Title: Four Isotope-Labeled Recombination Pathways of Ozone Formation

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 ΔZPE-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. Altogether, the distribution of lifetimes ismore » found to be very similar for the metastable states in symmetric and asymmetric ozone isotopomers.« less

Authors:

Babikov, Dmitri  ^[1];

• Search DOE PAGES for author "Babikov, Dmitri"
• Search DOE PAGES for ORCID "0000-0002-4667-7645"

Grushnikova, Elizaveta ^[1]; Gayday, Igor  ^[1];

• Search DOE PAGES for author "Gayday, Igor"
• Search DOE PAGES for ORCID "0000-0002-3950-3356"

Teplukhin, Alexander ^[2]

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+ Show Author Affiliations

1. Marquette Univ., Milwaukee, WI (United States)
2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Publication Date:

Sat Feb 27 00:00:00 EST 2021

Research Org.:

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Org.:

USDOE National Nuclear Security Administration (NNSA); National Science Found (NSF)

OSTI Identifier:

1807875

Report Number(s):

LA-UR-21-20550
Journal ID: ISSN 1420-3049

Grant/Contract Number:  

89233218CNA000001; AGS-1920523; ACI-1547580

Resource Type:

Accepted Manuscript

Journal Name:

Molecules

Additional Journal Information:

Journal Volume: 26; Journal Issue: 5; Journal ID: ISSN 1420-3049

Publisher:

MDPI

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and physical chemistry; ozone; spectra; isotope effect; scattering resonances; hyperspherical coordinates