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Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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Association Kinetics for Perfluorinated n-Alkyl Radicals.

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This study provides crucial theoretical data on the thermal decomposition of perfluoroalkanes (PFAS). The findings offer reliable kinetic models for understanding PFAS degradation in high-temperature environments.

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Area of Science:

  • Chemical Kinetics
  • Environmental Chemistry
  • Computational Chemistry

Background:

  • Radical-radical reactions are key in per- and polyfluoroalkyl substances (PFAS) pyrolysis and oxidation.
  • Unbranched perfluoroalkyl chains' unimolecular dissociation and association reactions significantly impact gas-phase thermal decomposition.
  • Experimental data for these reactions are scarce and uncertain, hindering accurate modeling.

Purpose of the Study:

  • To investigate the chemical kinetics of association/decomposition reactions for C2-C4 unbranched n-perfluoroalkanes.
  • To provide reliable theoretical predictions for these reactions, addressing the lack of experimental data.
  • To generate data suitable for comprehensive chemical kinetic models of PFAS thermal destruction.

Main Methods:

  • Utilized state-of-the-art ab initio transition-state-theory-based master-equation calculations.
  • Employed variable-reaction-coordinate transition-state theory (VRC-TST) for microcanonical and canonical rates.
  • Applied composite quantum chemistry and a connectivity-based hierarchy for thermochemistry; direct dynamics for collision parameters.

Main Results:

  • Calculated microcanonical and canonical rates for association reactions of C2-C4 perfluoroalkanes.
  • Determined temperature- and pressure-dependent rate constants for association and dissociation reactions.
  • Generated data in standardized formats for integration into chemical kinetic models.

Conclusions:

  • The study provides essential theoretical kinetic data for key PFAS decomposition pathways.
  • The generated data can improve the accuracy of models predicting PFAS behavior in thermal processes.
  • This work addresses a critical knowledge gap in PFAS environmental chemistry and remediation.