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dc.creatorSprague, Matthew K.en_US
dc.creatorOkumura, Mitchioen_US
dc.creatorSander, Stanley P.en_US
dc.creatorSprague, Matthew K.en_US
dc.creatorOkumura, Mitchioen_US
dc.creatorSander, Stanley P.en_US
dc.date.accessioned2011-07-12T17:31:34Z
dc.date.available2011-07-12T17:31:34Z
dc.date.issued2011en_US
dc.identifier2011-TD-09en_US
dc.identifier.urihttp://hdl.handle.net/1811/49452
dc.descriptionAuthor Institution: California Institute of Technology, Division of Chemistry, MC 127-72, Pasadena, CA 91125; Jet Propulsion Laboratory, California Institute of Technology, MS 183-901, Pasadena, CA 91109; California Institute of Technology, Division of Chemistry, MC 127-72, Pasadena, CA 91125; NASA Jet Propulsion Laboratory, MS 183-901, Pasadena, CA 91109en_US
dc.description.abstractAlkoxy 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 \textit{n}-butoxy radical is the smallest alkoxy to undergo isomerization, forming the $\gamma$-hydroxybutylperoxy radical (HOC$_4$H$_8$OO). Direct detection of HOC$_4$H$_8$OO opens the door to measuring alkoxy reaction kinetics with higher precision than previous end product studies. \textbf{2006}, \textit{6}, 3625.} In this talk, we report the first detection of the \~{A}-\~{X} electronic spectrum of the HOC$_4$H$_8$OO radical. The spectrum is similar in shape to the \~{A}-\~{X} spectrum of \textit{n}-butyl peroxy: \textbf{2005}, \textit{109}, 11191.} a broad spectroscopic band due to the multiple molecular conformers that are present. We also use the \~{A}-\~{X} band to measure the alkoxy isomerization kinetics relative to the alkoxy radical's reaction with O$_2$, similar to the previous kinetics studies. Alkoxy radicals are atmospherically important species, playing a direct role in the HO$_x$ and NO$_x$ cycles that affect troposperic 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 \textit{n}-butoxy radical is the smallest alkoxy to undergo isomerization, forming the $\gamma$-hydroxybutylperoxy radical (HOC$_4$H$_8$OO). Direct detection of HOC$_4$H$_8$OO opens the door to measuring alkoxy reaction kinetics with higher precision than previous end product studies. \textbf{2006}, \textit{6}, 3625.} In this talk, we report the first detection of the \~{A}-\~{X} electronic spectrum of the HOC$_4$H$_8$OO radical. The spectrum is similar in shape to the \~{A}-\~{X} spectrum of \textit{n}-butyl peroxy: \textbf{2005}, \textit{109}, 11191.} a broad spectroscopic band due to the multiple molecular conformers that are present. We also use the \~{A}-\~{X} band to measure the alkoxy isomerization kinetics relative to the alkoxy radical's reaction with O$_2$, similar to the previous kinetics studies.en_US
dc.language.isoenen_US
dc.publisherOhio State Universityen_US
dc.titleCAVITY RINGDOWN SPECTROSCOPY AND KINETICS OF BUTOXY ISOMERIZATION: DETECTION OF THE \ {A}-\ {XCAVITY RINGDOWN SPECTROSCOPY AND KINETICS OF BUTOXY ISOMERIZATION: DETECTION OF THE \ {A}-\ {Xen_US
dc.typeArticleen_US
dc.typeImageen_US
dc.typePresentationen_US


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