RAMAN SPECTRA OF $Cl_{2}O$, ClClO AND THE ClO FREE RADICAL IN ARGON MATRICES
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Date
1973
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Ohio State University
Abstract
Raman spectra of $Cl_{2}O$, ClClO and ClO have been observed in argon matrices at $16^{\circ} K$ using argon plasma excitation. The symmetric, antisymmetric stretching, and bending modes of $Cl_{2}O$ produced signals at 638, 678, and $297 cm^{-1}$, respectively. The ClClO isomeric species and the ClO radical were formed by the in situ laser photolysis of $Cl_{2}O$. ClClO has frequencies at 963 (Cl - O stretch), 374 (Cl - Cl stretch), and $241 cm^{-1}$ (ClClO bend). The Raman spectra of $Cl_{2}O$ and ClClO are in good agreement with their argon matrix infrared counterparts. A Raman band at $850 cm^{-1}$ is attributed to the fundamental frequency of ClO. This assignment, which is in good agreement with hot band spacings in a very recent vacuum ultraviolet spectrum (845 + 4 $cm^{-1}$), suggests a reassignment of the $850 cm^{-1}$ infrared band observed following M + $Cl_{2}O$ matrix reactions to ClO monomer and the $995 cm^{-1}$ band to ClO dimer.
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Author Institution: Chemistry Department, University of Virginia