TIME-RESOLVED RESONANCE RAMAN SPECTROSCOPY OF DIHALIDE RADICAL ANIONS.
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Date
1984
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Publisher
Ohio State University
Abstract
Resonance enhanced Raman scattering from dihalide radical anions $(Cl^{-}_{2}, Br^{-}_{2}, I^{-}_{2})$ produced by the pulse radiolysis of aqueous solutions of alkali halides has been investigated by time-resolved Raman technique. Raman excitation was at 359 nm and 370 nm for $Cl^{-}_{2}$ and $Br^{-}_{2}$ (absorption peaks at 340 and 360 nm respectively) and at 380 nm for $I^{-}_{2}$ (absorption peak at 380 nm). The fundamental vibrations and a number of overtones were observed. Anharmonicity in the radical vibrations was observed to be small. Spectral line-widths were found to increase with vibrational quantum number. In the pulse radiolysis of NaCl (0.1 to 1M) mixed with KBr (0.01 to 0.2 M) a weak Raman signal from a transient species, tentatively assigned to $BrCl^{-}$ has also been observed. These radicals are observed to decay at microsecond times by diffusion controlled second order reactions.
Description
Author Institution: Radiation Laboratory and Department of Chemistry, University of Notre Dame