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Exact quantum, quasiclassical, and semiclassical reaction probabilities for the collinear F+H2 --> FH+H reaction

Schatz, George C. and Bowman, Joel M. and Kuppermann, Aron (1975) Exact quantum, quasiclassical, and semiclassical reaction probabilities for the collinear F+H2 --> FH+H reaction. Journal of Chemical Physics, 63 (2). pp. 374-684. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:SCHAjcp75a

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Abstract

Exact quantum, quasiclassical, and semiclassical reaction probabilities and rate constants for the collinear reaction F+H2 --> FH+H are presented and compared. The exact quantum results indicate a large degree of population inversion of the FH product with P<sup>R</sup><sub>02</sub> and P<sup>R</sup><sub>03</sub> being the dominant reaction probabilities. The energy dependence of these two probabilities at low translational energies are quite different. P<sup>R</sup><sub>02</sub> shows an effective threshold of 0.005 eV which can largely be interpreted as resulting from tunneling through a vibrationally adiabatic barrier. P<sup>R</sup><sub>03</sub> has a much larger effective threshold (0.045 eV) apparently resulting from dynamical effects. Quasiclassical probabilities for the collinear F+H2 reaction were calculated by both the forward (initial conditions chosen for reagent F+H2) and reverse (initial conditions for product H+FH) trajectory methods. The results of both calculations correctly indicate that P<sup>R</sup><sub>03</sub> and P<sup>R</sup><sub>02</sub> should be the dominant reaction probabilities. However, the threshold behavior of the quasiclassical forward P<sup>R</sup><sub>03</sub> disagrees strongly with the corresponding exact quantum threshold energy dependence. By contrast, there is good agreement between the reversed trajectory results and the exact quantum ones. The uniform semiclassical results also agree well with the corresponding exact quantum ones indicating that the quasiclassical reverse and the semiclassical methods are preferable to the quasiclassical forward method for this reaction. The important differences between the threshold behavior of the exact quantum and quasiclassical forward reaction probabilities are manifested in the corresponding rate constants primarily as large differences in their activation energies. Additional exact quantum results at higher total energies indicate that threshold effects are no longer important for reactions with vibrationally excited H2. Resonances play an important role in certain reaction probabilities primarily at higher relative translational energies.


Item Type:Article
Additional Information:Copyright © 1975 American Institute of Physics. Received 22 October 1974. We thank Ambassador College for the use of their computational facilities in most of the work reported here. [J.M.B.'s] Work supported in part by the United States Air Force Office of Scientific Research. [G.C.S.] performed [this work] in partial fulfillment of the requirements for the Ph.D. degree in Chemistry at the California Institute of Technology. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 4988.
Record Number:CaltechAUTHORS:SCHAjcp75a
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:SCHAjcp75a
Alternative URL:http://dx.doi.org/10.1063/1.431390
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10044
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:08 Apr 2008
Last Modified:26 Dec 2012 09:56

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