## 摘要

The reactions of N_{2}O with NO and OH radicals have been studied using ab initio molecular orbital theory. The energetics and molecular parameters, calculated by the modified Gaussian-2 method (G2M), have been used to compute the reaction rate constants on the basis of the TST and RRKM theories. The reaction N_{2}O + NO → N_{2} + NO_{2} (1) was found to proceed by direct oxygen abstraction and to have a barrier of 47 kcal/mol. The theoretical rate constant, k_{1} = 8.74 × 10^{-19} × T^{2.23} exp (-23,292/T) cm^{3}3 molecule^{-1} s^{-1}, is in close agreement with earlier estimates. The reaction of N_{2}O with OH at low temperatures and atmospheric pressure is slow and dominated by association, resulting in the HONNO intermediate. The calculated rate constant for 300 K ≤ T ≤ 500 K is lower by a few orders than the upper limits previously reported in the literature. At temperatures higher than 1000 K, the N_{2} O + OH reaction is dominated by the N_{2} + O_{2} H channel, while the HNO + NO channel is slower by 2-3 orders of magnitude. The calculated rate constants at the temperature range of 1000-5000 K for N_{2} O + OH → N_{2} + O_{2} H (2A) and N_{2} O + OH → HNO + NO (2B) are fitted by the following expressions: k_{2A} = 2.15 × 10^{-26} X T^{-4.72} × exp(-18,400/T), k_{2B} = 1.96 × 10^{-28} X T^{4.33} × exp(-12,623/T), in units of cm^{3} molecule^{-1} s^{-1}. Both N_{2}O + NO and N_{2}O + OH reactions are confirmed to enhance, albeit inefficiently, the N_{2}O decomposition by reducing its activation energy.

原文 | English |
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頁（從 - 到） | 693-703 |

頁數 | 11 |

期刊 | International Journal of Chemical Kinetics |

卷 | 28 |

發行號 | 9 |

DOIs | |

出版狀態 | Published - 9月 1996 |

## 指紋

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