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The reactions of 3-pentoxy radicals with O 2  and their unimolecular decomposition were investigated using time-resolved and simultaneous detection of NO 2  and OH in the laser flash initiated oxidation of bromopentane combined with numerical simulation of the experimentally obtained concentration-time profiles. NO 2  was monitored by cw-LIF, whereas OH was detected by laser long-path absorption at 308 nm. 3-pentoxy radicals were produced selectively by the excimer-laser photolysis of 3-bromopentane at 248 nm and subsequent reaction of the 3-pentyl radicals with O 2  in the presence of NO. All experiments were performed at a temperature of 293±3 K and 50 mbar total pressure. The following rate coefficients for reaction with oxygen (kO 2 ) and for thermal decomposition (k decomp ) of 3-pentoxy radicals were obtained: k O2  = (7.2±3.5)× 10 -15  cm 3  molecule -1  s-1  and k decomp  = (5.0±2.5)× 10 3  s -1 .

A Combined Experimental and Theoretical Investigation of the Reactions of 3-Pentoxy Radicals: Reaction with O 2 and Unimolecular Decomposition