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

George C Schatz, Joel M. Bowman, Aron Kuppermann

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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 P02R and P03R being the dominant reaction probabilities. The energy dependence of these two probabilities at low translational energies are quite different. P02R shows an effective threshold of 0.005 eV which can largely be interpreted as resulting from tunneling through a vibrationally adiabatic barrier. P03R 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+H 2) and reverse (initial conditions for product H+FH) trajectory methods. The results of both calculations correctly indicate that P 03R and P02R should be the dominant reaction probabilities. However, the threshold behavior of the quasiclassical forward P03R 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.

Original languageEnglish
Pages (from-to)674-684
Number of pages11
JournalJournal of Chemical Physics
Volume63
Issue number2
Publication statusPublished - 1975

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thresholds
Rate constants
Trajectories
energy
trajectories
population inversion
products
Activation energy
reagents
activation energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Exact quantum, quasiclassical, and semiclassical reaction probabilities for the collinear F+H2 → FH+H reaction. / Schatz, George C; Bowman, Joel M.; Kuppermann, Aron.

In: Journal of Chemical Physics, Vol. 63, No. 2, 1975, p. 674-684.

Research output: Contribution to journalArticle

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