Abstract The detailed kinetic mechanism of the C2H4 + NH2 reaction, an important reaction in both combustion and atmospheric chemistry, is first theoretically reported for a wide range of conditions (T = 250 – 2000 K & P = 1 – 76,000 Torr). The accurate composite electronic structure method W1U was used to explore the potential energy surface (PES) on which the temperature-and pressure-dependent kinetic behaviors of the title reaction were characterized using the complementary deterministic and stochastic Master Equation/Rice–Ramsperger–Kassel–Marcus (ME/RRKM) rate models. Corrections of the hindered internal rotation (HIR) treatment and quantum tunneling effect were included in the calculations. It is revealed that the title reaction can proceed via addition and H-abstraction channels leading to four different products (i.e., three addition products: CH2=CH-NH2 + H (P1), CH3-CH=NH + H (P2), CH2=NH + CH3 (P3) and one H-abstraction product: C2H3 + NH3 (P4)). The addition pathway is found favorable at low temperatures and high pressures: e.g., it dominates at temperatures lower than 650 K and 1250 K at P = 1 and 76 000 Torr, respectively. The computed rate constants are in good accordance with literature values; thus, the kinetic parameters, together with the thermodynamic data of the species involved, can be used confidently for modeling/simulation of nitrogen-related applications in atmospheric and combustion conditions.

中文翻译：

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C2H4 + NH2 反应的理论动力学

摘要 C2H4 + NH2 反应的详细动力学机制是燃烧和大气化学中的重要反应，首次在理论上报道了各种条件（T = 250 – 2000 K & P = 1 – 76,000 Torr）。准确的复合电子结构方法 W1U 用于探索势能面 (PES)，在该势能面 (PES) 上，使用互补确定性和随机主方程/Rice-Ramsperger-Kassel-表征标题反应的温度和压力依赖性动力学行为。 Marcus (ME/RRKM) 汇率模型。受阻内旋 (HIR) 处理和量子隧道效应的校正包括在计算中。结果表明，标题反应可以通过加成和 H-抽象通道进行，产生四种不同的产物（即，三种加成产物：CH2=CH-NH2 + H (P1)、CH3-CH=NH + H (P2)、CH2=NH + CH3 (P3) 和一种 H 抽象产物：C2H3 + NH3 (P4)）。发现添加途径在低温和高压下是有利的：例如，它在低于 650 K 和 1250 K 的温度下分别占主导地位，P = 1 和 76 000 Torr。计算出的速率常数与文献值吻合良好；因此，动力学参数以及所涉及物种的热力学数据可以自信地用于建模/模拟大气和燃烧条件下与氮相关的应用。它分别在低于 650 K 和 1250 K 的 P = 1 和 76 000 Torr 的温度下占主导地位。计算出的速率常数与文献值吻合良好；因此，动力学参数以及所涉及物种的热力学数据可以自信地用于建模/模拟大气和燃烧条件下与氮相关的应用。它分别在低于 650 K 和 1250 K 的 P = 1 和 76 000 Torr 的温度下占主导地位。计算出的速率常数与文献值吻合良好；因此，动力学参数以及所涉及物种的热力学数据可以自信地用于建模/模拟大气和燃烧条件下与氮相关的应用。