Stochastic theory of vibrational energy transfer in collinear atom-diatom collisions: The role of non-markovian effects

Frederick W. King, George C. Schatz

Research output: Contribution to journalArticle

5 Scopus citations

Abstract

The role of non-markovian effects in the stochastic treatment of vibrational- translational energy transfer in collinear atom—diatom collisions is examined. A comparison of transition probabilities using both markovian and nonmarkovian types of master equations, as well as exact time dependent quantum mechanics, is made for various values of the system parameters m and a. We find that for certain ranges of the system parameters, the deviations between markovian and non-markovian theories are substantial. Only in the perturbation theory limit and in the limit of low m/α2 values and high enough initial translational energies such that an impulsive approximation for translational motion is accurate are the markovian and non-markovian results similar. An analysis of the collision dynamics indicates that the markovian and non-markovian probabilities agree with each other and with the exact probabilities when action-angle correlations are weak while none of these theories agree (except by accident) when such effects are strong.

Original languageEnglish (US)
Pages (from-to)257-272
Number of pages16
JournalMolecular Physics
Volume38
Issue number1
DOIs
StatePublished - Jul 1979

ASJC Scopus subject areas

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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