Unimolecular Dissociations and Free Radical Recombination Reactions
The Journal of Chemical Physics · 1952 · 924 citations · 3 references
EngineeringMolecular BiologyExcitation Energy TransferOrganic RadicalsComputational ChemistryChemistryElectronic Excited StateMethyl RadicalsReaction IntermediateMolecular KineticsBiophysicsIodine AtomsPhysicsRadical (Chemistry)Physical ChemistryQuantum ChemistryUnimolecular DissociationsExcited State PropertyNatural SciencesActivated ComplexChemical Kinetics
Steric and pressure effects in free‑radical recombination depend on the activated complex and are closely linked. This paper extends a prior theory on methyl radical–iodine atom recombination. The authors derive equations for these effects from unimolecular dissociation, extending earlier transition‑state and quasi‑unimolecular theories and introducing a new density‑of‑states expression for high‑energy molecules. Applications indicate that all vibrational modes can transfer energy to excited molecules, highlighting vibrational anharmonicity as a key factor in intramolecular energy transfer.
The steric and pressure effects associated with the recombination of free radicals both depend on the nature of the activated complex, and are therefore intimately related. From a consideration of the reverse process of unimolecular dissociation, some equations are derived for these properties using an extension of earlier transition state and quasi-unimolecular theories. The present formalism differs from previous formulations of the latter in a number of ways, particularly in the expression used for the density of quantum states of the high energy molecules. Subsequent applications of the theory tentatively suggest that essentially all vibrational degrees of freedom of these molecules can contribute their energy to the vibrationally excited molecules. Consequently, vibrational anharmonicity would appear to be an important factor in intramolecular energy transfer. The present paper is an extension of a previously developed theory for the recombination of methyl radicals and iodine atoms.
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The Activated Complex in Chemical Reactions
Henry Eyring · The Journal of Chemical Physics · 1935
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The Kinetics of the Recombination of Methyl Radicals and Iodine Atoms.
R. A. Marcus, O. K. Rice · The Journal of Physical Chemistry · 1951
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Entropy and the Absolute Rate of Chemical Reactions I. The Steric Factor of Bimolecular Associations
O. K. Rice, Harold Gershinowitz · The Journal of Chemical Physics · 1934
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