Resonance Raman and quantum chemical studies of short polyene radical cations

TitleResonance Raman and quantum chemical studies of short polyene radical cations
Publication TypeJournal Article
Year of Publication1997
AuthorsKeszthelyi, T, Wilbrandt, R, Bailey, CA
JournalJournal of Molecular Structure
Volume410
Pagination339–342
Date Publishedjun
Abstract

The results of our investigations of the geometric and vibrational structures of some short conjugated polyene radical cations are reported. The radical cations of 1,3-butadiene and three of its deuterated isotopomers, trans- and cis-1,3-pentadiene, 2-methyl-1,3-butadiene, and E- and Z-1,3,5-hexatriene have been studied. The radical cations were generated radiolytically in a glassy Freon matrix and investigated by optical absorption and resonance Raman spectroscopy. Ab initio and density functional molecular-orbital calculations have been carried out to predict equilibrium structures and to assist assignment of the resonance Raman spectra. A new and improved scaled quantum mechanical force field for the butadiene radical cation was also determined. The presence of more than one rotamer was observed in all the polyene radical cations we investigated. (C) 1997 Elsevier Science B.V.

URLhttp://www.sciencedirect.com/science/article/pii/S0022286096096329
DOI10.1016/s0022-2860(96)09632-9