Reactivity of the anti-Criegee intermediate of β-pinene with prevalent atmospheric species

• Published in: Structural chemistry Vol. 30; no. 4; pp. 1353 - 1364
• Main Authors: Elayan, Ismael A., Almatarneh, Mansour H., Hollett, Joshua W.
• Format: Journal Article
• Language: English
• Published: New York Springer US 15.08.2019; Springer Nature B.V
• Subjects: Activation energy; Ammonia; Chemistry; Chemistry and Materials Science; Computer Applications in Chemistry; Mathematical analysis; Organic chemistry; Original Research; Oxidation; Oxidizing agents; Physical Chemistry; Quantum chemistry; Sulfur trioxide; Theoretical and Computational Chemistry; Ozonolysis; Oxidation; Bimolecular reactions; Criegee; Secondary Ozonide
• ISSN: 1040-0400; 1572-9001
• DOI: 10.1007/s11224-019-1288-4

The reaction of the anti -Criegee intermediate ( anti -CI) of β-pinene with prevalent atmospheric species has been investigated using quantum-chemical calculations. The calculations predict that the ozone addition to CI occurs with a Gibbs energy of activation (Δ G ‡ ) of 77 kJ mol −1 . The CI reaction with CH 4 , C 2 H 6 , NH 3 , and chlorinated ethanes is not energetically favored and has high barriers in the range of 253 to 362 kJ mol −1 . The more probable reaction with SO 2 forms a secondary ozonide (SOZ) intermediate with a barrier of 9 kJ mol −1 , while the Δ G ‡ to dissociation is 101 kJ mol −1 . Among the reactions studied, the one with N ̇ O had the lowest Δ G ‡ for its rate-determining step. The Δ G ‡ values of the first step addition of O 3 , NH 3 , SO 2 , and N ̇ O do not exceed 84 kJ mol −1 . In contrast to previous predictions, the N ̇ O reaction with the CI did not proceed through cyclic adduct formation. The findings agree with previous studies which found that CIs act as oxidizing agents, converting SO 2 to SO 3 , and N ̇ O to N ̇ O 2 . Thus, the CIs of biogenic compounds should be added to the list of atmospheric oxidizing agents along with O 3 , NO 3 , and OH radicals.