Mechanism of OH formation from ozonolysis of isoprene: a quantum-chemical study.

Abstract

The formation and unimolecular reactions of primary ozonides and carbonyl oxides arising from the O(3)-initiated reactions of isoprene have been investigated using density functional theory and ab initio molecular orbital calculations. The activation energies of O(3) cycloaddition to the two double bonds of isoprene are found to be comparable (3.3-3.4 kcal mol(-1)), implying that the initial two O(3) addition pathways are nearly equally accessible. The reaction energies of O(3) addition to isoprene are between -47 and -48 kcal mol(-1). Cleavage of primary ozonides to form carbonyl oxides occurs with a barrier of 11-16 kcal mol(-1) above the ground state of the primary ozonide, and the decomposition energies range from -5 to -13 kcal mol(-1). OH formation is shown to occur primarily via decomposition of the carbonyl oxides with the syn-positioned methyl (alkyl) group, which is more favorable than isomerization to form dioxirane (by 1.1-3.3 kcal mol(-1)). Using the transition-state theory and master equation formalism, we determine an OH yield of 0.25 from prompt and thermal decomposition of the carbonyl oxides.