Reaction Kinetics of Methyl Vinyl Ketone Oxide with Carboxylic Acids: Experimental and Theoretical Insights into Atmospheric Conditions

COOH, respectively, indicating near-collision-limited reactivity. Complementary quantum chemical calculations combined with variational transition state theory identify barrierless reaction pathways for MVKO reactions with carboxylic acids, driven by the formation of strong hydrogen-bonding interactions. The calculated high-pressure-limit rate coefficients are in good agreement with the experimental values, with small deviations attributable to falloff effects. Incorporating the derived kinetics into a chemical transport model indicates that reactions with organic acids provide an efficient sink for MVKO in isoprene-rich regions, leading to a maximum reduction of approximately 3% in the carboxylic acid concentration. These results provide robust kinetic constraints for MVKO-acid reactions and improve the representation of isoprene-derived CI chemistry in atmospheric models.