Issue 18, 2011

Energy dependent dynamics of the O(1D) + HCl reaction: A quantum, quasiclassical and statistical study

Abstract

The dynamics of the reaction O(1D) + HCl → ClO + H, OH + Cl has been investigated in detail by means of a time-dependent wave packet (TDWP) method in comparison with quasiclassical trajectory (QCT) and statistical approaches on the ground potential energy surface by Martínez et al. [Phys. Chem. Chem. Phys., 2000, 2, 589]. Fully coupled quantum mechanical (QM) reaction probabilities for high values of the total angular momentum (J ≤ 50) are reported for the first time. At the low collision energy regime (Ec ≤ 0.4 eV) the TDWP probabilities are well reproduced by the QCT and statistical results for the ClO forming product channel, but for the OH + Cl arrangement, only QCT probabilities are found to agree with the QM values. The good accordance found between the rigorous statistical models and the dynamical QM and QCT calculations for the O + HCl → ClO + H process underpins the assumption that the reaction pathway leading to ClO is predominantly governed by a complex-forming mechanism. In addition, to further test the statistical character of this reaction channel, the laboratory angular distribution and time-of-flight spectra obtained in a crossed molecular beam study by Balucani et al. [Chem. Phys. Lett. 1991, 180, 34] at a collision energy as high as 0.53 eV have been simulated using the state resolved differential cross section obtained with the statistical approaches yielding a satisfactory agreement with the experimental results. For the other channel, O + HCl → OH + Cl, noticeable differences between the statistical results and those found with the QCT calculation suggest that the dynamics of the reaction are controlled by a direct mechanism. The comparison between the QCT and QM-TDWP results in the whole range of collision energies lends credence to the QCT description of the dynamics of this reaction.

Graphical abstract: Energy dependent dynamics of the O(1D) + HCl reaction: A quantum, quasiclassical and statistical study

Article information

Article type
Paper
Submitted
22 Nov 2010
Accepted
02 Mar 2011
First published
23 Mar 2011

Phys. Chem. Chem. Phys., 2011,13, 8502-8514

Energy dependent dynamics of the O(1D) + HCl reaction: A quantum, quasiclassical and statistical study

P. Bargueño, P. G. Jambrina, J. M. Alvariño, M. Menéndez, E. Verdasco, M. Hankel, S. C. Smith, F. J. Aoiz and T. González-Lezana, Phys. Chem. Chem. Phys., 2011, 13, 8502 DOI: 10.1039/C0CP02619K

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