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 + 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.
| Original language | English |
|---|---|
| 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
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.
In: Chemical Physics Letters, Vol. 24, No. 3, 01.02.1974, p. 378-380.Research output: Contribution to journal › Article
}
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.
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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 -