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Analytical Mechanics of Chemical Reactions. V. Application to the Linear Reactive H +H_2 Systems

Wu, Shiou-Fu and Marcus, R. A. (1970) Analytical Mechanics of Chemical Reactions. V. Application to the Linear Reactive H +H_2 Systems. Journal of Chemical Physics, 53 (10). pp. 4026-4035. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120814-085632625

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Abstract

Natural collision coordinates and a zeroth‐order vibrational–adiabatic approximation are used to treat linear reactive collisions. Nonadiabatic effects on barrier transmission and on vibrational state of products are calculated. The present results are classical and are compared with exact classical numerical results for the H+H_2 reaction in the range 7–20 kcal/mol of initial relative translational energy. The agreement is encouraging and the results support the concepts introduced earlier of statistical adiabaticity and of nonadiabatic leak. At low energies the reaction is adiabatic on the average (initial vibrational phase average), thus justifying activated complex theory for this system. The relative importance of reaction path curvature and of vibrational frequency variation along the reaction path in inducing nonadiabatic effects is described. Implications for a quantum treatment, activated complex theory, and highly nonadiabatic systems are noted.


Item Type:Article
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http://dx.doi.org/10.1063/1.1673874 DOIUNSPECIFIED
http://jcp.aip.org/resource/1/jcpsa6/v53/i10/p4026_s1PublisherUNSPECIFIED
Additional Information:© 1970 American Institute of Physics. Received 8 July 1970. Online Publication Date: 18 September 2003. Acknowledgement is made to the donors of the Petroleum Research Fund administrated by the American Chemical Society, for partial support of this research. This research was also supported by a grant from the National Science Foundation at the University of Illinois.
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American Chemical Society Petroleum Research FundUNSPECIFIED
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Record Number:CaltechAUTHORS:20120814-085632625
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120814-085632625
Official Citation: Analytical Mechanics of Chemical Reactions. V. Application to the Linear Reactive H +H2 Systems Shiou‐fu Wu and R. A. Marcus J. Chem. Phys. 53, 4026 (1970); http://dx.doi.org/10.1063/1.1673874
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:33157
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:14 Aug 2012 16:16
Last Modified:26 Dec 2012 15:58

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