2 Calculations of accurate quantal-dynamical reactive scattering transition probabilities and their use to test semiclassical applications

John Z.H. Zhang, Yici Zhang, Donald J. Kouri, Bruce C. Garrett, Kenneth Haug, David W. Schwenke, Donald G. Truhlar

Research output: Contribution to journalArticle

Abstract

We discuss the calculation of quantum-mechanical amplitudes for reactive scattering based on the Fock scheme for coupling arrangement channels and expansion of the coupled amplitude densities in terms of square-integrable (ℒ2) basis functions. First, we provide a derivation of the coupled equations for the amplitude densities from the Fock-scheme integrodifferential equations for wavefunction components. Then we discuss the solution of these equations by ℒ2 techniques. The methods are applied to calculate the thresholds and tunnelling probabilities for the reactions O + H2(υ = 0, 1) → OH + H and H + OH(υ = 0, 1) → O + H2, where υ denotes the vibrational quantum number. The results, which represent accurate quantal dynamics for a given potential-energy surface, are used to test the predictions of variational transition-state theory for threshold energies and the least-action semiclassical method for tunnelling probabilities.

Original languageEnglish (US)
Pages (from-to)371-385
Number of pages15
JournalFaraday Discussions of the Chemical Society
Volume84
DOIs
StatePublished - 1987

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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