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Unimolecular dissociations and free radical recombination reactions

Marcus, R. A. (1952) Unimolecular dissociations and free radical recombination reactions. Journal of Chemical Physics, 20 (3). pp. 359-364. ISSN 0021-9606. doi:10.1063/1.1700424.

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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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Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1952 American Institute of Physics. Received August 3, 1951. This work was financially assisted by the ONR Contract No. N8onr-77900. I should like to express my appreciation to Professor O.K. Rice for stimulating discussions and suggestions about the many problems associated with these reactions.
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Office of Naval ResearchN8onr-77900
Issue or Number:3
Record Number:CaltechAUTHORS:MARjcp52b
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11405
Deposited By: Tony Diaz
Deposited On:13 Aug 2008 23:59
Last Modified:08 Nov 2021 21:58

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