Pathways for the OH + Cl2 → HOCl + Cl and HOCl + Cl → HCl + ClO Reactions

Hongyan Wang, Yudong Qiu, G. Czakó, Henry F. Schaefer

Research output: Contribution to journalArticle

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Abstract

High level coupled-cluster theory, with spin-orbit coupling evaluated via the Breit-Pauli operator in the interacting-states approach, is used to investigate the OH radical reaction with Cl2 and the subsequent reaction HOCl + Cl. The entrance complex, transition state, and exit complex for both reactions have been determined using the CCSD(T) method with correlation consistent basis sets up to cc-pV6Z. Also reported are CCSDT computations. The OH + Cl2 reaction is predicted to be endothermic by 2.2 kcal/mol, compared to the best experiments, 2.0 kcal/mol. The above theoretical results include zero-point vibrational energy corrections and spin-orbit contributions. The activation energy (Ea) of the OH + Cl2 reaction predicted here, 2.3 kcal/mol, could be as much as 1 kcal/mol too high, but it falls among the four experimental Ea values, which span the range 1.1-2.5 kcal/mol. The exothermicity of the second reaction HOCl + Cl → HCl + ClO is 8.4 kcal/mol, compared to experiment 8.7 kcal/mol. The activation energy for latter reaction is unknown experimentally, but predicted here to be large, 11.5 kcal/mol. There are currently no experiments relevant to the theoretical entrance and exit complexes predicted here.

Original languageEnglish
Pages (from-to)7802-7809
Number of pages8
JournalJournal of Physical Chemistry A
Volume119
Issue number28
DOIs
Publication statusPublished - Jul 16 2015

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Orbits
Activation energy
Experiments
entrances
activation energy
orbits
operators
energy

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Pathways for the OH + Cl2 → HOCl + Cl and HOCl + Cl → HCl + ClO Reactions. / Wang, Hongyan; Qiu, Yudong; Czakó, G.; Schaefer, Henry F.

In: Journal of Physical Chemistry A, Vol. 119, No. 28, 16.07.2015, p. 7802-7809.

Research output: Contribution to journalArticle

Wang, Hongyan ; Qiu, Yudong ; Czakó, G. ; Schaefer, Henry F. / Pathways for the OH + Cl2 → HOCl + Cl and HOCl + Cl → HCl + ClO Reactions. In: Journal of Physical Chemistry A. 2015 ; Vol. 119, No. 28. pp. 7802-7809.
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