Quantum initial conditions in quasi-classical trajectory calculations

Joel M. Bowman, Aron Kuppermann, George C. Schatz

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)


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
Issue number1
Publication statusPublished - 1973

ASJC Scopus subject areas

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

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