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Title: Infrared spectroscopy of the acetyl cation and its protonated ketene isomer

Abstract

[C{sub 2},H{sub 3},O]{sup +} ions are generated with a pulsed discharge in a supersonic expansion containing methyl acetate or acetone. These ions are mass selected and their infrared spectra are recorded via laser photodissociation and the method of argon tagging. Computational chemistry is employed to investigate structural isomers and their spectra. The acetyl cation (CH{sub 3}CO{sup +}) is the global minimum and protonated ketene (CH{sub 2}COH{sup +}) is the next lowest energy isomer (+176.2 kJ/mol). When methyl acetate is employed as the precursor, the infrared spectrum reveals that only the acetyl cation is formed. Partially resolved rotational structure reveals rotation about the C{sub 3} axis. When acetone is used as the precursor, acetyl is still the most abundant cation, but there is also a minor component of protonated ketene. Computations reveal a significant barrier to interconversion between the two isomers (+221 kJ/mol), indicating that protonated ketene must be obtained via kinetic trapping. Both isomers may be present in interstellar environments, and their implications for astrochemistry are discussed.

Authors:
; ;  [1]
  1. Department of Chemistry, University of Georgia, Athens, Georgia 30602 (United States)
Publication Date:
OSTI Identifier:
22308989
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 2; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; ACETONE; ARGON; CALCULATION METHODS; CATIONS; DISSOCIATION; INFRARED SPECTRA; ISOMERS; KETENES; METHYL ACETATE; PHOTOLYSIS; PRECURSOR; PULSES

Citation Formats

Mosley, J. D., Young, J. W., and Duncan, M. A.. Infrared spectroscopy of the acetyl cation and its protonated ketene isomer. United States: N. p., 2014. Web. doi:10.1063/1.4887074.
Mosley, J. D., Young, J. W., & Duncan, M. A.. Infrared spectroscopy of the acetyl cation and its protonated ketene isomer. United States. doi:10.1063/1.4887074.
Mosley, J. D., Young, J. W., and Duncan, M. A.. 2014. "Infrared spectroscopy of the acetyl cation and its protonated ketene isomer". United States. doi:10.1063/1.4887074.
@article{osti_22308989,
title = {Infrared spectroscopy of the acetyl cation and its protonated ketene isomer},
author = {Mosley, J. D. and Young, J. W. and Duncan, M. A.},
abstractNote = {[C{sub 2},H{sub 3},O]{sup +} ions are generated with a pulsed discharge in a supersonic expansion containing methyl acetate or acetone. These ions are mass selected and their infrared spectra are recorded via laser photodissociation and the method of argon tagging. Computational chemistry is employed to investigate structural isomers and their spectra. The acetyl cation (CH{sub 3}CO{sup +}) is the global minimum and protonated ketene (CH{sub 2}COH{sup +}) is the next lowest energy isomer (+176.2 kJ/mol). When methyl acetate is employed as the precursor, the infrared spectrum reveals that only the acetyl cation is formed. Partially resolved rotational structure reveals rotation about the C{sub 3} axis. When acetone is used as the precursor, acetyl is still the most abundant cation, but there is also a minor component of protonated ketene. Computations reveal a significant barrier to interconversion between the two isomers (+221 kJ/mol), indicating that protonated ketene must be obtained via kinetic trapping. Both isomers may be present in interstellar environments, and their implications for astrochemistry are discussed.},
doi = {10.1063/1.4887074},
journal = {Journal of Chemical Physics},
number = 2,
volume = 141,
place = {United States},
year = 2014,
month = 7
}
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