Quantum initial conditions in quasi-classical trajectory calculations

Joel M. Bowman, Aron Kuppermann, George C Schatz

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The quantum distribution of initial conditions suggested recently by Careless and Hyatt as a means of "phase-averaging" classical trajectories is shown to lead to reaction probabilities which depend on the initial distance between the reagents even when this distance is sufficiently large for the corresponding interaction energy to vanish. We used that distribution to calculate reaction probabilities for the collinear H + H2 exchange reaction on a potential energy surface for which quasi-classical and exact quantum results had been previously obtained. The dependence of the resulting reaction probabilities on the arbitrarily chosen value of the initial atom-molecule separation was substantial. We conclude that the use of such quantum distributions for initial conditions is physically unacceptable.

Original languageEnglish
Pages (from-to)21-25
Number of pages5
JournalChemical Physics Letters
Volume19
Issue number1
DOIs
Publication statusPublished - 1973

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Trajectories
trajectories
Potential energy surfaces
Ion exchange
reagents
Atoms
Molecules
potential energy
atoms
molecules
interactions
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Surfaces and Interfaces

Cite this

Quantum initial conditions in quasi-classical trajectory calculations. / Bowman, Joel M.; Kuppermann, Aron; Schatz, George C.

In: Chemical Physics Letters, Vol. 19, No. 1, 1973, p. 21-25.

Research output: Contribution to journalArticle

Bowman, Joel M. ; Kuppermann, Aron ; Schatz, George C. / Quantum initial conditions in quasi-classical trajectory calculations. In: Chemical Physics Letters. 1973 ; Vol. 19, No. 1. pp. 21-25.
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