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Quantum chemical and theoretical kinetics studies on the reaction of hydroperoxyl radical with chlorine atom

  • Vahid SahebEmail author
  • Reza Darijani
Regular Article
  • 41 Downloads

Abstract

The singlet and triplet potential energy surfaces for the reaction of HO2 radical with Cl atom are explored by using high-level combination W1BD and W1U methods. Statistical rate theories are employed to compute the rate coefficients of the main product channels including HCl + O2(\( ^{1} \Sigma _{u}^{ - } \)), HCl + O2(\( ^{3} \Sigma _{g}^{ + } \)), OH + ClO and HOOCl as a function of pressure and temperature. It is found that the rate coefficients for the product channels OH + ClO and HOOCl are strongly depended on temperature and pressure. At lower pressures and higher temperatures, the product OH + ClO is important, while at higher pressures and lower temperatures, HOOCl is the dominant product. At some moderate temperatures and pressures, the rate coefficients for the formation of OH + ClO and HOOCl could be equal. The product channel HCl + O2(\( ^{3} \Sigma _{g}^{ + } \)) proceeds via formation of a van der Waals complex Cl..HOO and, next, passes through a saddle point structure with a negative energy of − 5.0 kJ mol−1 relative to the reactants. It is shown that a two transition state model suitably describes the kinetics of this product channel.

Keywords

Chlorine Hydroperoxyl radical Quantum chemical methods Theoretical Kinetic studies 

Supplementary material

214_2018_2394_MOESM1_ESM.docx (33 kb)
Supplementary material 1 (DOCX 32 kb)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of ChemistryShahid Bahonar University of KermanKermanIran

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