## 摘要

The kinetics and mechanisms of the reactions of cyanomidyl radical (HNCN) with oxygen atoms and molecules have been investigated by ab initio calculations with rate constant prediction. The doublet and quartet state potential energy surfaces (PESs) of the two reactions have been calculated by single-point calculations at the CCSD(T)/6-311+G(3df, 2p) level based on geometries optimized at the CCSD/6-311++G(d, p) level. The rate constants for various product channels of the two reactions in the temperature range of 300-3000 K are predicted by variational transition state and RRKM theories. The predicted total rate constants of the O(^{3}P) + HNCN reaction at 760 Torr Ar pressure can be represented by the expressions k_{total} (O+ HNCN) = 3.12 × 10^{-10} × T^{-0.05} exp (-37/T) cm^{3} molecule^{-1} s^{-1} at T= 300-3000 K. The branching ratios of primary channels of the O(^{3}P) + HNCN are predicted: k_{1} for producing the NO + CNH accounts for 0.72-0.64, k_{2} + k_{9} for producing the ^{3}NH + NCO accounts for 0.27-0.32, and k_{6} for producing the CN + HNO accounts for 0.01-0.07 in the temperature range studied. Meanwhile, the predicted total rate constants of the O_{2} + HNCN reaction at 760 Torr Ar pressure can be represented by the expression, k_{total}(O_{2} + HNCN) = 2.10 × 10^{-16} × T^{1.28}exp (-12200/T) cm^{3} molecule^{-1} s ^{-1} at T= 300-3000 K. The predicted branching ratio for k _{11}+k_{13} producing HO_{2} + ^{3}NCN as the primary products accounts for 0.98-1.00 in the temperature range studied.

原文 | English |
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頁（從 - 到） | 99-106 |

頁數 | 8 |

期刊 | Proceedings of the Combustion Institute |

卷 | 32 I |

發行號 | 1 |

DOIs | |

出版狀態 | Published - 1 1月 2009 |

事件 | 32nd International Symposium on Combustion - Montreal, QC, Canada 持續時間: 3 8月 2008 → 8 8月 2008 |

## 指紋

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