The kinetics of the reaction of with has been studied from 120 to 1400 K using both a selected ion flow tube and high-temperature flowing afterglow. The rate constant decreases from 120 K to ∼1200 K and then increases slightly up to the maximum temperature studied, 1400 K. The rate constant compares well to most of the previous measurements in the overlapping temperature range. Comparing the results to drift tube data shows that there is not a large difference between increasing the translational energy available for reaction and increasing the internal energy of the reactants over much of the range, i.e., all types of energies drive the reactivity equally. The reaction produces both and the latter of which is shown to be the higher energy linear isomer. The ratio of to decreases from a value of over 2 at 120 K to less than 0.01 at 1400 K because of dissociation of at the higher temperatures. This ratio decreases exponentially with increasing temperature. High-level theoretical calculations have also been performed to compliment the data. Calculations using multi-reference configuration interaction theory at the MRCISD(Q)/cc-pVTZ level of theory show that singlet is linear and is 4.5 eV higher in energy than A barrier of 0.9 eV prevents dissociation into and however, a crossing to a triplet surface connects to and products. A singlet and a triplet potential energy surface leading to products have been determined using coupled cluster theory at the CCSD(T)/aug-cc-pVQZ level on structures optimized at the Becke3-Lee, Yang, and Parr (B3LYP)/aug-cc-pVTZ level of theory. The experimental results and reaction mechanism are evaluated using these surfaces.
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15 November 2004
Research Article|
November 15 2004
Ion-molecule rate constants and branching ratios for the reaction of from 120 to 1400 K
Svetozar Popovic;
Svetozar Popovic
Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Massachusetts 01731-3010
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Anthony J. Midey;
Anthony J. Midey
Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Massachusetts 01731-3010
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Skip Williams;
Skip Williams
Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Massachusetts 01731-3010
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Abel I. Fernandez;
Abel I. Fernandez
Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Massachusetts 01731-3010
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A. A. Viggiano;
A. A. Viggiano
Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Massachusetts 01731-3010
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Peng Zhang;
Peng Zhang
Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322
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K. Morokuma
K. Morokuma
Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322
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J. Chem. Phys. 121, 9481–9488 (2004)
Article history
Received:
July 07 2004
Accepted:
August 25 2004
Citation
Svetozar Popovic, Anthony J. Midey, Skip Williams, Abel I. Fernandez, A. A. Viggiano, Peng Zhang, K. Morokuma; Ion-molecule rate constants and branching ratios for the reaction of from 120 to 1400 K. J. Chem. Phys. 15 November 2004; 121 (19): 9481–9488. https://doi.org/10.1063/1.1807376
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