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Title: Electronic Spectroscopy and Dissociation Dynamics of Vinyl-Substituted Criegee Intermediates: 2-Butenal Oxide and Comparison with Methyl Vinyl Ketone Oxide and Methacrolein Oxide Isomers

Abstract

The 2-butenal oxide Criegee intermediate [(CH3CH=CH)CHOO], an isomer of the four-carbon unsaturated Criegee intermediates derived from isoprene ozonolysis, is characterized on its first π*←π electronic transition and by the resultant dissociation dynamics to O (1D) + 2-butenal [(CH3CH=CH)CHO] products. The electronic spectrum of 2-butenal oxide under jet-cooled conditions is observed to be broad and unstructured with peak absorption at 373 nm, spanning to half maxima at 320 and 420 nm, and in good accord with the computed vertical excitation energies and absorption spectra obtained for its lowest energy conformers. The distribution of total kinetic energy released to products is ascertained through velocity map imaging of the O (1D) products. About half of the available energy, deduced from the theoretically computed asymptotic energy, is accommodated as internal excitation of the 2-butenal fragment. A reduced impulsive model is introduced to interpret the photodissociation dynamics, which accounts for the geometric changes between 2-butenal oxide and the 2-butenal fragment, and vibrational activation of associated modes in the 2-butenal product. Application of the reduced impulsive model to the photodissociation of isomeric methyl vinyl ketone oxide reveals greater internal activation of the methyl vinyl ketone product arising from methyl internal rotation and rock, which is distinctlymore » different than the dissociation dynamics of 2-butenal oxide or methacrolein oxide.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Univ. of Louisiana, Lafayette, LA (United States)
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1903781
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: 127; Journal Issue: 1; 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

Wang, Guanghan, Liu, Tianlin, Zou, Meijun, Sojdak, Christopher A., Kozlowski, Marisa C., Karsili, Tolga V., and Lester, Marsha I. Electronic Spectroscopy and Dissociation Dynamics of Vinyl-Substituted Criegee Intermediates: 2-Butenal Oxide and Comparison with Methyl Vinyl Ketone Oxide and Methacrolein Oxide Isomers. United States: N. p., 2022. Web. doi:10.1021/acs.jpca.2c08025.
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Wang, Guanghan, Liu, Tianlin, Zou, Meijun, Sojdak, Christopher A., Kozlowski, Marisa C., Karsili, Tolga V., & Lester, Marsha I. Electronic Spectroscopy and Dissociation Dynamics of Vinyl-Substituted Criegee Intermediates: 2-Butenal Oxide and Comparison with Methyl Vinyl Ketone Oxide and Methacrolein Oxide Isomers. United States. https://doi.org/10.1021/acs.jpca.2c08025
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Wang, Guanghan, Liu, Tianlin, Zou, Meijun, Sojdak, Christopher A., Kozlowski, Marisa C., Karsili, Tolga V., and Lester, Marsha I. Tue . "Electronic Spectroscopy and Dissociation Dynamics of Vinyl-Substituted Criegee Intermediates: 2-Butenal Oxide and Comparison with Methyl Vinyl Ketone Oxide and Methacrolein Oxide Isomers". United States. https://doi.org/10.1021/acs.jpca.2c08025. https://www.osti.gov/servlets/purl/1903781.
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@article{osti_1903781,
title = {Electronic Spectroscopy and Dissociation Dynamics of Vinyl-Substituted Criegee Intermediates: 2-Butenal Oxide and Comparison with Methyl Vinyl Ketone Oxide and Methacrolein Oxide Isomers},
author = {Wang, Guanghan and Liu, Tianlin and Zou, Meijun and Sojdak, Christopher A. and Kozlowski, Marisa C. and Karsili, Tolga V. and Lester, Marsha I.},
abstractNote = {The 2-butenal oxide Criegee intermediate [(CH3CH=CH)CHOO], an isomer of the four-carbon unsaturated Criegee intermediates derived from isoprene ozonolysis, is characterized on its first π*←π electronic transition and by the resultant dissociation dynamics to O (1D) + 2-butenal [(CH3CH=CH)CHO] products. The electronic spectrum of 2-butenal oxide under jet-cooled conditions is observed to be broad and unstructured with peak absorption at 373 nm, spanning to half maxima at 320 and 420 nm, and in good accord with the computed vertical excitation energies and absorption spectra obtained for its lowest energy conformers. The distribution of total kinetic energy released to products is ascertained through velocity map imaging of the O (1D) products. About half of the available energy, deduced from the theoretically computed asymptotic energy, is accommodated as internal excitation of the 2-butenal fragment. A reduced impulsive model is introduced to interpret the photodissociation dynamics, which accounts for the geometric changes between 2-butenal oxide and the 2-butenal fragment, and vibrational activation of associated modes in the 2-butenal product. Application of the reduced impulsive model to the photodissociation of isomeric methyl vinyl ketone oxide reveals greater internal activation of the methyl vinyl ketone product arising from methyl internal rotation and rock, which is distinctly different than the dissociation dynamics of 2-butenal oxide or methacrolein oxide.},
doi = {10.1021/acs.jpca.2c08025},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 1,
volume = 127,
place = {United States},
year = {Tue Dec 27 00:00:00 EST 2022},
month = {Tue Dec 27 00:00:00 EST 2022}
}
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