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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Computational Study on the Mechanism and Rate Constant for the C_6H_5 + C_6H_5NO Reaction
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Computational Study on the Mechanism and Rate Constant for the C_6H_5 + C_6H_5NO Reaction

机译：C_6H_5 + C_6H_5NO反应机理和速率常数的计算研究

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The reaction mechanism of C_6H_5 + C_6H_5NO involving four product channels on the doublet-state potential energy surface has been studied at the B3LYP/6-31+G(d,p) level of theory.The first reaction channel occurs by barrierless association forming (C_6H_5)_2NO (biphenyl nitroxide),which can undergo isomerization and decomposition.The second channel takes place by substitution reaction producing C_12)H_10) (biphenyl) and NO.The third and fourth channels involve direct hydrogen abstraction reactions producing C_6H_4NO + C_6H_6 and C_6H_5NOH + C_6H_4,respectively.Bimolecular rate constants of the above four product channels have been calculated in the temperature range 300-2000 K by the microcanonical Rice-Ramsperger-Kassel-Marcus theory and/or variational transition-state theory.The result shows the dominant reactions are channel 1 at lower temperatures (T < 800 K) and channel 3 at higher temperatures (r > 800 K).The total rate constant at 7 Torr He is predicted to be k_t = 3.94 x 10~(21) T~(-3.09) exp(-699/T) for 300-500 K,2.09 x 10~(20) T~(-3.56) exp(2315/7) for 500-1000 K,and 1.51 x 10~2 T~(3.30) exp(-3043/T) for 1000-2000 K (in units of cm~3 mol~(-1) s~(-1)),agreeing reasonably with the experimental data within their reported errors.The heats of formation of key products including biphenyl nitroxide,hydroxyl phenyl amino radical,and ,N-hydroxyl carbazole have been estimated.
机译：在理论上的B3LYP / 6-31 + G（d，p）水平上研究了C_6H_5 + C_6H_5NO在双态势能面上涉及四个产物通道的反应机理。第一个反应通道通过无障碍缔合形成（ C_6H_5）_2NO（联苯一氧化氮），可发生异构化和分解反应。第二通道通过取代反应生成C_12）H_10）（联苯）和NO。第三和第四通道涉及直接氢提取反应，生成C_6H_4NO + C_6H_6和C_6H_5NOH分别通过+典型的莱斯-拉姆斯伯格-卡塞尔-马库斯理论和/或变分过渡态理论计算了在300-2000 K温度范围内上述四个产品通道的双分子速率常数。反应是在较低温度（T <800 K）下的通道1和在较高温度（r> 800 K）下的通道3。在7 Torr He下的总速率常数预计为k_t = 3.94 x 10〜（2 1）对于300-500 K，T〜（-3.09）exp（-699 / T），2.09 x 10〜（20）对于500-1000 K，T〜（-3.56）exp（2315/7），以及1.51 x 10 1000-2000 K时〜2 T〜（3.30）exp（-3043 / T）（以cm〜3 mol〜（-1）s〜（-1）为单位），在报告的误差范围内合理地同意了实验数据估计了关键产物包括联苯硝态氮，羟基苯基氨基自由基和N-羟基咔唑的形成热。

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