N+NO_2反应动力学研究

Kinetic Investigations on the Reaction of N with NO_2

采用UMP2（full）／6-31G^＊方法从理论上对N和NO2的反应进行了研究，计算了各反应通道上所有驻点的构型参数和振动频率，根据相对的G2MP2能量绘制的势能剖面图详细给出了N和NO2的反应机理。在此基础上，应用经Wigner校正的Eyring过渡态理论计算了在280～1500K温度范围内，1大气压下该反应3个反应通道的活化热力学量、反应速率常数、频率因子。计算结果表明：N＋NO2→IM→TS1→N2＋O2是主要反应通道，N2和O2为主要产物。

In this paper the reaction of N with NO2 has been studied theoretically using UMP2（full）/6-31G^＊ method. The structure parameters and the vibrational frequencies of each stationary point for all reaction channels are given on the same level, and the particular reaction mechanism has been given by the potential energy surface which is drawn according to the relative G2MP2 energy. On the basis of geometry optimization, using Eyring transition state theory with Wigner correction, the activation thermodynamic data, rate constant and frequency factors for the three reaction channels also have been given ranging from 280 to 1 500 K at standard pressure. The results show that the reaction channel N＋ NO2 → IM→ TS1→ N2 ＋ O2 of producing N2 ＋ O2 is the main reaction channel in the reaction of N with NO2.