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Computational Tests of Models for Kinetic Parameters of Unimolecular Reactions of Organophosphorus and Organosulfur Compounds

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Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849-5312, United States
Cite this: J. Phys. Chem. A 2011, 115, 49, 14143–14152
Publication Date (Web):November 3, 2011
https://doi.org/10.1021/jp206344r
Copyright © 2011 American Chemical Society

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    Abstract

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    A computational study of the kinetics of isomerization and elimination reactions of organophosphorus and organosulfur reactions is presented with a view to characterizing the predictive capabilities of widely applied techniques for processes that pertain to the destruction of chemical warfare agents. A set of 22 reactions has been studied, and the results have been compared to experimentally derived data. The BMK functional and the MG3S basis set have been used to compute minimum energy paths. Corrections have been added from CBS-QB3, CASSCF, and CASMP2 calculations. Thermal rate constants at experimental temperatures have been calculated with canonical variational transition state theory and small-curvature tunneling theory. The quality of these results may depend on recrossing of the variational transition state, the amount of radical or diradical character found in the minimum energy paths, or the accuracy of barrier heights.

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    Cartesian coordinates, total energies, and harmonic frequencies for reactants, products, and saddle points. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cited By

    This article is cited by 6 publications.

    1. Emil O. Lidman Olsson, Peter Glarborg, Kim Dam-Johansen, Hao Wu. Review of Phosphorus Chemistry in the Thermal Conversion of Biomass: Progress and Perspectives. Energy & Fuels 2023, 37 (10) , 6907-6998. https://doi.org/10.1021/acs.energyfuels.2c04048
    2. Rebecca S. Thompson, Michelle R. Brann, Ellen H. Purdy, Jacob D. Graham, Alison A. McMillan, S. J. Sibener. Rapid Laser-Induced Temperature Jump Decomposition of the Nerve Agent Simulant Diisopropyl Methylphosphonate under Atmospheric Conditions. The Journal of Physical Chemistry C 2019, 123 (35) , 21564-21570. https://doi.org/10.1021/acs.jpcc.9b05381
    3. Sneha Neupane, Ramees K. Rahman, Artëm E. Masunov, Subith S. Vasu. Theoretical Calculation of Reaction Rates and Combustion Kinetic Modeling Study of Triethyl Phosphate (TEP). The Journal of Physical Chemistry A 2019, 123 (22) , 4764-4775. https://doi.org/10.1021/acs.jpca.9b00636
    4. Sneha Neupane, Frank Barnes, Samuel Barak, Erik Ninnemann, Zachary Loparo, Artëm E. Masunov, Subith S. Vasu. Shock Tube/Laser Absorption and Kinetic Modeling Study of Triethyl Phosphate Combustion. The Journal of Physical Chemistry A 2018, 122 (15) , 3829-3836. https://doi.org/10.1021/acs.jpca.8b00800
    5. J.-C. Lizardo-Huerta, B. Sirjean, L. Verdier, R. Fournet, P.-A. Glaude. The decisive role of pericyclic reactions in the thermal decomposition of organophosphorus compounds. Proceedings of the Combustion Institute 2021, 38 (1) , 719-727. https://doi.org/10.1016/j.proci.2020.08.007
    6. Lucía Aristizabal, Mariana Ángel, Camila Orozco, Pablo Ruiz, Jairo Quijano, Rafael Notario. Computational study of the thermal decomposition and the thermochemistry of allyl ethers and allyl sulfides. Structural Chemistry 2018, 29 (3) , 897-907. https://doi.org/10.1007/s11224-018-1074-8

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