NEAR IR CAVITY RINGDOWN SPECTROSCOPY OF CHLORO-ALKYL PEROXYL RADICALS
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Date
2004
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Publisher
Ohio State University
Abstract
Chloro-alkyl peroxyl radicals are intermediates of alkene oxidation in the marine boundary layer, and serve as models for hydroxy-alkyl peroxyl radicals. Cavity ringdown spectra of the electronic $\tilde{A} - \tilde{X}$ transition of chloro-ethyl, -propyl, -butyl and -butenyl peroxyl radicals will be reported. The spectra observed have more complex structure than the spectra of alkyl peroxyl radicals. DFT calculations predict multiple conformers of the radicals with the energies within 2 kcal/mol. These spectra reveal the subtle substituent effects on the $\tilde{A} - \tilde{X}$ transition of the O-O chromophore. An integrated cross-section for chloro-ethyl peroxyl is estimated from the known rate of self-reaction.
Description
Author Institution: Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology