractNote = {Photodissociation of the i-C3H7O radical is investigated using fast beam photofragment translational spectroscopy. Neutral i-C3H7O radicals are produced through the photodetachment of a fast beam of i-C3H7O- anions and are subsequently dissociated at 248 nm (5.0 eV). Furthermore, the dominant product channels are CH3 + CH3CHO and OH + C3H6 with some contribution from H + C3H6O. The CH3 and H loss channels are attributed to dissociation on the ground electronic state of i-C3H7O, but in a nonstatistical manner because calculated RRKM dissociation rates exceed the rate of energy randomization. Translational energy and angular distributions for OH loss are consistent with ground state dissociation, but the branching ratio for this channel is considerably higher than predicted from RRKM rate calculations. Additionally, i-C3H7O undergoes three-body fragmentation to CH3 + CH3 + HCO and CH3 + CH4 + CO. These three-body channels are attributed to dissociation of i-C3H7O to CH3 + CH3CHO, followed by secondary dissociation of CH3CHO on its ground electronic state.},
doi = {10.1039/d0cp02493g},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 31,
volume = 22,
place = {United States},
year = {2020},
month = {7}
}

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