Cavity Ringdown Spectroscopy and Kinetics of HO_2+HCHO: Detection of the ν_1 and {A}- {X} Bands of HOCH_2OOCAVITY Ringdown Spectroscopy and Kinetics of HO_2+HCHO: Detection of the ν_1 and {A}- {X} Bands of HOCH_2OO

Details Cavity Ringdown Spectroscopy and Kinetics of HO_2+HCHO: Detection of the ν_1 and {A}- {X} Bands of HOCH_2OOCAVITY Ringdown Spectroscopy and Kinetics of HO_2+HCHO: Detection of the ν_1 and {A}- {X} Bands of HOCH_2OO Cavity Ringdown Spectroscopy and Kinetics of HO_2+HCHO: Detection of the ν_1 and {A}- {X} Bands of HOCH_2OOCAVITY Ringdown Spectroscopy and Kinetics of HO_2+HCHO: Detection of the ν_1 and {A}- {X} Bands of HOCH_2OO

Jun 2011

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2011mss..confetd08s&link_type=abstract

"International Symposium On Molecular Spectroscopy, 66th Meeting, Held 20-24 June, 2011 at Ohio State University. http://molspec

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The reactions of HO_2 with carbonyl compounds are believed to be a sink for carbonyl compounds in the upper troposphere and lower stratosphere. These reactions proceed through a hydrogen bound intermediate before isomerizing. The reaction of HO_2 + formaldehyde (HCHO) serves as a prototype for this class of reactions, forming the isomerization product hydroxymethylperoxy (HOCH_2OO, HMP). Previous studies measured the spectrum and kinetics of HMP using either FTIR detection of the end products or direct detection of HMP by the unstructured tilde{B}-tilde{X} transition. Despite these studies, considerable uncertainty exists in the rate constant of HMP formation (±80%, 2σ). In this talk, we report the first detection of the ν_1 (OH stretch) and tilde{A}-tilde{X} electronic spectra of the HMP radical. The OH stretch spectrum is broad and featureless, while the tilde{A}(0)-tilde{X}(0) origin and combination band with the OOCO torsion tilde{A}(NOOCO=1)-tilde{X}(0) are rotationally resolved. Quantum chemistry calculations have been performed on both the tilde{A} and tilde{X} states as a function of the OOCO and HOCO dihedral angles to estimate the tilde{A}-tilde{X} transition frequency and to assess the coupling between the two torsional modes. We also present kinetics data showing the rates of production and destruction of HMP.
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