## 摘要

The mechanism and kinetics for the gas-phase hydrolysis of N _{2}O_{4} isomers have been investigated at the CCSD(T)/6-311++G(3df,2p)//B3LYP/6-311++G(3df,2p) level of theory in conjunction with statistical rate constant calculations. Calculated results show that the contribution from the commonly assumed redox reaction of sym-N_{2}O _{4} to the homogeneous gas-phase hydrolysis of NO_{2} can be unequivocally ruled out due to the high barrier (37.6 kcal/mol) involved; instead, t-ONONO_{2} directly formed by the association of 2NO _{2}, was found to play the key role in the hydrolysis process. The kinetics for the hydrolysis reaction, 2NO_{2} + H_{2}O HONO + HNO_{3} (A) can be quatitatively interpreted by the two step mechanism: 2NO_{2} → t-ONONO_{2}, t-ONONO_{2} + H_{2}O → HONO + HNO_{3}. The predicted total forward and reverse rate constants for reaction (A), k_{tf} = 5.36 ×10^{-50}T ^{3.95}exp(1825/T) cm^{6} molecule^{-2} s^{-1} and k_{tr} = 3.31 ×10^{-19}T^{2.478}exp(-3199/T) cm^{3} molecule^{-1} s^{-1}, respectively, in the temperature range 200-2500 K, are in good agreement with the available experimental data.

原文 | English |
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頁（從 - 到） | 4466-4472 |

頁數 | 7 |

期刊 | Journal of Physical Chemistry A |

卷 | 116 |

發行號 | 18 |

DOIs | |

出版狀態 | Published - 10 5月 2012 |

## 指紋

深入研究「Ab initio chemical kinetics for the hydrolysis of N_{2}O

_{4}isomers in the gas phase」主題。共同形成了獨特的指紋。