Theoretical study on reactions of HO2 radical with photodissociation products of Cl2so (ClSO and SO)

Milan Szori, I. Csizmadia, Christa Fittschen, B. Viskolcz

Research output: Contribution to journalArticle

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Abstract

The possible reactions of HO2 radical with the intermediates of the Cl2SO photolysis (ClSO and SO) were studied using G3MP2//B3LYP/cc-pVTZ+d level of theory and Martin's WlU method. For the reaction between HO2 and ClSO radicals, the following mechanisms are supposed to be the main reaction pathways HO2 + ClSO →3HOO × ClSO→HOO(Cl)SO →OH + ClSO2 →HO + Cl + SO 2 HO2 + ClSO →3HOO × ClSO →HOO(Cl)SO →OH + ClSO2 →HO(Cl)SO2 On the basis of G3MP2//B3LYP/cc-pVTZ+d and highly accurate WlU calculations, the reaction of HOO with 3SO species has also been explored, and the following dominant consecutive reactions may describe the fast oxygen transfer HO2 + 3SO →4HOO × SO →2HOOSO →OH + SO2 In both reaction mechanisms, the first step is a barrierless formation of relatively stable van der Waals complexes that lead via intersystem crossing to intermediate adducts. Thermodynamically favored decomposition products of 2HOOSO are OH radical and SO2. In the case of the ClSO and HO2 reaction, the dissociation of HOO(Cl)SO resulted in OH and ClSO2. Further decomposition of ClSO2 to Cl atom and SO2 competes with formation of HO(Cl)SO2 via OH addition reaction to ClSO2. We also report on high-level quantum chemical calculation (WlU) to predict values for the heat of formation of 2HSO3, 2HOOSO, and 2OOS(H)O radicals using the most reliable thermodynamic data of OH and SO3: △fH298.15K(2HSO 3) = -256.2 kJ/mol, △fH298.15K( 2HOOSO) = -152.6 kJ/ mol, and △fH 298.15K(2OOS(H)O) = -8.3 kJ/mol. On the basis of WlU standard reaction enthalpy for the reaction ClSO + HOO -HCl + SO3, the heat of formation for the ClSO radical was also computed to be △fH298.15K(ClSO) = 102.6 kJ/mol within 4 kJ mol -1 error.

Original languageEnglish
Pages (from-to)9981-9987
Number of pages7
JournalJournal of Physical Chemistry A
Volume113
Issue number37
DOIs
Publication statusPublished - Sep 17 2009

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Photodissociation
photodissociation
Decomposition
Addition reactions
Photolysis
products
Enthalpy
Thermodynamics
Oxygen
Atoms
heat of formation
Hot Temperature
decomposition
adducts
photolysis
enthalpy
dissociation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical study on reactions of HO2 radical with photodissociation products of Cl2so (ClSO and SO). / Szori, Milan; Csizmadia, I.; Fittschen, Christa; Viskolcz, B.

In: Journal of Physical Chemistry A, Vol. 113, No. 37, 17.09.2009, p. 9981-9987.

Research output: Contribution to journalArticle

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title = "Theoretical study on reactions of HO2 radical with photodissociation products of Cl2so (ClSO and SO)",
abstract = "The possible reactions of HO2 radical with the intermediates of the Cl2SO photolysis (ClSO and SO) were studied using G3MP2//B3LYP/cc-pVTZ+d level of theory and Martin's WlU method. For the reaction between HO2 and ClSO radicals, the following mechanisms are supposed to be the main reaction pathways HO2 + ClSO →3HOO × ClSO→HOO(Cl)SO →OH + ClSO2 →HO + Cl + SO 2 HO2 + ClSO →3HOO × ClSO →HOO(Cl)SO →OH + ClSO2 →HO(Cl)SO2 On the basis of G3MP2//B3LYP/cc-pVTZ+d and highly accurate WlU calculations, the reaction of HOO with 3SO species has also been explored, and the following dominant consecutive reactions may describe the fast oxygen transfer HO2 + 3SO →4HOO × SO →2HOOSO →OH + SO2 In both reaction mechanisms, the first step is a barrierless formation of relatively stable van der Waals complexes that lead via intersystem crossing to intermediate adducts. Thermodynamically favored decomposition products of 2HOOSO are OH radical and SO2. In the case of the ClSO and HO2 reaction, the dissociation of HOO(Cl)SO resulted in OH and ClSO2. Further decomposition of ClSO2 to Cl atom and SO2 competes with formation of HO(Cl)SO2 via OH addition reaction to ClSO2. We also report on high-level quantum chemical calculation (WlU) to predict values for the heat of formation of 2HSO3, 2HOOSO, and 2OOS(H)O radicals using the most reliable thermodynamic data of OH and SO3: △fH298.15K(2HSO 3) = -256.2 kJ/mol, △fH298.15K( 2HOOSO) = -152.6 kJ/ mol, and △fH 298.15K(2OOS(H)O) = -8.3 kJ/mol. On the basis of WlU standard reaction enthalpy for the reaction ClSO + HOO -HCl + SO3, the heat of formation for the ClSO radical was also computed to be △fH298.15K(ClSO) = 102.6 kJ/mol within 4 kJ mol -1 error.",
author = "Milan Szori and I. Csizmadia and Christa Fittschen and B. Viskolcz",
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T1 - Theoretical study on reactions of HO2 radical with photodissociation products of Cl2so (ClSO and SO)

AU - Szori, Milan

AU - Csizmadia, I.

AU - Fittschen, Christa

AU - Viskolcz, B.

PY - 2009/9/17

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N2 - The possible reactions of HO2 radical with the intermediates of the Cl2SO photolysis (ClSO and SO) were studied using G3MP2//B3LYP/cc-pVTZ+d level of theory and Martin's WlU method. For the reaction between HO2 and ClSO radicals, the following mechanisms are supposed to be the main reaction pathways HO2 + ClSO →3HOO × ClSO→HOO(Cl)SO →OH + ClSO2 →HO + Cl + SO 2 HO2 + ClSO →3HOO × ClSO →HOO(Cl)SO →OH + ClSO2 →HO(Cl)SO2 On the basis of G3MP2//B3LYP/cc-pVTZ+d and highly accurate WlU calculations, the reaction of HOO with 3SO species has also been explored, and the following dominant consecutive reactions may describe the fast oxygen transfer HO2 + 3SO →4HOO × SO →2HOOSO →OH + SO2 In both reaction mechanisms, the first step is a barrierless formation of relatively stable van der Waals complexes that lead via intersystem crossing to intermediate adducts. Thermodynamically favored decomposition products of 2HOOSO are OH radical and SO2. In the case of the ClSO and HO2 reaction, the dissociation of HOO(Cl)SO resulted in OH and ClSO2. Further decomposition of ClSO2 to Cl atom and SO2 competes with formation of HO(Cl)SO2 via OH addition reaction to ClSO2. We also report on high-level quantum chemical calculation (WlU) to predict values for the heat of formation of 2HSO3, 2HOOSO, and 2OOS(H)O radicals using the most reliable thermodynamic data of OH and SO3: △fH298.15K(2HSO 3) = -256.2 kJ/mol, △fH298.15K( 2HOOSO) = -152.6 kJ/ mol, and △fH 298.15K(2OOS(H)O) = -8.3 kJ/mol. On the basis of WlU standard reaction enthalpy for the reaction ClSO + HOO -HCl + SO3, the heat of formation for the ClSO radical was also computed to be △fH298.15K(ClSO) = 102.6 kJ/mol within 4 kJ mol -1 error.

AB - The possible reactions of HO2 radical with the intermediates of the Cl2SO photolysis (ClSO and SO) were studied using G3MP2//B3LYP/cc-pVTZ+d level of theory and Martin's WlU method. For the reaction between HO2 and ClSO radicals, the following mechanisms are supposed to be the main reaction pathways HO2 + ClSO →3HOO × ClSO→HOO(Cl)SO →OH + ClSO2 →HO + Cl + SO 2 HO2 + ClSO →3HOO × ClSO →HOO(Cl)SO →OH + ClSO2 →HO(Cl)SO2 On the basis of G3MP2//B3LYP/cc-pVTZ+d and highly accurate WlU calculations, the reaction of HOO with 3SO species has also been explored, and the following dominant consecutive reactions may describe the fast oxygen transfer HO2 + 3SO →4HOO × SO →2HOOSO →OH + SO2 In both reaction mechanisms, the first step is a barrierless formation of relatively stable van der Waals complexes that lead via intersystem crossing to intermediate adducts. Thermodynamically favored decomposition products of 2HOOSO are OH radical and SO2. In the case of the ClSO and HO2 reaction, the dissociation of HOO(Cl)SO resulted in OH and ClSO2. Further decomposition of ClSO2 to Cl atom and SO2 competes with formation of HO(Cl)SO2 via OH addition reaction to ClSO2. We also report on high-level quantum chemical calculation (WlU) to predict values for the heat of formation of 2HSO3, 2HOOSO, and 2OOS(H)O radicals using the most reliable thermodynamic data of OH and SO3: △fH298.15K(2HSO 3) = -256.2 kJ/mol, △fH298.15K( 2HOOSO) = -152.6 kJ/ mol, and △fH 298.15K(2OOS(H)O) = -8.3 kJ/mol. On the basis of WlU standard reaction enthalpy for the reaction ClSO + HOO -HCl + SO3, the heat of formation for the ClSO radical was also computed to be △fH298.15K(ClSO) = 102.6 kJ/mol within 4 kJ mol -1 error.

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