Abstract
Exact quantum, quasiclassical, and semiclassical reaction probabilities and rate constants for the collinear reaction F+D2 → FD+D are presented. In all calculations, a high degree of population inversion is predicted with P03R and P04R being the dominant reaction probabilities. In analogy with the F+H2 reaction (preceding paper), the exact quantum 0→3 and 0→4 probabilities show markedly different energy dependence with P03 R having a much smaller effective threshold energy (ET = 0.014 eV) than P04R (0.055 eV). The corresponding quasiclassical forward probabilities P03R and P 04R are in poor agreement with the exact quantum ones, while their quasiclassical reverse and semiclassical counterparts provide much better approximations to the exact results. Similar comparisons are also made in the analysis of the corresponding EQ, QCF, QCR, and USC rate constants. An information theoretic analysis of the EQ and QCF reaction probabilities indicates nonlinear surprisal behavior as well as a significant isotope dependence. Additional quantum results at higher energies are presented and discussed in terms of threshold behavior and resonances. Exact quantum reaction probabilities for the related F+HD → FH+D and F+DH → FD+H reactions are given and an attempt to explain the observed isotope effects is made.
| Original language | English |
|---|---|
| Pages (from-to) | 685-696 |
| Number of pages | 12 |
| Journal | Journal of Chemical Physics |
| Volume | 63 |
| Issue number | 2 |
| Publication status | Published - 1975 |
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ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
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Exact quantum, quasiclassical, and semiclassical reaction probabilities for the collinear F+D2 → FD+D reaction. / Schatz, George C; Bowman, Joel M.; Kuppermann, Aron.
In: Journal of Chemical Physics, Vol. 63, No. 2, 1975, p. 685-696.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Exact quantum, quasiclassical, and semiclassical reaction probabilities for the collinear F+D2 → FD+D reaction
AU - Schatz, George C
AU - Bowman, Joel M.
AU - Kuppermann, Aron
PY - 1975
Y1 - 1975
N2 - Exact quantum, quasiclassical, and semiclassical reaction probabilities and rate constants for the collinear reaction F+D2 → FD+D are presented. In all calculations, a high degree of population inversion is predicted with P03R and P04R being the dominant reaction probabilities. In analogy with the F+H2 reaction (preceding paper), the exact quantum 0→3 and 0→4 probabilities show markedly different energy dependence with P03 R having a much smaller effective threshold energy (ET = 0.014 eV) than P04R (0.055 eV). The corresponding quasiclassical forward probabilities P03R and P 04R are in poor agreement with the exact quantum ones, while their quasiclassical reverse and semiclassical counterparts provide much better approximations to the exact results. Similar comparisons are also made in the analysis of the corresponding EQ, QCF, QCR, and USC rate constants. An information theoretic analysis of the EQ and QCF reaction probabilities indicates nonlinear surprisal behavior as well as a significant isotope dependence. Additional quantum results at higher energies are presented and discussed in terms of threshold behavior and resonances. Exact quantum reaction probabilities for the related F+HD → FH+D and F+DH → FD+H reactions are given and an attempt to explain the observed isotope effects is made.
AB - Exact quantum, quasiclassical, and semiclassical reaction probabilities and rate constants for the collinear reaction F+D2 → FD+D are presented. In all calculations, a high degree of population inversion is predicted with P03R and P04R being the dominant reaction probabilities. In analogy with the F+H2 reaction (preceding paper), the exact quantum 0→3 and 0→4 probabilities show markedly different energy dependence with P03 R having a much smaller effective threshold energy (ET = 0.014 eV) than P04R (0.055 eV). The corresponding quasiclassical forward probabilities P03R and P 04R are in poor agreement with the exact quantum ones, while their quasiclassical reverse and semiclassical counterparts provide much better approximations to the exact results. Similar comparisons are also made in the analysis of the corresponding EQ, QCF, QCR, and USC rate constants. An information theoretic analysis of the EQ and QCF reaction probabilities indicates nonlinear surprisal behavior as well as a significant isotope dependence. Additional quantum results at higher energies are presented and discussed in terms of threshold behavior and resonances. Exact quantum reaction probabilities for the related F+HD → FH+D and F+DH → FD+H reactions are given and an attempt to explain the observed isotope effects is made.
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M3 - Article
VL - 63
SP - 685
EP - 696
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 2
ER -