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Multiconfigurational study on the synchronous mechanisms of the ClO self-reaction leading to Cl or Cl2

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Abstract

For studying the adiabatic and nonadiabatic mechanisms of the ClO (X 2Π) + ClO (X 2Π) → ClOOCl → 2Cl (2 P u) + O2 (X 3Σ − g ) reaction (1) and the ClO (X 2Π) + ClO (X 2Π) → ClOOCl → Cl2 (X 1Σ + g ) + O2 (X 3Σ − g ) reaction (2), we calculated, by partial geometry optimizations under the C2 constraint, the O–O and O–Cl dissociation potential energy curves (PECs) from the five low-lying states of ClOOCl at the CASPT2 level. The CASSCF minimum-energy crossing point (MECP) between the potential energy surfaces of the 1 1A ground state [correlating with the product of reaction (1)] and the 1 3B state [correlating with the product of reaction (2)] states was also determined. Based on the CAS calculation results (PECs, energies, and spin–orbit coupling at the MECP), we predict that reaction (1) occurs along pathway 1: ClO (X 2Π) + ClO (X 2Π) → ClOOCl (1 1A) → 2Cl (2 P u) + O2 (X 3Σ − g ) and that reaction (2) occurs along pathway 2: ClO (X 2Π) + ClO (X 2Π) → ClOOCl (1 1A) → 1 1A/1 3B MECP (142.4 cm−1) → ClOOCl (1 3B) → Cl2 (X 1Σ + g ) + O2 (X 3Σ − g ). The needed energies (relative to the reactant) for pathways 1 and 2 are predicted to be 5.3 and 11.1 kcal/mol, respectively, which indicates that reaction (1) is more favorable than reaction (2). The present work supports the traditional photochemical model for ozone degradation: ClOOCl (1 1A), formed by two ClO (X 2Π), can directly produce O2 plus two Cl atoms.

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Acknowledgments

We appreciate the financial support for this work that was provided by National Natural Science Foundation of China through Contract No. 20773161. We thank the anonymous referees for their constructive suggestions to improve the work.

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Graduate University of Chinese Academy of Sciences, P.O. Box 4588, Beijing, 100049, People’s Republic of China

    Qingyong Meng, Hua Dong & Ming-Bao Huang

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  1. Qingyong Meng
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  2. Hua Dong
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  3. Ming-Bao Huang
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Correspondence to Qingyong Meng.

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Meng, Q., Dong, H. & Huang, MB. Multiconfigurational study on the synchronous mechanisms of the ClO self-reaction leading to Cl or Cl2 . Theor Chem Acc 131, 1194 (2012). https://doi.org/10.1007/s00214-012-1194-y

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