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

Bargueno, P., Jambrina, P. G., Alvarino, J. M., Hernandez, M. L., Aoiz, F. J., Menendez, v, Verdasco, E., Hankel, M., Smith, S. C. and Gonzalez-Lezana, T. (2011) Energy dependent dynamics of the O(1D) + HCl reaction: a quantum, quasiclassical and statistical study. Physical Chemistry Chemical Physics, 13 18: 8502-8514. doi:10.1039/c0cp02619k


Author Bargueno, P.
Jambrina, P. G.
Alvarino, J. M.
Hernandez, M. L.
Aoiz, F. J.
Menendez, v
Verdasco, E.
Hankel, M.
Smith, S. C.
Gonzalez-Lezana, T.
Title Energy dependent dynamics of the O(1D) + HCl reaction: a quantum, quasiclassical and statistical study
Formatted title
Energy dependent dynamics of the O(1D) + HCl reaction: A quantum, quasiclassical and statistical study
Journal name Physical Chemistry Chemical Physics   Check publisher's open access policy
ISSN 1463-9076
1463-9084
Publication date 2011-04-14
Sub-type Article (original research)
DOI 10.1039/c0cp02619k
Open Access Status Not Open Access
Volume 13
Issue 18
Start page 8502
End page 8514
Total pages 13
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Collection year 2012
Language eng
Formatted 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 (E c ≤ 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.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2012 Collection
Australian Institute for Bioengineering and Nanotechnology Publications
 
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Created: Thu, 21 Jul 2011, 15:32:13 EST by Dr Marlies Hankel on behalf of Aust Institute for Bioengineering & Nanotechnology