ClONO_2与H的反应机理  

The Reaction Mechanism Between ClONO_2 and H

作　　者：孙仁安[1,2] 陶占良[1] 孙延波[2] 靳菲[1] 韩克利[3] 

机构地区：[1]辽宁师范大学化学系,大连116029 [2]吉林大学理论化学研究所,理论化学计算国家重点实验室,长春130023 [3]中国科学院大连化学物理研究所,分子反应动力学国家重点实验室,大连116023

出　　处：《高等学校化学学报》2002年第11期2129-2132,共4页Chemical Journal of Chinese Universities

基　　金：吉林大学理论化学计算国家重点实验室;辽宁省教育委员基金资助

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 .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\}.

关 键 词：C1ONO2 反应机理 硝酸氯 密度泛函理论 过渡态 氢 大气污染物 臭氧层空调 

分 类 号：X131[环境科学与工程—环境科学] O643.1[理学—物理化学]