ChemInform Abstract: A Flash Photolysis Investigation of the Gas Phase UV Absorption Spectrum and Self-Reaction Kinetics of the Neopentylperoxy Radical

Abstract

The ultraviolet absorption spectrum of the neopentylperoxy radical, (CH 3 ) 3 CCH 2 O 2 (or C 5 H 11 O 2 ), and the kinetics of its self-reaction have been studied in the gas phase using a flash photolysis technique. The room temperature absorption cross-section at 250 nm was determined to be σC 5 H 11 O 2 (250 nm)=(5.18±0.78)×10 −18 cm 2 molecule −1 and was used to normalize the radical absorption spectrum between 210 and 300 nm. Detailed modeling of the self-reaction system was used to interpret the transient absorption kinetic decay curves over the temperature range 228-380 K, at total pressures between 25 and 100 torr. The results are discussed in relation to previous measurements of alkylperoxy radical spectra and kinetics