A Reactive Molecular Dynamics Study of Chlorinated Organic Compounds. Part II: A ChemTraYzer Study of Chlorinated Dibenzofuran Formation and Decomposition Processes

In our two‐paper series, we first present the development of ReaxFF CHOCl parameters using the recently published ParAMS parametrization tool. In this second part, we update the reactive Molecular Dynamics – Quantum Mechanics coupling scheme ChemTraYzer and combine it with our new ReaxFF parameters...

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Bibliographic Details
Published in:Chemphyschem 2023-04, Vol.24 (7), p.e202200783-n/a
Main Authors: Krep, Lukas, Schmalz, Felix, Solbach, Florian, Komissarov, Leonid, Nevolianis, Thomas, Kopp, Wassja A., Verstraelen, Toon, Leonhard, Kai
Format: Article
Language:English
Subjects:
ChemTraYzer
Chlorinated organic compounds
Chlorination
Coupling (molecular)
Decomposition
Dibenzofurans
Molecular dynamics
Organic compounds
Oxidation
Parameterization
Parameters
ParAMS
Pyrolysis
Quantum mechanics
Reactive force fields
Self-learning transition-state search
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Summary:In our two‐paper series, we first present the development of ReaxFF CHOCl parameters using the recently published ParAMS parametrization tool. In this second part, we update the reactive Molecular Dynamics – Quantum Mechanics coupling scheme ChemTraYzer and combine it with our new ReaxFF parameters from Part I to study formation and decomposition processes of chlorinated dibenzofurans. We introduce a self‐learning method for recovering failed transition‐state searches that improves the overall ChemTraYzer transition‐state search success rate by 10 percentage points to a total of 48 %. With ChemTraYzer, we automatically find and quantify more than 500 reactions using transition state theory and DFT. Among the discovered chlorinated dibenzofuran reactions are numerous reactions that are new to the literature. In three case studies, we discuss the set of reactions that are most relevant to the dibenzofuran literature: (i) bimolecular reactions of the chlorinated‐dibenzofuran precursors phenoxy radical and 1,3,5‐trichlorobenzene, (ii) dibenzofuran chlorination and pyrolysis, and (iii) oxidation of chlorinated dibenzofurans. The MD‐QM coupling scheme ChemTraYzer is updated to achieve higher computational efficiency and higher TS search success rates. A self‐learning TS search is introduced. ChemTrayzer is applied to dibenzofurane chemistry. ChemTraYzer automatically discovers and quantifies hundreds of dibenzofurane reactions.
ISSN:1439-4235
1439-7641
DOI:10.1002/cphc.202200783