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Generalization of the Activated Complex Theory of Reaction Rates. II. Classical Mechanical Treatment

Marcus, R. A. (1964) Generalization of the Activated Complex Theory of Reaction Rates. II. Classical Mechanical Treatment. Journal of Chemical Physics, 41 (9). pp. 2624-2633. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120827-131805519

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Abstract

In its usual classical form, activated‐complex theory assumes a particular expression for the kinetic energy of the reacting system, one being associated with a rectilinear motion along the reaction coordinate. The derivation of the rate expression given in the present paper is based on the general kinetic‐energy expression. A rate equation of the customary form is obtained: k_rate = (kT/h)exp[−(F‡−F^r)/kT], where F‡ is the free energy of a system constrained to exist on a hypersurface in n‐dimensional space and Fr is the free energy of the reactants. The usual derivation is then reinterpreted, in terms of geodesic normal coordinates, to be somewhat more general than it appears. Normally, rotation—vibration interaction is neglected, as in the above derivation, although not in treatments of some special reactions in the literature for which the centrifugal potential is important. A derivation is given which includes the influence of this centrifugal potential but which omits Coriolis effects.


Item Type:Article
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http://dx.doi.org/10.1063/1.1726330DOIUNSPECIFIED
http://link.aip.org/link/doi/10.1063/1.1726330PublisherUNSPECIFIED
Additional Information:© 1964 American Institute of Physics. Received 20 July 1964. Research performed in part under the auspices of the U.S. Atomic Energy Commission. This research was supported in part by a fellowship from the Alfred P. Sloan Foundation.
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Atomic Energy CommissionUNSPECIFIED
Alfred P. Sloan Foundation Fellowship UNSPECIFIED
Record Number:CaltechAUTHORS:20120827-131805519
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120827-131805519
Official Citation:Generalization of the Activated Complex Theory of Reaction Rates. II. Classical Mechanical Treatment R. A. Marcus, J. Chem. Phys. 41, 2624 (1964), DOI:10.1063/1.1726330
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:33569
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:27 Aug 2012 21:33
Last Modified:26 Dec 2012 16:03

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