CH2（^3B1）＋H2→CH3＋H的反应途径及动态学理论研究  

Theoretical Studies on the Reaction Path and Dynamics of the ReactionCH_2(~3B_1)+H_2→CH_3+H

作　　者：刘若庄[1] 马思渝[1] 李宗和[1] 

机构地区：[1]北京师范大学化学系,北京100875

出　　处：《化学学报》1994年第12期1170-1176,共7页Acta Chimica Sinica

基　　金：国家自然科学基金资助课题.

摘　　要：用从头算的UHF/6-31G方法、反应途径哈密顿理论以及变分过渡态理论,计算了反应CH_2(~3B_1)+H_2→CH_3+H的反应途径、沿反应途径的动态学性质和正则变分过渡态理论的速率常数.在此基础上,计算了振动选态反应的速率常数.结果表明:经典过渡态理论高估了反应速率常数,用变分过渡态方法处理效果明显;较低温度下考虑隧道效应更重要,而用小曲率近似的校正是有效的;H_2分子的振动激发对反应速率常数有较大增进.The dynamic properties along the reaction path and CVT reaction rates of CH2(3B1)+H2 → CH3+H have been investigated by ab initio calculation, reaction path Hamiltonian theory and variational transition state theory. On this basis, the vibrational state-selected reaction rates were calculated. The results show that the effects of CVT method are notable and the rate enhancement is also notable while H2 is vibrationally excited.

关 键 词：亚甲基 氢 还原反应 反应动态学 

分 类 号：O623.1[理学—有机化学]