Physics
Scientific paper
Jun 2011
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2011mss..confetd09s&link_type=abstract
"International Symposium On Molecular Spectroscopy, 66th Meeting, Held 20-24 June, 2011 at Ohio State University. http://molspec
Physics
Electronic
Scientific paper
Alkoxy radicals are atmospherically important species, playing a direct role in the HO_x and NO_x cycles that affect tropospheric air pollution. Alkoxy radicals that can form a six membered transition state can isomerize into a hydroxyalkyl radical. In the presence of O_2, a rapid association reaction occurs, forming a hydroxyalkylperoxy radical. The n-butoxy radical is the smallest alkoxy to undergo isomerization, forming the γ-hydroxybutylperoxy radical (HOC_4H_8OO). Direct detection of HOC_4H_8OO opens the door to measuring alkoxy reaction kinetics with higher precision than previous end product studies. In this talk, we report the first detection of the tilde{A}-tilde{X} electronic spectrum of the HOC_4H_8OO radical. The spectrum is similar in shape to the tilde{A}-tilde{X} spectrum of n-butyl peroxy: a broad spectroscopic band due to the multiple molecular conformers that are present. We also use the tilde{A}-tilde{X} band to measure the alkoxy isomerization kinetics relative to the alkoxy radical's reaction with O_2, similar to the previous kinetics studies.
R. Atkinson, D. L. Baulch, R. A. Cox, J. N. Crowley, R. F. Hampson, R. G. Hynes, M. E. Jenkin, M. J. Rossi, and J. Troe J. Atmos. Chem. and Phys. 2006, 6, 3625.
B. G. Glover and T. A. Miller. J. Phys. Chem. A 2005, 109, 11191.
Okumura Mitchio
Sander Stanley P.
Sprague Matthew K.
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