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Title: Dynamics on the HOCO potential energy surface studied by dissociative photodetachment of HOCO{sup -} and DOCO{sup -}

Abstract

An experimental study of the dissociative photodetachment (DPD) dynamics of HOCO{sup -} and DOCO{sup -} at a photon energy of 3.21 eV has been carried out to probe the potential energy surface of the HOCO free radical and the dynamics of the OH+CO{yields}H+CO{sub 2} reaction. These photoelectron-photofragment coincidence experiments allow the identification of photodetachment processes leading to the production of stable HOCO free radicals and both the H+CO{sub 2} and OH+CO dissociation channels on the neutral surface. Isotopic substitution by deuterium in the parent ion is observed to reduce the product branching ratio for the D+CO{sub 2} channel, consistent with tunneling playing a role in this dissociation pathway. Other isotope effects on the detailed partitioning of kinetic energy between photoelectrons and photofragments are also discussed. The results are compared to recent theoretical predictions of this DPD process, and evidence for the involvement of vibrationally excited HOCO{sup -} anions is discussed.

Authors:
; ; ;  [1]
  1. Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0340 (United States)
Publication Date:
OSTI Identifier:
20991270
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 126; Journal Issue: 19; Other Information: DOI: 10.1063/1.2731787; (c) 2007 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; CARBON DIOXIDE; DEUTERIUM; DISSOCIATION; ELECTRON DETACHMENT; EV RANGE 01-10; ISOTOPE EFFECTS; ISOTOPIC EXCHANGE; KINETIC ENERGY; MOLECULAR DYNAMICS METHOD; ORGANIC COMPOUNDS; PHOTOLYSIS; POTENTIAL ENERGY; RADICALS; REACTION KINETICS; SURFACES; TUNNEL EFFECT; VIBRATIONAL STATES

Citation Formats

Lu, Zhou, Hu, Qichi, Oakman, Jonathan E., and Continetti, Robert E. Dynamics on the HOCO potential energy surface studied by dissociative photodetachment of HOCO{sup -} and DOCO{sup -}. United States: N. p., 2007. Web. doi:10.1063/1.2731787.
Lu, Zhou, Hu, Qichi, Oakman, Jonathan E., & Continetti, Robert E. Dynamics on the HOCO potential energy surface studied by dissociative photodetachment of HOCO{sup -} and DOCO{sup -}. United States. doi:10.1063/1.2731787.
Lu, Zhou, Hu, Qichi, Oakman, Jonathan E., and Continetti, Robert E. Mon . "Dynamics on the HOCO potential energy surface studied by dissociative photodetachment of HOCO{sup -} and DOCO{sup -}". United States. doi:10.1063/1.2731787.
@article{osti_20991270,
title = {Dynamics on the HOCO potential energy surface studied by dissociative photodetachment of HOCO{sup -} and DOCO{sup -}},
author = {Lu, Zhou and Hu, Qichi and Oakman, Jonathan E. and Continetti, Robert E.},
abstractNote = {An experimental study of the dissociative photodetachment (DPD) dynamics of HOCO{sup -} and DOCO{sup -} at a photon energy of 3.21 eV has been carried out to probe the potential energy surface of the HOCO free radical and the dynamics of the OH+CO{yields}H+CO{sub 2} reaction. These photoelectron-photofragment coincidence experiments allow the identification of photodetachment processes leading to the production of stable HOCO free radicals and both the H+CO{sub 2} and OH+CO dissociation channels on the neutral surface. Isotopic substitution by deuterium in the parent ion is observed to reduce the product branching ratio for the D+CO{sub 2} channel, consistent with tunneling playing a role in this dissociation pathway. Other isotope effects on the detailed partitioning of kinetic energy between photoelectrons and photofragments are also discussed. The results are compared to recent theoretical predictions of this DPD process, and evidence for the involvement of vibrationally excited HOCO{sup -} anions is discussed.},
doi = {10.1063/1.2731787},
journal = {Journal of Chemical Physics},
number = 19,
volume = 126,
place = {United States},
year = {Mon May 21 00:00:00 EDT 2007},
month = {Mon May 21 00:00:00 EDT 2007}
}