乙烯与臭氧反应机理的理论研究  

Theoretical Study on Reaction Mechanism of Ethylene with Ozone

作　　者：李来才[1] 

机构地区：[1]四川师范大学化学学院,四川成都610066

出　　处：《四川师范大学学报（自然科学版）》2003年第4期388-392,共5页Journal of Sichuan Normal University（Natural Science）

基　　金：国家自然科学基金(29873029);四川省教育厅重点基金资助项目

摘　　要：用量子化学MP2方法,在6 311++G 基组水平上研究了乙烯与臭氧反应机理,对乙烯的臭氧化Criegee机理进行了理论计算,全参数优化了反应过程中反应物、中间体、过渡态和产物的几何构型,在QCISD(T)/6 311++g 水平上计算了它们的能量.并对它们进行了振动分析,以确定中间体和过渡态的真实性.研究结果表明:乙烯与臭氧反应沿Criegee机理是最可行的.但对于CH2CH2+O3→M1→TS1→H2COO+H2CO→H2CO2+H2CO→M4→TS4→P反应通道没说明,虽然相对而言该反应通道发生的可能性很小,但这条反应通道是存在的.通过研究,对乙烯臭氧化反应Criegee机理进行了补充.同时研究还发现:就乙烯与臭氧反应活性而言,乙烯与臭氧反应其控制步骤的活化能不大,也就是说乙烯与臭氧反应活性较强,它对臭氧有一定的损耗.Ab initio MP2 method has been employed to study the Criegee reaction mechanism of ethylene with ozone at 6311++G** base sets level, to optimize the geometric configurations of reactants, products, intermediates, and transition states. Energies of various reaction compounds have been calculated using QCISD(T) method at 6311++G** base sets level, and vibrational analysis has been performed. The results show that the Criegee reaction mechanism of ethylene with ozone is reliable, but CH2CH2+O3→M1→TS1→H2COO+H2CO→H2CO2+H2CO→M4→TS4→P reaction channel is not explained. Although possibility of the latter is very small, it exists. Some supplements are given to the Criegee reaction mechanism of ethylene with ozone by our study results. And we also find that the activation energy of the controlling step during the reaction between ethylene and ozone is not high. That is to say, the reaction between ethylene and ozone has a strong activity and the ethylene may deplete ozone.

关 键 词：乙烯 过渡态 反应通道 活化能 

分 类 号：O641.2[理学—物理化学]