### 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 |

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### ASJC Scopus subject areas

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

### Cite this

*Chemical Physics Letters*,

*24*(3), 378-380. https://doi.org/10.1016/0009-2614(74)85282-6

**Violation of microscopic reversibility and the use of reverse quais-classical trajectories for calculating reaction cross sections.** / Bowman, Joel M.; Schatz, George C; Kupperman, Aron.

Research output: Contribution to journal › Article

*Chemical Physics Letters*, vol. 24, no. 3, pp. 378-380. https://doi.org/10.1016/0009-2614(74)85282-6

}

TY - JOUR

T1 - Violation of microscopic reversibility and the use of reverse quais-classical trajectories for calculating reaction cross sections

AU - Bowman, Joel M.

AU - Schatz, George C

AU - Kupperman, Aron

PY - 1974/2/1

Y1 - 1974/2/1

N2 - 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 + H2(ν = 0) → FH(ν = 2, 3)+ H reaction (and its D2 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 + H2(0) → H2(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.

AB - 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 + H2(ν = 0) → FH(ν = 2, 3)+ H reaction (and its D2 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 + H2(0) → H2(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.

UR - http://www.scopus.com/inward/record.url?scp=21544475214&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=21544475214&partnerID=8YFLogxK

U2 - 10.1016/0009-2614(74)85282-6

DO - 10.1016/0009-2614(74)85282-6

M3 - Article

VL - 24

SP - 378

EP - 380

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 3

ER -