Violation of microscopic reversibility and the use of reverse quasi- classical trajectories for calculating reaction cross sections
Journal Article
·
· Chem. Phys. Lett., v. 24, no. 3, pp. 378-380
OSTI ID:4354629
In order to calculate the transition probabilities (or cross sections) for reactive collisions, such as A + BC(v,j) yields AB(v',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/sub 2/(v = 0) FH(v = 2,3) + H reaction (and its D/ sub 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/sub 2/(O) yields H/sub 2/(1) + H reaction. It is suggested that in doi ng 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. (auth)
- Research Organization:
- California Inst. of Tech., Pasadena
- NSA Number:
- NSA-29-025206
- OSTI ID:
- 4354629
- Journal Information:
- Chem. Phys. Lett., v. 24, no. 3, pp. 378-380, Journal Name: Chem. Phys. Lett., v. 24, no. 3, pp. 378-380; ISSN CHPLB
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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