Oxidation of Isoprene to Methyl vinyl ketone and Methacrolein via Hydroxyl Radical : A Regenerative Mechanism for the Hydroxyl Radical

Abstract

Isoprene is an important molecule in atmospheric chemistry. Belonging to a class of molecules known as volatile organic compounds, it undergoes reactions with several different oxidizers in the atmosphere, including OH(hydroxyl radical). In 2005 the concentrations of isoprene, OH and a few other isoprene derivatives were measured above the Amazonian rain forest. OH was found to be in concentrations far above levels predicted by computer models. As a result, a mechanism involving a 1,5-H shift was proposed to help explain the high levels of OH. Four reaction pathways, two different conformations of two different oxidation products, for the oxidation of isoprene and regeneration of the hydroxyl radical involving a 1,5-H shift mechanism were studied using the M062X density functional and the maug-cc-PVTZ basis set.