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 language | English (US) |
|---|---|
| Pages (from-to) | 257-272 |
| Number of pages | 16 |
| Journal | Molecular Physics |
| Volume | 38 |
| Issue number | 1 |
| DOIs | |
| State | Published - Jul 1979 |
Funding
Acknowledgement is made to the Research Corporation and to the Donors of the Petroleum Research Fund of the American Chemical Society for partial support of this research.
ASJC Scopus subject areas
- Biophysics
- Molecular Biology
- Condensed Matter Physics
- Physical and Theoretical Chemistry