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Generalization of Activated-Complex Theory. III. Vibrational Adiabaticity, Separation of Variables, and a Connection with Analytical Mechanics

Marcus, R. A. (1965) Generalization of Activated-Complex Theory. III. Vibrational Adiabaticity, Separation of Variables, and a Connection with Analytical Mechanics. Journal of Chemical Physics, 43 (5). pp. 1598-1605. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120829-134411768

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Abstract

In Part I, activated‐complex theory was extended by including the possibility of a curvilinear reaction coordinate. A separation‐of‐variables approximation was made in the neighborhood of the activated‐complex region of configuration space. In the present paper a more general yet simpler derivation of the final equation is given. It permits subsequent introduction of analytical mechanics in the above neighborhood in a variety of ways such as separation of variables, vibrational adiabaticity, or a method combining certain features of both, the separable—adiabatic approximation. The relationship of these methods is discussed. Some numerical quantum‐ and classical‐mechanical results obtained for transmission coefficients of nonrotating atom‐transfer reactions (linear complexes), using computers, are interpreted in terms of an adiabatic approximation with reasonable agreement. Attention is also called to a modified WBK expression for the transmission coefficient, which generalizes the usual WBK formula in a simple way.


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http://dx.doi.org/10.1063/1.1696977 DOIUNSPECIFIED
http://jcp.aip.org/resource/1/jcpsa6/v43/i5/p1598_s1PublisherUNSPECIFIED
Additional Information:© 1965 American Institute of Physics. Received 12 May 1965. Online Publication Date: 18 May 2004. Supported by a grant from the National Science Foundation.
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Record Number:CaltechAUTHORS:20120829-134411768
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120829-134411768
Official Citation: Generalization of Activated‐Complex Theory. III. Vibrational Adiabaticity, Separation of Variables, and a Connection with Analytical Mechanics R. A. Marcus J. Chem. Phys. 43, 1598 (1965); http://dx.doi.org/10.1063/1.1696977
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ID Code:33671
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:29 Aug 2012 21:12
Last Modified:26 Dec 2012 16:04

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