| CH与H2分子反应动力学及选态反应的理论研究 |
| |
| 引用本文： | 刘若庄,马思渝,李宗和.CH与H2分子反应动力学及选态反应的理论研究[J].物理化学学报,1993,9(2):155-160. |
| |
| 作者姓名： | 刘若庄 马思渝 李宗和 |
| |
| 作者单位： | Department of Chemistry, Beijing Normal University, Beijing 100875 |
| |
| 摘 要： | 次甲基作为化学反应源曾引起广泛的兴趣.Schaefer 及其合作者于1977年对反应CH(~4Σ~-)+H_2→CH_2(~3B_1)+H 进行过量子化学研究,但是计算中限制了一些自由度.近年来,由于能量梯度方法的发展,反应途径哈密顿理论和变分过渡态理论的提出,有可能进一步对该反应进行分子反应动力学性质的研究.本文用从头算UHF/6-31G 方法和能量梯度方法首先优化出上述反应(原子编号为CH_a+H_bH_c→H_bCH_a+H_c)的过渡态;再用
|
| 关 键 词： | 次甲基 从头算 变分过渡态 分子反应动力学 振动选态反应速率常数 |
| 收稿时间： | 1992-09-21 |
| 修稿时间： | 1992-11-16 |
Theoretical Study on the Dynamic Properties and State-Selected rate Constants of the Reaction CH(4Σ-)+H2→CH2(3B1)+H |
| |
| Liu Ruozhuang Ma Siyu Li Zonghe.Theoretical Study on the Dynamic Properties and State-Selected rate Constants of the Reaction CH(4Σ-)+H2→CH2(3B1)+H[J].Acta Physico-Chimica Sinica,1993,9(2):155-160. |
| |
| Authors: | Liu Ruozhuang Ma Siyu Li Zonghe |
| |
| Institution: | Department of Chemistry, Beijing Normal University, Beijing 100875 |
| |
| Abstract: | Tbe reaction path (IRC or MEP) of the reaction CH(~4∑~-)+H_2→CH_2(~3B_1)+H has been traced by Fukui's theory and ab initio calculation. Furthermore, the dynamic properties along the reaction path and CVT rate constants have been investi-gated by reaction path Hamiltonian theory and variational transition state theory. On this basis, the adiabatic and diabatic vibrational-state-selected rate constants were calculated. The results show that the effects of CVT method are notable, and the rate enhancement is also notable while H_2 stretch mode is vibrationally excited. |
| |
| Keywords: | Methylidyne Ab initio calculation Variational transition state Reaction dynamics Vibrational-state-selected rate constant |
| 本文献已被 CNKI 维普 等数据库收录！ |
| 点击此处可从《物理化学学报》浏览原始摘要信息 |
| 点击此处可从《物理化学学报》下载免费的PDF全文 |
