Four Isotope-Labeled Recombination Pathways of Ozone Formation

Authors

Dmitri Babikov, Marquette UniversityFollow
Elizaveta Grushnikova, Marquette University
Igor Gayday, Marquette University
Alexander Teplukhin, Los Alamos National LaboratoryFollow

Document Type

Article

Publication Date

2-2021

Publisher

MDPI

Source Publication

Molecules

Source ISSN

1420-3049

Abstract

A theoretical approach is developed for the description of all possible recombination pathways in the ozone forming reaction, without neglecting any process a priori, and without decoupling the individual pathways one from another. These pathways become physically distinct when a rare isotope of oxygen is introduced, such as ¹⁸O, which represents a sensitive probe of the ozone forming reaction. Each isotopologue of O₃ contains two types of physically distinct entrance channels and two types of physically distinct product wells, creating four recombination pathways. Calculations are done for singly and doubly substituted isotopologues of ozone, eight rate coefficients total. Two pathways for the formation of asymmetric ozone isotopomer exhibit rather different rate coefficients, indicating large isotope effect driven by -difference. Rate coefficient for the formation of symmetric isotopomer of ozone (third pathway) is found to be in between of those two, while the rate of insertion pathway is smaller by two orders of magnitude. These trends are in good agreement with experiments, for both singly and doubly substituted ozone. The total formation rates for asymmetric isotopomers are found to be somewhat larger than those for symmetric isotopomers, but not as much as in the experiment. Overall, the distribution of lifetimes is found to be very similar for the metastable states in symmetric and asymmetric ozone isotopomers.

Comments

Accepted version. Molecules, Vol. 26, No. 5 (February 27, 2021): 1289. DOI. © 2021 by the authors. Licensee MDPI, Basel, Switzerland. Used with permission.

Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

Recommended Citation

Babikov, Dmitri; Grushnikova, Elizaveta; Gayday, Igor; and Teplukhin, Alexander, "Four Isotope-Labeled Recombination Pathways of Ozone Formation" (2021). Chemistry Faculty Research and Publications. 1038.
https://epublications.marquette.edu/chem_fac/1038