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On the Analytical Mechanics of Chemical Reactions. Classical Mechanics of Linear Collisions

Marcus, R. A. (1966) On the Analytical Mechanics of Chemical Reactions. Classical Mechanics of Linear Collisions. Journal of Chemical Physics, 45 (12). pp. 4500-4504. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120829-110842187

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Abstract

The classical mechanics of chemically reactive linear collisions is investigated for vibrationally near‐adiabatic reactions. A coordinate system which passes smoothly from one suited to the reactants to one suited to the products is used. The Hamilton—Jacobi equation is then solved in the adiabatic approximation by introduction of an "adiabatic‐separable" method. Nonadiabatic corrections, which describe the probability of vibrational transitions, are also calculated. They involve the Fourier component of local internal centrifugal and vibration frequency‐change terms. The reaction coordinate for the adiabatic system is shown to be that curve on which local vibrational and internal centrifugal forces balance pointwise. Applications can be made to the role of translational—vibrational energy interchange in reactions, reaction‐cross‐section theory, bobsled effect, and other topics. The results may be compared with electronic computer calculations as they become available.


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http://dx.doi.org/10.1063/1.1727529DOIUNSPECIFIED
http://link.aip.org/link/doi/10.1063/1.1727529PublisherUNSPECIFIED
Additional Information:© 1966 American Institute of Physics. Received 3 June 1966. Supported by a grant from the National Science Foundation.
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Record Number:CaltechAUTHORS:20120829-110842187
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120829-110842187
Official Citation:On the Analytical Mechanics of Chemical Reactions. Classical Mechanics of Linear Collisions R. A. Marcus, J. Chem. Phys. 45, 4500 (1966), DOI:10.1063/1.1727529
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:33653
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:29 Aug 2012 18:24
Last Modified:26 Dec 2012 16:04

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