Helicity decoupled quantum dynamics and capture model cross sections and rate constants for O(1D) + H2 → OH + H

Stephen K. Gray*, Evelyn M. Goldfield, George C Schatz, Gabriel G. Balint-Kurti

*Corresponding author for this work

Research output: Contribution to journalArticle

108 Scopus citations

Abstract

We study, within a helicity decoupled quantum approximation, the total angular momentum J dependence of reaction probabilities for the reaction O(1D) + H2 → OH + H. A recently developed real wave packet approach is employed for the quantum calculations. The ab initio based, ground electronic (X̄ 1A') potential energy surface of Ho et al. (T-S. Ho, T. Hollebeeck, H. Rabitz, L. B. Harding and G. C. Schatz, J. Chem. Phys., 1996, 105, 10472) is assumed for most of our calculations, although some calculations are also performed with a recent surface due to Dobbyn and Knowles. We find that the low J reaction probabilities tend to be, on average, slightly lower than the high J probabilities. This effect is also found to be reproduced in classical trajectory calculations. A new capture model is proposed that incorporates the available quantum data within an orbital angular momentum or l-shifting approximation to predict total cross sections and rate constants. The results agree well with classical trajectory results and the experimental rate constant at room temperature. However, electronically non-adiabatic effects may become important at higher temperature.

Original languageEnglish (US)
Pages (from-to)1141-1148
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume1
Issue number6
DOIs
StatePublished - Mar 15 1999

ASJC Scopus subject areas

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

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