## Abstract

In order to calculate the transition probabilities (or cross sections) for reactive collisions, such as A + BC(ν, j)→ AB(ν′, j) + C, using the quasi-classical trajectory method, one quantizes the internal energy of the reagents and in addition adopts some algorithm for calculating the internal quantum numbers of the products. A serious consequence of this procedure is that the quasi-classical results do not obey microscopic reversibility. It is shown that for the collinear F + H_{2}(ν = 0) → FH(ν = 2, 3)+ H reaction (and its D_{2} counterpart), the quasi-classical trajectory probabilities for the reverse reaction not only differ substantially from the forward ones but in general are in much better agreement with accurate quantum calculations. A similar situation was found for the collinear H + H_{2}(0) → H_{2}(1) + H reaction. We suggest that in doing quasi-classical calculations, the reverse of the process of interest should also be considered. Comparison of forward and reverse quasi-classical collinear calculations with accurate collinear quantum results could give an indication of whether forward or reverse calculations should be used for the three-dimensional case.

Original language | English |
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Pages (from-to) | 378-380 |

Number of pages | 3 |

Journal | Chemical Physics Letters |

Volume | 24 |

Issue number | 3 |

DOIs | |

Publication status | Published - Feb 1 1974 |

## ASJC Scopus subject areas

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