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

TitleResonance raman investigation of the radical-cation of 1,3,5-hexatriene
Publication TypeJournal Article
Year of Publication1994
AuthorsKeszthelyi, T, Wilbrandt, R, Cave, RJ, Johnson, JL
JournalJournal of Physical Chemistry
Volume98
Pagination5632–5638
Date Publishedjun
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.

URLhttp://dx.doi.org/10.1021/j100073a010
DOI10.1021/j100073a010