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Published July 15, 1975 | public
Journal Article Open

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

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 PR02 and PR03 being the dominant reaction probabilities. The energy dependence of these two probabilities at low translational energies are quite different. PR02 shows an effective threshold of 0.005 eV which can largely be interpreted as resulting from tunneling through a vibrationally adiabatic barrier. PR03 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 PR03 and PR02 should be the dominant reaction probabilities. However, the threshold behavior of the quasiclassical forward PR03 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.

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.

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August 22, 2023
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