Theoretical Investigation of Atmospheric Oxidation of Biogenic Hydrocarbons: A Critical Review

Publisher Summary This chapter discusses the recent advances in the application of theoretical methods to the atmospheric oxidation of biogenic hydrocarbons. It introduces the backgrounds on the quantum chemical calculations and kinetic rate theories, recent progress on theoretical studies of isoprene and α -, β -pinenes, and studies on other monoterpenes and sesquiterpenes. The mechanism of isoprene oxidation is better understood than those of other biogenic hydrocarbons. The initial isoprene-oxidant adducts, the peroxy radicals, the alkoxy radicals and the first generation products hae been investigated by means of quantum chemical calculations. The roles of the intermediate species were assessed using kinetic methods and the overall picture of the isoprene oxidation mechanism was obtained. Some of the aspects need to be considered for application of quantum chemical calculations and kinetic methods to the atmospheric biogenic hydrocarbons: (1) the accuracy of the geometries of the species, (2) the accuracy of the reaction energy and activation energy, (3) and other thermochemical data. These thermochemical data are very helpful to atmospheric modeling to understand the complex chemical reactions.