^1CH2＋N2O反应的势能面  

Potential Energy Surface of 1CH2＋N2O Reaction

作　　者：刘建军[1] 封继康[1] 付伟[1] 任爱民[1] 刘桂霞[1] 

机构地区：[1]吉林大学理论化学计算国家重点实验室,长春130023

出　　处：《物理化学学报》2001年第7期586-593,共8页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金资助项目(29892168)

摘　　要：利用密度泛函理论（B3LYP）计算了1CH2＋N2O反应的反应物、中间体、过渡态及产物的几何构型.进而用从头算方法（QCISD（T））计算了单点能量.由此描绘了反应的势能面，确定了反应的最终产物通道为N2＋H2CO和NO＋HCN＋H.后者比前者有更大的分支比.N2、H2CO、NO、HCN的存在有待于实验检测.作者认为反应在室温下是加成-消除机理，而在高温下可以通过直接取代的机理获得N2＋H2CO.DFT-B3LYP was used to calculate the geometries of intermediates,transition states reactants products for ~1CH_2＋N_2O reaction using the 6-31G(d,p) basis set. Single point energies were calculated on the QCISD(T)/6-311G(d,p) level. The potential energy surfaces on the title reaction were characterized. The final product channels including N_2＋H_2CO and NO＋HCN＋H were found. The product channel of NO＋HCN＋H is more competitive than that of N_2＋H_2CO. The products N_2, H_2CO, NO, and HCN should be observed in the experiment. We think that the title reaction proceeds by an addition-elimination mechanism at room temperature. At higher temperature, directive abstraction channel with N_2＋H_2CO products becomes a possible pathway. The present work assists the experimental worker to determine reaction products.

关 键 词：亚甲基 一氧化二氮 密度泛函 从头算 势能面 反应动力学 反应机理 

分 类 号：O642[理学—物理化学]