TIME RESOLVED RESONANCE RAMAN SPECTROSCOPY OF PHENOXYL RADICALS

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1983

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Ohio State University

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Time resolved resonance enhanced Raman spectra of a number of phenoxyl radicals, produced in the pulse radiolytic oxidation of aqueous solutions of phenols, have been obtained and analysed. These radicals absorb in the spectral region 390--450 nm $(\varepsilon\sim 3-7\times 10^{3}\ { M}^{-1}{ cm}^{-1})$ and exhibit moderate but sufficient resonance enhancement when excited at their absorption peaks to be detected at microsecond times at $\sim 10^{-10}M$ concentration. They are highly reactive and have been observed to decay at diffusioin controlled rates $(k>10^{9}\ M^{-1}s^{-1})$. The observed resonance Raman spectra, their structural implications and decay kinetics will be discussed.

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Author Institution: Radiation Laboratory and Department of Chemistry, University of Notre Dame

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