物理化学学报 >> 2001, Vol. 17 >> Issue (07): 586-593.doi: 10.3866/PKU.WHXB20010703

研究论文 上一篇    下一篇

1CH2+N2O反应的势能面

刘建军;封继康;付伟;任爱民;刘桂霞   

  1. 吉林大学理论化学计算国家重点实验室,长春 130023
  • 收稿日期:2000-11-14 修回日期:2001-01-31 发布日期:2001-07-15
  • 通讯作者: 封继康 E-mail:liujj1209@263.net

Potential Energy Surface of 1CH2+N2O Reaction

Liu Jian-Jun;Feng Ji-Kang;Fu Wei;Ren Ai-Min;Liu Gui-Xia   

  1. State Key Laboratory of Theoretical and Computational Chemistry, Jilin Universi ty, Changchun 130061
  • Received:2000-11-14 Revised:2001-01-31 Published:2001-07-15
  • Contact: Feng Ji-Kang E-mail:liujj1209@263.net

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.

关键词: 亚甲基, 一氧化二氮, 密度泛函, 从头算, 势能面

Abstract: DFT-B3LYP was used to calculate the geometries of intermediates,trans ition states reactants products for 1CH2+N2O reaction using the 6-31G(d,p) b asis set. Single point energies were calculated on the QCISD(T)/6-311G(d,p) lev el. The potential energy surfaces on the title reaction were characterized. The final product channels including N2+H2CO and NO+HCN+H were found. The product channel of NO+HCN+H is more competitive than that of N2+H2CO. The products N 2, H2CO, NO, and HCN should be observed in the experiment. We think that the tit le reaction proceeds by an addition-elimination mechanism at room temperature. At higher temperature, directive abstraction channel with N2+H2CO products beco mes a possible pathway. The present work assists the experimental worker to dete rmine reaction products.

Key words: Methylene, Nitrous oxide, Density function theory, Ab initio, Potential energy surface