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.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
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.
