How Does Energized NCCCCCN Lose Carbon in the Gas Phase? A Joint Experimental and Theoretical Study

Tianfang Wang; S Dua; J H Bowie

doi:10.1021/jp909911b

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How Does Energized NCCCCCN Lose Carbon in the Gas Phase? A Joint Experimental and Theoretical Study

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How Does Energized NCCCCCN Lose Carbon in the Gas Phase? A Joint Experimental and Theoretical Study

Tianfang Wang, S Dua and J H Bowie

Journal of Physical Chemistry Part A, Vol.114(2), pp.949-955

2010

DOI: https://doi.org/10.1021/jp909911b

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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- â†’ H2O + NCCCC-(OEt)(CN) â†’ (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 â†’ CNCCCCN â†’ NCCCCN + C.

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Title: How Does Energized NCCCCCN Lose Carbon in the Gas Phase? A Joint Experimental and Theoretical Study
Authors: Tianfang Wang (Author) - University of Adelaide
S Dua (Author) - University of Adelaide
J H Bowie (Author) - University of Adelaide
Publication details: Journal of Physical Chemistry Part A, Vol.114(2), pp.949-955
Publisher: American Chemical Society
Date published: 2010
DOI: 10.1021/jp909911b
ISSN: 1089-5639
Organisation Unit: School of Science and Engineering - Legacy; University of the Sunshine Coast, Queensland; School of Science, Technology and Engineering; Centre for Bioinnovation
Language: English
Record Identifier: 99450255002621
Output Type: Journal article

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