## Abstract

The unimolecular decomposition of symmetric ClO_{3} has been investigated at the G2M(CC2)//PW91PW91/ 6-311+G(3df) level of theory. The results Show that the main dissociation products are ^{3}O + OClO instead of the commonly assumed ClO + O_{2}. The rate constants at high- and low-pressure limits were predicted to be k_{2}^{∞} = 1.5 × 10^{20}T^{-1.1} exp(-18360/T) s^{-1} and k_{2}^{0} = 3.76 × 10^{25}T^{-3.28} exp(-13890/T) cm^{3} mol^{-1} s^{-1} in the temperature range 500-2500 K. For the bimolecular processes, the sum of the predicted abstraction (k_{3}) and association (k_{-2}) values can reasonably explain the experimental nonzero intercepts of the strong pressure-dependent rate constants, with the predicted total rate constants agreeing closely with the experimental values. The association and abstraction rate constants in the temperature range 200-500 K can be represented respectively by k_{-2} = 40.1T^{-6.16} exp(-403/T) for 1 Torr He and k_{3} = 1.0 × 10^{-16}T^{1.44} exp(-469/T) cm^{3} molecule^{-1} s^{-1}. The abstraction rate constant for 500-2500 K can be expressed by k_{3} = 8.69 × 10^{-17}T^{1.45} exp(-441/T) cm^{3} molecule^{-1} s^{-1}.

Original language | English |
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Pages (from-to) | 8386-8390 |

Number of pages | 5 |

Journal | Journal of Physical Chemistry A |

Volume | 106 |

Issue number | 36 |

DOIs | |

State | Published - 12 Sep 2002 |