### Abstract

A comprehensive survey of the quantum scattering methodology that results from applying the S-matrix version of the Kohn variational principle to the reactive scattering formulation given by Miller [J. Chem. Phys. 50, 407 (1969)] is presented. Results of calculations using this approach are reported for the reaction D + H_{2} → HD + H. The 3-d calculations include total angular momentum values from J = 0 up to 31 in order to obtain converged integral and differential cross sections over a wide range of energy (0.4-1.35 eV total energy). Results are given for reaction probabilities for individual values of J, integral and differential cross sections for a number of energies, and state-to-state rate constants (i.e., a Boltzmann average over translational energy), and comparisons are made to a variety of different experimental results. A particularly interesting qualitative feature which is observed in the calculations is that the energy dependence of the differential cross section in the backward direction (θ = 180°) shows a resonance structure (due to a short-lived DH_{2} collision complex) which is very similar to that in the J = 0 reaction probability. This resonance structure does not appear in the energy dependence of the integral cross section, being averaged out by the sum over J.

Original language | English (US) |
---|---|

Pages (from-to) | 1528-1547 |

Number of pages | 20 |

Journal | The Journal of chemical physics |

Volume | 91 |

Issue number | 3 |

State | Published - 1989 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*The Journal of chemical physics*,

*91*(3), 1528-1547.

**Quantum reactive scattering via the S-matrix version of the Kohn variational principle : Differential and integral cross sections for D+H 2 → HD+H.** / Zhang, John; Miller, William H.

Research output: Contribution to journal › Article

*The Journal of chemical physics*, vol. 91, no. 3, pp. 1528-1547.

}

TY - JOUR

T1 - Quantum reactive scattering via the S-matrix version of the Kohn variational principle

T2 - Differential and integral cross sections for D+H 2 → HD+H

AU - Zhang, John

AU - Miller, William H.

PY - 1989

Y1 - 1989

N2 - A comprehensive survey of the quantum scattering methodology that results from applying the S-matrix version of the Kohn variational principle to the reactive scattering formulation given by Miller [J. Chem. Phys. 50, 407 (1969)] is presented. Results of calculations using this approach are reported for the reaction D + H2 → HD + H. The 3-d calculations include total angular momentum values from J = 0 up to 31 in order to obtain converged integral and differential cross sections over a wide range of energy (0.4-1.35 eV total energy). Results are given for reaction probabilities for individual values of J, integral and differential cross sections for a number of energies, and state-to-state rate constants (i.e., a Boltzmann average over translational energy), and comparisons are made to a variety of different experimental results. A particularly interesting qualitative feature which is observed in the calculations is that the energy dependence of the differential cross section in the backward direction (θ = 180°) shows a resonance structure (due to a short-lived DH2 collision complex) which is very similar to that in the J = 0 reaction probability. This resonance structure does not appear in the energy dependence of the integral cross section, being averaged out by the sum over J.

AB - A comprehensive survey of the quantum scattering methodology that results from applying the S-matrix version of the Kohn variational principle to the reactive scattering formulation given by Miller [J. Chem. Phys. 50, 407 (1969)] is presented. Results of calculations using this approach are reported for the reaction D + H2 → HD + H. The 3-d calculations include total angular momentum values from J = 0 up to 31 in order to obtain converged integral and differential cross sections over a wide range of energy (0.4-1.35 eV total energy). Results are given for reaction probabilities for individual values of J, integral and differential cross sections for a number of energies, and state-to-state rate constants (i.e., a Boltzmann average over translational energy), and comparisons are made to a variety of different experimental results. A particularly interesting qualitative feature which is observed in the calculations is that the energy dependence of the differential cross section in the backward direction (θ = 180°) shows a resonance structure (due to a short-lived DH2 collision complex) which is very similar to that in the J = 0 reaction probability. This resonance structure does not appear in the energy dependence of the integral cross section, being averaged out by the sum over J.

UR - http://www.scopus.com/inward/record.url?scp=0342726450&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0342726450&partnerID=8YFLogxK

M3 - Article

VL - 91

SP - 1528

EP - 1547

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 3

ER -