Rapid Atmospheric Reactions between Criegee Intermediates and Hypochlorous Acid

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 128; no. 5; pp. 909 - 917
• Main Authors: Zhang, Yu-Qiong, Francisco, Joseph S., Long, Bo
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 08.02.2024
• Subjects: A: Aerosols; Environmental and Atmospheric Chemistry; Astrochemistry
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.3c06144

Hypochlorous acid (HOCl) is a paramount compound in the atmosphere due to its significant contribution to both tropospheric oxidation capacity and ozone depletion. The main removal routes for HOCl are photolysis and the reaction with OH during the daytime, while these processes are unimportant during the nighttime. Here, we report the rapid reactions of Criegee intermediates (CH2OO and anti/syn-CH3CHOO) with HOCl by using high-level quantum chemical methods as the benchmark; their accuracy is close to coupled cluster theory with single, double, and triple excitations and quasiperturbative connected quadruple excitations with a complete basis limit by extrapolation [CCSDT­(Q)/CBS]. Their rate constants have been calculated by using a dual-level strategy; this combines conventional transition state theory calculated at the benchmark level with variational transition state theory with small-curvature tunneling by a validated density functional method. We find that the introduction of the methyl group into Criegee intermediates not only affects their reactivities but also exerts a remarkable influence on anharmonicity. The calculated results uncover that anharmonicity increases the rate constants of CH2OO + HOCl by a factor of 18–5, while it is of minor importance in the anti/syn-CH3CHOO + HOCl reaction at 190–350 K. The present findings reveal that the loose transition state for anti-CH3CHOO and HOCl is a rate-determining step at 190–350 K. We also find that the reaction of Criegee intermediates with HOCl contributes significantly to the sink of HOCl during the nighttime in the atmosphere.