### Abstract

Exact quantum, quasiclassical, and semiclassical reaction probabilities and rate constants for the collinear reaction F+D_{2} → FD+D are presented. In all calculations, a high degree of population inversion is predicted with P_{03}^{R} and P_{04}^{R} being the dominant reaction probabilities. In analogy with the F+H_{2} reaction (preceding paper), the exact quantum 0→3 and 0→4 probabilities show markedly different energy dependence with P_{03} ^{R} having a much smaller effective threshold energy (E_{T} = 0.014 eV) than P_{04}^{R} (0.055 eV). The corresponding quasiclassical forward probabilities P_{03}^{R} and P _{04}^{R} 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

### Cite this

_{2}→ FD+D reaction.

*Journal of Chemical Physics*,

*63*(2), 685-696.

**Exact quantum, quasiclassical, and semiclassical reaction probabilities for the collinear F+D _{2} → FD+D reaction.** / Schatz, George C; Bowman, Joel M.; Kuppermann, Aron.

Research output: Contribution to journal › Article

_{2}→ FD+D reaction',

*Journal of Chemical Physics*, vol. 63, no. 2, pp. 685-696.

_{2}→ FD+D reaction. Journal of Chemical Physics. 1975;63(2):685-696.

}

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 -