Browsing by Subject "Peroxy radical recombination"

The oxidation mechanisms of atmospheric organic compounds are an important puzzle piece for many atmospherically relevant topics, including but not limited to air quality and climate change. One poorly understood step in this oxidation process is peroxy radical recombination, in some conditions the most important sink reaction for peroxy radicals, which are formed in abundance due to gas phase reactions in the lower troposphere. After a few initial steps, the peroxy radical recombination reaction results in the ejection of O_2 leaving behind a pair of alkoxy radicals in close proximity. This reactive complex has three known reaction pathways: Hydrogen shift forming an alcohol and a carbonyl compound, radical recombination forming a ROOR dimer, and diffusive break-up forming two free alkoxy radicals. In this thesis, alkoxy bond scission followed by radical recombination resulting in the formation of a ROR is proposed as a fourth reaction pathway. To test the hypothesis, computational chemistry was used to determine alkoxy bond scission rates for radicals of atmospheric significance, and gas-phase oxidation experiments were realized on three peroxy radical precursor molecules to look for signs of ROR formation. More precisely, the Eyring equation was used to calculate the rate of alkoxy bond scission on a potential energy surface determined using density functionals, with corrections to electronic energy using coupled-cluster calculations. In the experiments, liquid phase alkenes were vaporized, and oxidized by O_3 in the gas phase, resulting in peroxy radical formation, after which the possible dimers were detected using a NO_3^- -atmospheric pressure chemical ionization time-of-flight mass spectrometer. A highly oxidized radical reaction partner was present in the chamber to improve the detectability of the formed dimers. The combined results of these two approaches suggest that the reaction pathway is possible in standard atmospheric conditions and may thus be important for a number of peroxy radicals.