Mechanistic Insight into the Reactivities of Aqueous-Phase Singlet Oxygen with Organic Compounds.

Singlet oxygen (O) is a selective reactive oxygen species that plays a key role for the fate of various organic compounds in the aquatic environment under sunlight irradiation, engineered water oxidation systems, atmospheric water droplets, and biomedical systems. While the initial rate-determining charge-transfer reaction mechanisms and kinetics of O have been studied extensively, no comprehensive studies have been performed to elucidate the reaction mechanisms with organic compounds that have various functional groups. In this study, we use density functional theory calculations to determine elementary reaction mechanisms with a wide variety of organic compounds. The theoretically calculated aqueous-phase free energies of activation of single electron transfer and O addition reactions are compared to the experimentally determined rate constants in the literature to determine linear free-energy relationships. The theoretically calculated free energies of activation for the groups of phenolates and phenols show excellent correlations with the Hammett constants that accept electron densities by through-resonance. The dominant elementary reaction mechanism is discussed for each group of compounds. As a practical implication, we demonstrate the fate of environmentally relevant organic compounds induced by photochemically produced intermediate species at different pH and evaluate the impact of predicting rate constants to the half-life.