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Computational Studies on Metathetical and Redox Processes of HOCl in the Gas Phase. 1. Reactions with H, O, HO, and HO2.

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Title: Computational Studies on Metathetical and Redox Processes of HOCl in the Gas Phase. 1. Reactions with H, O, HO, and HO2.
Authors: Z. F. Xu1, M. C. Lin1
Source: Journal of Physical Chemistry A. Jul2009, Vol. 113 Issue 30, p8811-8817. 7p.
Subjects: Potential energy surfaces, Oxidation-reduction reaction, Acids, Intermediates (Chemistry), Temperature effect, Chemical reactions, Metathesis reactions
Abstract: The potential energy surfaces of four reactions including (a) HOCl + H, (b) HOCl + O, (c) HOCl + HO, (d) HOCl + HO2, have been studied by the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVDZ, CCSD(T)/aug-cc-pVTZ//CCSD/cc-pVDZ, and CCSD(T)/6-311+G(3df,2p)//BH&HLYP/6-311+G(3df,2p) levels of theory. For both HOCl + H and HOCl + O, the direct Cl-abstraction channels take place via the lowest energy barriers; for both HOCl + HO and HOCl + HO2, the lowest energy barrier channels are the indirect H-abstraction reactions by HOx(x= 1, 2) via long-lived reaction intermediates. The rate constants for the low barrier channels have been calculated in the temperature range 200−3000 K by statistical theory. The predicted rate constants for HOCl + H and HOCl + HO are in good agreement with experimental results whereas that for HOCl + O was found to be in disagreement with the majority of available experimental data, suggesting a need for further improvement in theory and/or experiment. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:The potential energy surfaces of four reactions including (a) HOCl + H, (b) HOCl + O, (c) HOCl + HO, (d) HOCl + HO2, have been studied by the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVDZ, CCSD(T)/aug-cc-pVTZ//CCSD/cc-pVDZ, and CCSD(T)/6-311+G(3df,2p)//BH&HLYP/6-311+G(3df,2p) levels of theory. For both HOCl + H and HOCl + O, the direct Cl-abstraction channels take place via the lowest energy barriers; for both HOCl + HO and HOCl + HO2, the lowest energy barrier channels are the indirect H-abstraction reactions by HOx(x= 1, 2) via long-lived reaction intermediates. The rate constants for the low barrier channels have been calculated in the temperature range 200−3000 K by statistical theory. The predicted rate constants for HOCl + H and HOCl + HO are in good agreement with experimental results whereas that for HOCl + O was found to be in disagreement with the majority of available experimental data, suggesting a need for further improvement in theory and/or experiment. [ABSTRACT FROM AUTHOR]
ISSN:10895639
DOI:10.1021/jp905136h