The laser-induced fluorescence spectra of jet-cooled alkoxy radicals were recorded. Spectra were observed for both isomers of propoxy and all three isomers of butoxy. In nearly all cases, the vibrational structure of the spectra are dominated by a C-O stretch progression, which, however, terminates much more abruptly for the primary isomers than for the more branched ones. For each of the radicals (except t-butoxy), a number of low-frequency (below the C-O stretch) vibrational modes were assigned by analogies among the alkoxy spectra and reference to frequencies from ab initio calculations. A few higher frequency modes were also assigned using similar approaches.
Laser induced fluorescence spectra of nearly 20 jet-cooled alkoxy free radicals, with up to 12 carbon atoms, have been observed. Trends, as a function of the number of carbon atoms, are reported for origin frequencies, and their dependence upon structural isomers are documented. The interpretation of various bands in the spectra, and their rotational contours, in terms of excited-state vibrations and/or different conformations is discussed.
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