The Ozonolysis of Cyclic Monoterpenes: A Computational Review

Monoterpenes are prevalent organic compounds emitted to the atmosphere, via biogenic activities in various types of plants. Monoterpenes undergo atmospheric decomposition reactions derived by the potent atmospheric oxidizing agents, OH, O3, and NOx. This review critically surveys literature pertinent to the atmospheric removal of monoterpenes by ozone. In general, the ozonolysis reactions of monoterpenes occur through the so-called Criegee mechanism. These classes of reactions generate a wide array of chemical organic and inorganic low vapor- pressure (LVP) species. Carbonyl oxides, commonly known as Criegee Intermediates (CI's) are the main intermediates from the gas-phase ozonolysis reaction. Herein, we present mechanistic pathways, reactions rate constants, product profiles, thermodynamic, and kinetic results dictating the ozonolysis reactions of selected monoterpenes (namely; carene, camphene, limonene, ι-pinene, β-pinene, and sabinene). Furthermore, the unimolecular (vinyl hydroperoxide- and ester-channels), and bimolecular reactions (cycloaddition, insertion, and radical recombination) of the resulting CI's are fully discussed. The orientations and conformations of the resulting Primary Ozonides (POZ's) and CI's of monoterpenes are classified to reveal their plausible effects on reported thermo-kinetic parameters.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author