Resonance Raman investigation of the radical cation of 1,3,5-hexatriene

T. Keszhelyi, R. Wilbrandt, R.J. Cave, J.L. Johnson

    Research output: Contribution to journalJournal articleResearchpeer-review

    Abstract

    The resonance Raman spectrum of the 1,3,5-hexatriene radical cation generated by gamma-irradiation in a Freon glass is reported. The spectrum is excited at 395 nm in resonance with the second absorption band. Identical spectra are obtained from ionized (E)- and (Z)-1,3,5-hexatriene. The presence of more than one rotamer has to be assumed to account for all the observed resonance Raman bands. The bands are assigned to a mixture of the two rotamers, calculated at lowest energy, the ttt and tct rotamers, on the basis of ab initio ROHF/6-31G calculated harmonic frequencies. The spectrum indicates that the ttt and tct rotamers are formed in a ratio in the range 0.4/0.6-0.6/0.4. Two possible mechanisms are proposed to explain the presence of these two rotamers.
    Original languageEnglish
    JournalJournal of Physical Chemistry
    Volume98
    Issue number22
    Pages (from-to)5632-5638
    ISSN0022-3654
    DOIs
    Publication statusPublished - 1994

    Cite this

    Keszhelyi, T., Wilbrandt, R., Cave, R. J., & Johnson, J. L. (1994). Resonance Raman investigation of the radical cation of 1,3,5-hexatriene. Journal of Physical Chemistry, 98(22), 5632-5638. https://doi.org/10.1021/j100073a010