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Type: Journal article
Title: How does energized NCCCCCN lose carbon in the gas phase? A joint experimental and theoretical study
Author: Wang, T.
Dua, S.
Bowie, J.
Citation: The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 2010; 114(2):949-955
Publisher: Amer Chemical Soc
Issue Date: 2010
ISSN: 1089-5639
Statement of
Tianfang Wang, Suresh Dua and John H. Bowie
Abstract: Neutral NCCCCCN may be prepared in a collision cell of a VG ZAB 2HF mass spectrometer by charge stripping of (NCCCCCN)(*-), formed in the ion source by the process NCCCCH(OEt)(CN) + HO(-) --> H(2)O + NCCCC(-)(OEt)(CN) --> (NCCCCCN)(*-) + EtO(*). A comparison of the neutralization/reionization ((-)NR(+)) and charge reversal ((-)CR(+)) spectra of (NCCCCCN)(*-) indicate that some neutrals NCCCCCN are energized and rearrange to an isomer which decomposes by loss of carbon. An ab initio study at the CCSD(T)/cc-pVTZ//B3LYP/6-311+G(3df) level of theory indicates that (i) triplet NCCCCCN is the ground state with a T/S energy gap of -14.9 kcal mol(-1); (ii) the structures of triplet and singlet NCCCCCN need to be described by molecular obital theory, and a simple valence bond approach cannot be used for this system; and (iii) there are several possible routes by which an energized neutral may lose carbon, but the major route involves the triplet nitrile to isonitrile rearrangement NCCCCCN --> CNCCCCN --> NCCCCN + C.
Rights: Copyright © 2009 American Chemical Society
DOI: 10.1021/jp909911b
Grant ID: ARC
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