【摘要】 在密度泛函理论 B3LYP/6 -31 G*基组下 ,研究 Cl ONO2 + H HONO2 + Cl和 Cl ONO2 + H OH+Cl ONO( cis)及 Cl ONO2 + H OH+ Cl ONO( trans)的反应机理 .计算得到各可能反应途径的过渡态 ,并经过内禀反应坐标 ( IRC)分析加以证实 .三个反应的活化能垒 (分别为 1 9.5 ,2 0 .0和 2 3.2 k J· mol- 1 )相差不大 ,可认为同时发生 .但第一个反应放出的热量较多 ,可以看成是反应的主通道 .更多还原

【Abstract】 The reaction mechanisms of reactions ClONO 2+HHONO 2+Cl (a), ClONO 2+HOH+ClONO (cis) (b) and ClONO 2+HOH+ClONO (trans) (c) have been studied with Gaussian 98 program and B3LYP/6-31G * method. The transition states of various possible reaction pathways were obtained and were verified by internal reaction coordinate (IRC) analysis. The results show that the activation energy of the three reactions are almost the same and are 19.5, 20.0 and 23.2 kJ·mol -1 respectively. In the dynamic way, considering the activation energy, we conclude that the three reactions can occur simultaneously. Reaction (a) gives so more energy than reaction (b) and (c) that it is more likely to \{occur\}.更多还原