Ab initio study of the H + ClONO2 reaction

Xiaofang Chen; Xin Zhang; Keli Han; António J.C. Varandas

doi:10.1016/j.cplett.2005.12.103

Ab initio study of the H + ClONO₂ reaction

Xiaofang Chen, Xin Zhang, Keli Han, António J.C. Varandas

Eberly College of Science

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

The mechanism of the H + ClONO₂ reaction is examined by performing QCISD calculations at geometries optimized at the MP2 level. Each of the six reaction channels involves stereoisomeric transition states that have identical energy barriers. The lowest energy barrier is 24.2 kcal mol^-1 for the indirect metathetical pathway leading to OH + cis-ClONO, being the corresponding rate constant calculated employing TST theory. The NO₂-elimination channel and the indirect metathetical pathway leading to OH + trans-ClONO should compete with each other as they have barriers of 24.8 and 25.1 kcal mol^-1. For Cl-substitution, Cl-abstraction, and N-attack, the barriers are 27.4, 35.1, and 41.3 kcal mol^-1.

Original language	English (US)
Pages (from-to)	453-459
Number of pages	7
Journal	Chemical Physics Letters
Volume	421
Issue number	4-6
DOIs	https://doi.org/10.1016/j.cplett.2005.12.103
State	Published - Apr 15 2006

All Science Journal Classification (ASJC) codes

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/j.cplett.2005.12.103

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title = "Ab initio study of the H + ClONO2 reaction",

abstract = "The mechanism of the H + ClONO2 reaction is examined by performing QCISD calculations at geometries optimized at the MP2 level. Each of the six reaction channels involves stereoisomeric transition states that have identical energy barriers. The lowest energy barrier is 24.2 kcal mol-1 for the indirect metathetical pathway leading to OH + cis-ClONO, being the corresponding rate constant calculated employing TST theory. The NO2-elimination channel and the indirect metathetical pathway leading to OH + trans-ClONO should compete with each other as they have barriers of 24.8 and 25.1 kcal mol-1. For Cl-substitution, Cl-abstraction, and N-attack, the barriers are 27.4, 35.1, and 41.3 kcal mol-1.",

author = "Xiaofang Chen and Xin Zhang and Keli Han and Varandas, {Ant{\'o}nio J.C.}",

note = "Funding Information: This work was supported by the Knowledge Innovation Program of the Chinese Academy of Sciences (INF105-SCE-02-08) and NSFC (20373071, 20333050). A.J.C.V. thanks the Dalian Institute of Chemical Physics for the hospitality during his sabbatical leave. The support of the Funda{\c c}{\~a}o para a Ci{\^e}ncia e Tecnologia, Portugal is also gratefully acknowledged.",

year = "2006",

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doi = "10.1016/j.cplett.2005.12.103",

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volume = "421",

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T1 - Ab initio study of the H + ClONO2 reaction

AU - Chen, Xiaofang

AU - Zhang, Xin

AU - Han, Keli

AU - Varandas, António J.C.

N1 - Funding Information: This work was supported by the Knowledge Innovation Program of the Chinese Academy of Sciences (INF105-SCE-02-08) and NSFC (20373071, 20333050). A.J.C.V. thanks the Dalian Institute of Chemical Physics for the hospitality during his sabbatical leave. The support of the Fundação para a Ciência e Tecnologia, Portugal is also gratefully acknowledged.

PY - 2006/4/15

Y1 - 2006/4/15

N2 - The mechanism of the H + ClONO2 reaction is examined by performing QCISD calculations at geometries optimized at the MP2 level. Each of the six reaction channels involves stereoisomeric transition states that have identical energy barriers. The lowest energy barrier is 24.2 kcal mol-1 for the indirect metathetical pathway leading to OH + cis-ClONO, being the corresponding rate constant calculated employing TST theory. The NO2-elimination channel and the indirect metathetical pathway leading to OH + trans-ClONO should compete with each other as they have barriers of 24.8 and 25.1 kcal mol-1. For Cl-substitution, Cl-abstraction, and N-attack, the barriers are 27.4, 35.1, and 41.3 kcal mol-1.

AB - The mechanism of the H + ClONO2 reaction is examined by performing QCISD calculations at geometries optimized at the MP2 level. Each of the six reaction channels involves stereoisomeric transition states that have identical energy barriers. The lowest energy barrier is 24.2 kcal mol-1 for the indirect metathetical pathway leading to OH + cis-ClONO, being the corresponding rate constant calculated employing TST theory. The NO2-elimination channel and the indirect metathetical pathway leading to OH + trans-ClONO should compete with each other as they have barriers of 24.8 and 25.1 kcal mol-1. For Cl-substitution, Cl-abstraction, and N-attack, the barriers are 27.4, 35.1, and 41.3 kcal mol-1.

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DO - 10.1016/j.cplett.2005.12.103

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EP - 459

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 4-6

ER -

Ab initio study of the H + ClONO₂ reaction

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