The optimized geometries of the intermediates, transition states computed at the PW91PW91/6–311+G(3df, 2p) level for the ClO–Cl2O2 systems. The bond lengths are given in Angstrom (Å), angles in degree (°).
Schematic energy diagrams (in kcal/mol) of the ClO–Cl2O2 systems computed at the CCSD(T)/6–311+G(3df,2p)//PW91PW91/6–311+G(3df, 2p) level. (a) ClO + ClOClO; (b) ClO + ClOOCl; (c) ClO + ClCO2. TS4 was calculated at the CBS-QB3 level.
The relative decomposition energy varies with the O′–O″ for the process of Cl′O′O″Cl″OCl (LM3) → Cl′O′ + ClOCl″O″, calculated at the PW91PW91/6- 311+G(3df,2p) level. Triangle symbol is the calculated value, the solid line is the fitted result with Varshni potential.
Predicted temperature dependent rate constants of different channels for the reactions of ClO + Cl2O2 systems: k 1, ClO + ClOClO → ClOCl + OClO; k 2, ClO + ClClO2 → ClOCl + OClO; k 3, ClO + ClOClO → ClOCl +ClOO; k 4, ClO + ClOOCl → ClOCl +ClOO.
Comparison of the predicted heats of formation (at 0 K, in kcal/mol) in this work for ClOOCl, ClOClO, and ClClO2 with the available literature data. Calculated values obtained at the CCSD(T)/6–311+G(3df, 2p)//PW91PW91/6–311+G(3df, 2p) level.
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