43) Analogous to those in the ' n r * states of ketones, studied via the circular polarization of the fluorescence, see: Schippers, P. H.; Dekkers, H. P. J. M. Chem. Phys. Lett. 1982.88, 512-516. Dekkers, H. P. J. M.; Moraal, P. F. InAbstract: The first Raman spectra of the allyl radical have been obtained. The intensities of the observed Raman spectra indicate excited-state dynamics consistent with a disrotary photoisomerization of the allyl radical to form a cyclopropyl radical. Prior to this work, direct examination of the photoisomerization pathway was not possible due to limitations of the techniques applied. The ground-state vibrational frequencies observed are found to be in excellent agreement with recent theoretical calculations suggesting a reassignment of the literature infrared frequencies. This work demonstrates that resonance Raman spectroscopy is a powerful method for examination of gas-phase free radicals.
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