Schatz, George C. and Bowman, Joel M. and Kuppermann, Aron (1975) Exact quantum quasiclassical, and semiclassical reaction probabilities for the collinear F+D_2 → FD+D reaction. Journal of Chemical Physics, 63 (2). pp. 685-696. ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:20120810-073044903
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Exact quantum, quasiclassical, and semiclassical reaction probabilities and rate constants for the collinear reaction F+D_2 → FD+D are presented. In all calculations, a high degree of population inversion is predicted with P^R_(03) and P^R(04) being the dominant reaction probabilities. In analogy with the F+H_2 reaction (preceding paper), the exact quantum 0→3 and 0→4 probabilities show markedly different energy dependence with PR03 having a much smaller effective threshold energy (E_T=0.014 eV) than P^R_(04) (0.055 eV). The corresponding quasiclassical forward probabilities P^R_(03) and P^R_(04) are in poor agreement with the exact quantum ones, while their quasiclassical reverse and semiclassical counterparts provide much better approximations to the exact results. Similar comparisons are also made in the analysis of the corresponding EQ, QCF, QCR, and USC rate constants. An information theoretic analysis of the EQ and QCF reaction probabilities indicates nonlinear surprisal behavior as well as a significant isotope dependence. Additional quantum results at higher energies are presented and discussed in terms of threshold behavior and resonances. Exact quantum reaction probabilities for the related F+HD → FH+D and F+DH → FD+H reactions are given and an attempt to explain the observed isotope effects is made.
|Additional Information:||© 1975 American Institute of Physics. Received 22 October 1974. Online Publication Date: 3 September 2008. We thank J. T. Muckerman, with whom we have exchanged results on the USC calculations, for useful discussions. We also thank Ambassador College for the use of their computational facilities in most of the work reported here. Work supported in part by the United states Air Force Office of Scientific Research. Work performed in partial fulfillment of the requirements for the Ph. D. degree in Chemistry at the California Institute of Technology. Contribution No. 4989.|
|Subject Keywords:||DEUTERIUM, ISOTOPE EFFECTS, HYDROFLUORIC ACID, CHEMICAL REACTION KINETICS, SEMICLASSICAL APPROXIMATION|
|Other Numbering System:|
|Classification Code:||PACS: 82.20.Fd|
|Official Citation:||Exact quantum, quasiclassical, and semiclassical reaction probabilities for the collinear F+D2 → FD+D reaction George C. Schatz, Joel M. Bowman, and Aron Kuppermann J. Chem. Phys. 63, 685 (1975); http://dx.doi.org/10.1063/1.431391|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Ruth Sustaita|
|Deposited On:||10 Aug 2012 15:30|
|Last Modified:||26 Dec 2012 15:56|
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