• Libraries
    • Log in to:
    View Item 
    •   MSpace Home
    • University of Manitoba Researchers
    • University of Manitoba Scholarship
    • View Item
    •   MSpace Home
    • University of Manitoba Researchers
    • University of Manitoba Scholarship
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    Dispersion-driven conformational preference in the gas phase: Microwave spectroscopic and theoretical study of allyl isocyanate

    Thumbnail
    View/Open
    Main article (1.045Mb)
    Supporting Information (1.402Mb)
    Date
    2019-11-19
    Author
    SUN, WENHAO
    Sogeke, Paul O.
    Silva, Weslley G. D. P.
    van Wijngaarden, Jennifer
    Metadata
    Show full item record
    Abstract
    The conformations of allyl isocyanate (CH2=CHCH2N=C=O) were explored in the gas phase by combining theoretical calculations and Fourier transform microwave spectroscopy, including the chirped pulse and Balle-Flygare types. Three conformers (I, II and III) were predicted using D3(BJ) dispersion-corrected B3LYP and MP2 methods, however, the lowest energy conformer (conf. I) was absent at the standard B3LYP level. The observed microwave spectra are consistent with the presence of both conf. I and III in the supersonic jet and surprisingly, this is the first report of the global minimum conf. I both experimentally and theoretically. Rotational transitions from the parent species of both conformers as well as their minor isotopologues (13C, 15N and 18O) in natural abundance were assigned allowing experimental geometries to be derived. For conf. I, in addition to the typical splitting pattern due to the 14N quadrupole nucleus, the transitions show a tunnelling splitting which arises from the interconversion motion between its two mirror images. The experimental observation of conf. I and the absence of conf. II in the jet are rationalized using quantum-chemical calculations to explore the importance of electron correlation and in particular, demonstrate the necessity of including dispersion effects in DFT calculations even for seemingly small molecules.
    URI
    http://hdl.handle.net/1993/36076
    DOI
    10.1063/1.5129526
    Collections
    • Faculty of Science Scholarly Works [209]
    • University of Manitoba Scholarship [1981]

    DSpace software copyright © 2002-2016  DuraSpace
    Contact Us | Send Feedback
    Theme by 
    Atmire NV
     

     

    Browse

    All of MSpaceCommunities & CollectionsBy Issue DateAuthorsTitlesSubjectsThis CollectionBy Issue DateAuthorsTitlesSubjects

    My Account

    Login

    Statistics

    View Usage Statistics

    DSpace software copyright © 2002-2016  DuraSpace
    Contact Us | Send Feedback
    Theme by 
    Atmire NV