### Abstract

We present the results of quasiclassical trajectory (QCT) and quantum centrifugal sudden hyperspherical (CSH) scattering calculations for the Cl+HCl→ClH+Cl reaction using a semiempirical potential energy surface. In particular, we report state-to-state integral and differential cross sections in the vicinity of a transition state resonance that occurs at a total energy E of 0.642 eV. This resonance, which is labeled by the transition state quantum numbers (0,0,2), strongly perturbs the cross sections for the initial rovibrational state HCl(v=1, j=5), which was therefore considered in all our calculations. For E≥0.680 eV, which is well removed from the resonance energy, the QCT and CSH results are in good agreement, but for E near the resonance energy, important quantum effects are found in the integral cross sections, product state distributions, and differential cross sections. The CSH integral cross sections show smooth steplike increases for E≈0.642 eV, which are not seen in the QCT results. Associated with these steps are increased branching to the v′=0 product HCl vibrational state, and a strong propensity for the production of rotational states with j′=15 and 16 for v′=0. These features of the product energy partitioning are not present in the QCT results, although the correct rotational distributions are approximately recovered if the final vibrational action is constrained to match its quantum value. The CSH differential cross sections show a sudden shift from backward to sideward scattering between 0.642 and 0.660 eV, while the QCT cross sections remain backward peaked. An analysis of the "number of atom-diatom encounters," during the course of a reactive collision, shows that there are chattering trajectories. These are associated with sideward scattering, but their probability is low and as a result they do not produce distinct features in the angular distributions. However, if the classical deflection function is weighted by the quantum reaction probability, angular distributions are obtained that are in reasonable agreement with the CSH angular distributions (including resonance features).

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

Pages (from-to) | 6451-6459 |

Number of pages | 9 |

Journal | Journal of Chemical Physics |

Volume | 97 |

Issue number | 9 |

Publication status | Published - 1992 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*Journal of Chemical Physics*,

*97*(9), 6451-6459.

**Comparison of quasiclassical and quantum dynamics for resonance scattering in the Cl+HCl→CIH+Cl reaction.** / Jakubetz, W.; Sokolovski, D.; Connor, J. N L; Schatz, George C.

Research output: Contribution to journal › Article

*Journal of Chemical Physics*, vol. 97, no. 9, pp. 6451-6459.

}

TY - JOUR

T1 - Comparison of quasiclassical and quantum dynamics for resonance scattering in the Cl+HCl→CIH+Cl reaction

AU - Jakubetz, W.

AU - Sokolovski, D.

AU - Connor, J. N L

AU - Schatz, George C

PY - 1992

Y1 - 1992

N2 - We present the results of quasiclassical trajectory (QCT) and quantum centrifugal sudden hyperspherical (CSH) scattering calculations for the Cl+HCl→ClH+Cl reaction using a semiempirical potential energy surface. In particular, we report state-to-state integral and differential cross sections in the vicinity of a transition state resonance that occurs at a total energy E of 0.642 eV. This resonance, which is labeled by the transition state quantum numbers (0,0,2), strongly perturbs the cross sections for the initial rovibrational state HCl(v=1, j=5), which was therefore considered in all our calculations. For E≥0.680 eV, which is well removed from the resonance energy, the QCT and CSH results are in good agreement, but for E near the resonance energy, important quantum effects are found in the integral cross sections, product state distributions, and differential cross sections. The CSH integral cross sections show smooth steplike increases for E≈0.642 eV, which are not seen in the QCT results. Associated with these steps are increased branching to the v′=0 product HCl vibrational state, and a strong propensity for the production of rotational states with j′=15 and 16 for v′=0. These features of the product energy partitioning are not present in the QCT results, although the correct rotational distributions are approximately recovered if the final vibrational action is constrained to match its quantum value. The CSH differential cross sections show a sudden shift from backward to sideward scattering between 0.642 and 0.660 eV, while the QCT cross sections remain backward peaked. An analysis of the "number of atom-diatom encounters," during the course of a reactive collision, shows that there are chattering trajectories. These are associated with sideward scattering, but their probability is low and as a result they do not produce distinct features in the angular distributions. However, if the classical deflection function is weighted by the quantum reaction probability, angular distributions are obtained that are in reasonable agreement with the CSH angular distributions (including resonance features).

AB - We present the results of quasiclassical trajectory (QCT) and quantum centrifugal sudden hyperspherical (CSH) scattering calculations for the Cl+HCl→ClH+Cl reaction using a semiempirical potential energy surface. In particular, we report state-to-state integral and differential cross sections in the vicinity of a transition state resonance that occurs at a total energy E of 0.642 eV. This resonance, which is labeled by the transition state quantum numbers (0,0,2), strongly perturbs the cross sections for the initial rovibrational state HCl(v=1, j=5), which was therefore considered in all our calculations. For E≥0.680 eV, which is well removed from the resonance energy, the QCT and CSH results are in good agreement, but for E near the resonance energy, important quantum effects are found in the integral cross sections, product state distributions, and differential cross sections. The CSH integral cross sections show smooth steplike increases for E≈0.642 eV, which are not seen in the QCT results. Associated with these steps are increased branching to the v′=0 product HCl vibrational state, and a strong propensity for the production of rotational states with j′=15 and 16 for v′=0. These features of the product energy partitioning are not present in the QCT results, although the correct rotational distributions are approximately recovered if the final vibrational action is constrained to match its quantum value. The CSH differential cross sections show a sudden shift from backward to sideward scattering between 0.642 and 0.660 eV, while the QCT cross sections remain backward peaked. An analysis of the "number of atom-diatom encounters," during the course of a reactive collision, shows that there are chattering trajectories. These are associated with sideward scattering, but their probability is low and as a result they do not produce distinct features in the angular distributions. However, if the classical deflection function is weighted by the quantum reaction probability, angular distributions are obtained that are in reasonable agreement with the CSH angular distributions (including resonance features).

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M3 - Article

VL - 97

SP - 6451

EP - 6459

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 9

ER -