### Abstract

Accurate three-dimensional reactive and nonreactive quantum mechanical cross sections for the H+H_{2} exchange reaction on the Porter-Karplus potential energy surface are presented. Tests of convergence in the calculations indicate an accuracy of better than 5% for most of the results in the energy range considered (0.3 to 0.7 eV total energy). The reactive differential cross sections are exclusively backward peaked, with peak widths increasing monotonically from about 32° at 0.4 eV to 51° at 0.7 eV. Nonreactive inelastic differential cross sections show backwards to sidewards peaking, while elastic ones are strongly forward peaked with a nearly monotonic decrease with increasing scattering angle. Some oscillations due to interferences between the direct and exchange amplitudes are obtained in the para-to-para and ortho-to-ortho antisymmetrized cross sections above the effective threshold for reaction. Nonreactive collisions do not show a tendency to satisfy a "j_{z}-conserving" selection rule. The reactive cross sections show significant rotational angular momentum polarization with the m _{j}=m′_{j}=0 transition dominating for low reagent rotational quantum number j. In constrast, the degeneracy averaged rotational distributions can be fitted to statistical temperaturelike expressions to a high degree of accuracy. The integral cross sections have an effective threshold total energy of about 0.55 eV, and differences between this quantity and the corresponding 1D and 2D results can largely be interpreted as resulting from bending motions in the transition state. In comparing these results with those of previous approximate dynamical calculations, we find best overall agreement between our reactive integral and differential cross sections and the quasiclassical ones of Karplus, Porter, and Sharma [J. Chem. Phys. 43, 3259 (1965)], at energies above the quasiclassical effective thresholds. This results in the near equality of the quantum and quasiclassical thermal rate constants at 600 K. At lower temperatures, however, the effects of tunneling become very important with the quantum rate constant achieving a value larger than the quasiclassical one by a factor of 3.2 at 300 K and 18 at 200 K.

Original language | English |
---|---|

Pages (from-to) | 4668-4692 |

Number of pages | 25 |

Journal | Journal of Chemical Physics |

Volume | 65 |

Issue number | 11 |

Publication status | Published - 1976 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

_{2}.

*Journal of Chemical Physics*,

*65*(11), 4668-4692.

**Quantum mechanical reactive scattering for three-dimensional atom plus diatom systems. II. Accurate cross sections for H+H _{2}.** / Schatz, George C; Kuppermann, Aron.

Research output: Contribution to journal › Article

_{2}',

*Journal of Chemical Physics*, vol. 65, no. 11, pp. 4668-4692.

_{2}. Journal of Chemical Physics. 1976;65(11):4668-4692.

}

TY - JOUR

T1 - Quantum mechanical reactive scattering for three-dimensional atom plus diatom systems. II. Accurate cross sections for H+H2

AU - Schatz, George C

AU - Kuppermann, Aron

PY - 1976

Y1 - 1976

N2 - Accurate three-dimensional reactive and nonreactive quantum mechanical cross sections for the H+H2 exchange reaction on the Porter-Karplus potential energy surface are presented. Tests of convergence in the calculations indicate an accuracy of better than 5% for most of the results in the energy range considered (0.3 to 0.7 eV total energy). The reactive differential cross sections are exclusively backward peaked, with peak widths increasing monotonically from about 32° at 0.4 eV to 51° at 0.7 eV. Nonreactive inelastic differential cross sections show backwards to sidewards peaking, while elastic ones are strongly forward peaked with a nearly monotonic decrease with increasing scattering angle. Some oscillations due to interferences between the direct and exchange amplitudes are obtained in the para-to-para and ortho-to-ortho antisymmetrized cross sections above the effective threshold for reaction. Nonreactive collisions do not show a tendency to satisfy a "jz-conserving" selection rule. The reactive cross sections show significant rotational angular momentum polarization with the m j=m′j=0 transition dominating for low reagent rotational quantum number j. In constrast, the degeneracy averaged rotational distributions can be fitted to statistical temperaturelike expressions to a high degree of accuracy. The integral cross sections have an effective threshold total energy of about 0.55 eV, and differences between this quantity and the corresponding 1D and 2D results can largely be interpreted as resulting from bending motions in the transition state. In comparing these results with those of previous approximate dynamical calculations, we find best overall agreement between our reactive integral and differential cross sections and the quasiclassical ones of Karplus, Porter, and Sharma [J. Chem. Phys. 43, 3259 (1965)], at energies above the quasiclassical effective thresholds. This results in the near equality of the quantum and quasiclassical thermal rate constants at 600 K. At lower temperatures, however, the effects of tunneling become very important with the quantum rate constant achieving a value larger than the quasiclassical one by a factor of 3.2 at 300 K and 18 at 200 K.

AB - Accurate three-dimensional reactive and nonreactive quantum mechanical cross sections for the H+H2 exchange reaction on the Porter-Karplus potential energy surface are presented. Tests of convergence in the calculations indicate an accuracy of better than 5% for most of the results in the energy range considered (0.3 to 0.7 eV total energy). The reactive differential cross sections are exclusively backward peaked, with peak widths increasing monotonically from about 32° at 0.4 eV to 51° at 0.7 eV. Nonreactive inelastic differential cross sections show backwards to sidewards peaking, while elastic ones are strongly forward peaked with a nearly monotonic decrease with increasing scattering angle. Some oscillations due to interferences between the direct and exchange amplitudes are obtained in the para-to-para and ortho-to-ortho antisymmetrized cross sections above the effective threshold for reaction. Nonreactive collisions do not show a tendency to satisfy a "jz-conserving" selection rule. The reactive cross sections show significant rotational angular momentum polarization with the m j=m′j=0 transition dominating for low reagent rotational quantum number j. In constrast, the degeneracy averaged rotational distributions can be fitted to statistical temperaturelike expressions to a high degree of accuracy. The integral cross sections have an effective threshold total energy of about 0.55 eV, and differences between this quantity and the corresponding 1D and 2D results can largely be interpreted as resulting from bending motions in the transition state. In comparing these results with those of previous approximate dynamical calculations, we find best overall agreement between our reactive integral and differential cross sections and the quasiclassical ones of Karplus, Porter, and Sharma [J. Chem. Phys. 43, 3259 (1965)], at energies above the quasiclassical effective thresholds. This results in the near equality of the quantum and quasiclassical thermal rate constants at 600 K. At lower temperatures, however, the effects of tunneling become very important with the quantum rate constant achieving a value larger than the quasiclassical one by a factor of 3.2 at 300 K and 18 at 200 K.

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M3 - Article

AN - SCOPUS:0000182188

VL - 65

SP - 4668

EP - 4692

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 11

ER -