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Title: Dynamics study of the reaction OH{sup -}+C{sub 2}H{sub 2}{yields}C{sub 2}H{sup -}+H{sub 2}O with crossed beams and density-functional theory calculations

Abstract

The proton transfer reaction between OH{sup -} and C{sub 2}H{sub 2}, the sole reactive process observed over the collision energy range from 0.37 to 1.40 eV, has been studied using the crossed beam technique and density-functional theory (DFT) calculations. The center of mass flux distributions of the product C{sub 2}H{sup -} ions at three different energies are highly asymmetric, characteristic of a direct process occurring on a time scale much less than a rotational period of any transient intermediate. The maxima in the flux distributions correspond to product velocities and directions close to those of the precursor acetylene reactants. The reaction quantitatively transforms the entire exothermicity into internal excitation of the products, consistent with an energy release motif in which the proton is transferred early, in a configuration in which the forming bond is extended. This picture is supported by DFT calculations showing that the first electrostatically bound intermediate on the reaction pathway is the productlike C{sub 2}H{sup -}{center_dot}H{sub 2}O species. Most of the incremental translational energy in the two higher collision energy experiments appears in product translational energy, and provides an example of induced repulsive energy release characteristic of the heavy+light-heavy mass combination.

Authors:
; ;  [1]
  1. Department of Chemistry, University of Rochester, Rochester, New York 14627 (United States)
Publication Date:
OSTI Identifier:
20783251
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 124; Journal Issue: 12; Other Information: DOI: 10.1063/1.2179799; (c) 2006 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; ACETYLENE; CHEMICAL BONDS; COLLIDING BEAMS; DENSITY FUNCTIONAL METHOD; EV RANGE 01-10; EXCITATION; HYDROXIDES; MOLECULE COLLISIONS; REACTION KINETICS; TRANSFER REACTIONS; WATER

Citation Formats

Liu Li, Li Yue, and Farrar, James M. Dynamics study of the reaction OH{sup -}+C{sub 2}H{sub 2}{yields}C{sub 2}H{sup -}+H{sub 2}O with crossed beams and density-functional theory calculations. United States: N. p., 2006. Web. doi:10.1063/1.2179799.
Liu Li, Li Yue, & Farrar, James M. Dynamics study of the reaction OH{sup -}+C{sub 2}H{sub 2}{yields}C{sub 2}H{sup -}+H{sub 2}O with crossed beams and density-functional theory calculations. United States. doi:10.1063/1.2179799.
Liu Li, Li Yue, and Farrar, James M. Tue . "Dynamics study of the reaction OH{sup -}+C{sub 2}H{sub 2}{yields}C{sub 2}H{sup -}+H{sub 2}O with crossed beams and density-functional theory calculations". United States. doi:10.1063/1.2179799.
@article{osti_20783251,
title = {Dynamics study of the reaction OH{sup -}+C{sub 2}H{sub 2}{yields}C{sub 2}H{sup -}+H{sub 2}O with crossed beams and density-functional theory calculations},
author = {Liu Li and Li Yue and Farrar, James M.},
abstractNote = {The proton transfer reaction between OH{sup -} and C{sub 2}H{sub 2}, the sole reactive process observed over the collision energy range from 0.37 to 1.40 eV, has been studied using the crossed beam technique and density-functional theory (DFT) calculations. The center of mass flux distributions of the product C{sub 2}H{sup -} ions at three different energies are highly asymmetric, characteristic of a direct process occurring on a time scale much less than a rotational period of any transient intermediate. The maxima in the flux distributions correspond to product velocities and directions close to those of the precursor acetylene reactants. The reaction quantitatively transforms the entire exothermicity into internal excitation of the products, consistent with an energy release motif in which the proton is transferred early, in a configuration in which the forming bond is extended. This picture is supported by DFT calculations showing that the first electrostatically bound intermediate on the reaction pathway is the productlike C{sub 2}H{sup -}{center_dot}H{sub 2}O species. Most of the incremental translational energy in the two higher collision energy experiments appears in product translational energy, and provides an example of induced repulsive energy release characteristic of the heavy+light-heavy mass combination.},
doi = {10.1063/1.2179799},
journal = {Journal of Chemical Physics},
number = 12,
volume = 124,
place = {United States},
year = {Tue Mar 28 00:00:00 EST 2006},
month = {Tue Mar 28 00:00:00 EST 2006}
}