Collisional-Induced Chemical Reactions between Methane and Criegee Intermediates CH2OO, CH3CHOO, and (CH3)2COO: Theoretical Study

Criegee intermediates, which are the result of ozonolysis of alkenes, play a key role in many chemical and physical processes in the Earth’s atmosphere. Their reactions with various atmospheric compounds are responsible for formation of hydroxyl radicals, atomic oxygen and hydrogen, sulfuric and nitric acids, and other chemically active radicals and molecules. In this work we have considered collisional-induced chemical reactions between three simple Criegee intermediate molecules: CH₂OO, CH₃CHOO, and (CH₃)₂COO with methane, which is a well-known active greenhouse gas. Methane concentration rapidly growths last decades that causes serious concern to the global scientific community. It was established that reactions between methane and Criegee Intermediates can follow through two main routes. One of them occurs over exchange of oxygen and hydrogen atoms upon collision and leads to the formation of methanol. Another one pass through the formation of an intermediate complex with a deep energy minimum, and produces OH radicals and a variety of other products, among which are acetone, acetaldehyde, formaldehyde, propaldehyde, methanol, water molecules, and others. In this work, the both kinds of the reactions have been studied, and the relative reaction rates of both pathways have been compared.