ClONO2与Cl（^2P3／2）的反应机理  

Reaction Mechanism Between ClONO2 and Cl(2P3/2)

作　　者：孙仁安[1] 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 [3]中国科学院大连化学物理研究所

出　　处：《高等学校化学学报》2002年第10期1903-1906,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基金资助;辽宁省教委基金资助

摘　　要：在密度泛函理论 B3 LYP/6-3 1 G* 水平上 ,研究了 Cl ONO2 +Cl(2 P3/2 ) Cl2 +NO3和 Cl ONO2 +Cl(2 P3/2 ) Cl O+Cl ONO(cis)及 Cl ONO2 +Cl(2 P3/2 ) Cl OCl+NO2 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 .反应 Cl ONO2 +Cl(2 P3/2 ) Cl2 +NO3反应活化能垒最低 ,为 4.5 k J/mol。The reaction mechanism of reaction ClONO 2+Cl( 2P 3/2) Cl 2+NO 3(a) and the reaction ClONO 2+Cl( 2P 3/2)ClO+ClONO(cis)(b) and the reaction ClONO 2+Cl( 2P 3/2)ClOCl+NO 2 has been studied with Gaussian 98, B3LYP/6-31G * method. The transition states of various possible reaction pathways are obtained and are verified by internal reaction coordinate (IRC) analysis. The results show that the activation energy of reactions (a), (b) and (c) are 4.5, 57.6 and 37.3 kJ·mol -1, respectively. In comparison with the reactions (b) and (c) , reaction (a) is the main reaction because of this activation energy.

关 键 词：ClONO2 硝酸氯 密度泛函理论 反应机理 过渡态 氯自由基 动力学 

分 类 号：O643.1[理学—物理化学] O641.121[理学—化学]