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Activated-complex theory: current status, extensions, and applications

Marcus, R. A. (1974) Activated-complex theory: current status, extensions, and applications. In: Investigation of rates and mechanisms of reactions, 3rd ed. Techniques of Chemistry. 2. No.6. Wiley , New York, NY, pp. 13-46. ISBN 9780471930952.

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The activated-complex theory of chemical reactions has proved to be very useful in interpreting rate data on a wide variety of chemical reactions. The topics so treated include preexponential factors of bimolecular gas-phase reactions, preexponential factors at high pressures of unimolecular reactions, salt and polar solvent effects on bimolecular-reaction rates, and recombination rates of radicals under certain conditions. In conjunction with additional concepts, the theory has also found extensive use in such subjects as pressure effects on unimolecular reactions (so-called RRKM theory}, chemical activation, and electron-transfer reactions both in solution and at electrodes. In the present chapter the assumptions and several derivations of the theory are considered. Some of the recent tests of activated-complex theory that are based on the numerical solution of the dynamical equations of motion of the reactants are summarized. Topics such as the "free-energy-maximization criterion" for the position of the activated complex are also considered. Several of the applications of activated-complex theory are treated, and some dynamical extensions of it are noted. Some of the work described in the present chapter is drawn from the writer's published studies, but the material in Sections 3 and 5 on an ensemble derivation for reactions in solution and on a basis for the usual free-energy-maximization criterion for location of the activated complex is drawn from unpublished work.

Item Type:Book Section
Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1974 Wiley. I am particularly indebted to my co-worker, Dr. Richard Ellis, for his helpful comments. Research on which some of the material in this chapter was based was supported by a grant from the National Science Foundation.
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Series Name:Techniques of Chemistry
Issue or Number:6
Record Number:CaltechAUTHORS:20150409-123823320
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:56535
Deposited By: George Porter
Deposited On:09 Apr 2015 20:38
Last Modified:22 Nov 2019 09:58

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