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HNNC Radical and Its Role in the CH + N2 Reaction
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    HNNC Radical and Its Role in the CH + N2 Reaction
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    Air Force Office of Scientific Research, 875 North Randolph Street, Arlington, Virginia 22203
    Quantum Theory Project, Department of Chemistry and Physics, University of Florida, Gainesville, Florida 32611
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2007, 111, 29, 6894–6899
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    https://doi.org/10.1021/jp0723618
    Published July 3, 2007
    Copyright © 2007 American Chemical Society

    Abstract

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    A previously unreported channel in the spin-allowed reaction path for the CH + N2 reaction that involves the HNNC radical is presented. The structures and energetics of the HNNC radical and its isomers HCNN and HNCN and the relevant intermediates and transition states that are involved in the proposed mechanism are obtained at the coupled cluster singles and doubles level of theory with noniterative triples correction (CCSD(T)) using a converging series of basis sets aug-cc-pVDZ, aug-cc-pVTZ, and aug-cc-pVQZ. The aug-cc-pVQZ basis is used for all the final single point energy calculations using the CCSD(T)/aug-cc-pVTZ optimized geometries. We find the HNNC radical to have a heat of formation of ΔfH0 (HNNC) = 116.5 kcal mol-1. An assessment of the quality of computed data of the radical species HNCN and HCNN is presented by comparison with the available experimental data. We find that HNNC can convert to HNCN, the highest barrier in this path being 14.5 kcal mol-1 above the energy of the CH + N2 reactants. Thus, HNNC can play a role in the high-temperature spin-allowed mechanism for the reaction of CH + N2 proposed by Moskaleva, Xia, and Lin (Chem. Phys. Lett. 2000, 331, 269).

    Copyright © 2007 American Chemical Society

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     Part of the special issue “M. C. Lin Festschrift”.

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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2007, 111, 29, 6894–6899
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp0723618
    Published July 3, 2007
    Copyright © 2007 American Chemical Society

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