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

  • Ismael A. ElayanEmail author
  • Mansour H. AlmatarnehEmail author
  • Joshua W. HollettEmail author
Original Research
  • 29 Downloads

Abstract

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 (ΔG) of 77 kJ mol−1. The CI reaction with CH4, C2H6, NH3, 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 SO2 forms a secondary ozonide (SOZ) intermediate with a barrier of 9 kJ mol−1, while the ΔG to dissociation is 101 kJ mol−1. Among the reactions studied, the one with \( \dot{\mathrm{N}} \)O had the lowest ΔG for its rate-determining step. The ΔG values of the first step addition of O3, NH3, SO2, and \( \dot{\mathrm{N}} \)O do not exceed 84 kJ mol−1. In contrast to previous predictions, the \( \dot{\mathrm{N}} \)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 SO2 to SO3, and \( \dot{\mathrm{N}} \)O to \( \dot{\mathrm{N}} \)O2. Thus, the CIs of biogenic compounds should be added to the list of atmospheric oxidizing agents along with O3, NO3, and OH radicals.

Keywords

Criegee Secondary Ozonide Ozonolysis Oxidation Bimolecular reactions 

Notes

Acknowledgments

We gratefully acknowledge the University of Manitoba for the compute time.

Funding information

M. H. Almatarneh thanks the Deanship of Academic Research at The University of Jordan for a research grant. J. W. Hollett thanks the Natural Sciences and Engineering Research Council of Canada (NSERC) for a Discovery Grant.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11224_2019_1288_MOESM1_ESM.docx (13.9 mb)
ESM 1 The potential energy surface (PES), full-optimized geometries, IRC analyses, electronic energies, cartesian coordinates, and vibrational frequencies. This material is available free of charge via the Internet. (DOCX 14221 kb)

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Authors and Affiliations

  1. 1.Department of ChemistryUniversity of ManitobaWinnipegCanada
  2. 2.Department of ChemistryUniversity of JordanAmmanJordan
  3. 3.Chemistry DepartmentMemorial University of NewfoundlandSt. John’sCanada
  4. 4.Department of ChemistryUniversity of WinnipegWinnipegCanada

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