Title: Kinetic isotope effects for dissociative recombination of tritiated ketenyl ion (3HCCO+): A surface-hopping ab initio molecular dynamics study

Journal Article · · Computational and Theoretical Chemistry
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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Dissociative recombination (DR) reactions are important when modeling charged species in the presence of free electrons. While experimental measurements of DR reaction rates are challenging, surface hopping ab initio molecular dynamics (SH-AIMD) simulations provide an attractive alternative. SH-AIMD is especially well-suited for estimating branching ratios, i.e., the relative rates of competing production channels, for DR reactions. Although the radiolysis of diatomic tritium has been studied experimentally, previous attempts to model these systems have failed to account for isotope effects in DR reactions. Previous SH-AIMD studies have also not investigated tritium isotope effects for the branching ratios of DR reactions. In this study, we compute the DR branching ratios of the protiated and tritiated ketenyl ion. Comparison with literature values for the protiated branching ratios provides confidence in the reliability of our SH-AIMD results. Our simulations predict a significant increase of the HC + CO branching ratio for the tritiated system.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
89233218CNA000001
OSTI ID:
1846917
Report Number(s):
LA-UR-21-29572
Journal Information:
Computational and Theoretical Chemistry, Journal Name: Computational and Theoretical Chemistry Vol. 1210; ISSN 2210-271X
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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