小分子反应体系的多电子态耦合势能面和微观动力学

项目名称： 小分子反应体系的多电子态耦合势能面和微观动力学

项目编号： No.21473218

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 边文生

作者单位： 中国科学院化学研究所

项目金额： 88万元

中文摘要： 旋轨耦合和锥型交叉会引起分子反应中多个电子态之间的耦合，在此情形下，量子态层次的微观动力学研究有赖于多级耦合势能面的构建。本项目拟围绕多个电子态耦合所衍生的重要科学问题，选取CH3Cl光解和C+H2反应为典型, 在高精度耦合势能面和量子动力学层次，深入研究典型反应体系的微观动力学。上述两类反应在大气化学、天体物理等领域中扮演了重要的角色。将会揭示出多个电子态耦合在分子反应中的重要作用，可望发现新的反应机理，认识旋轨耦合、锥型交叉等与分子振动结构和反应性的关系。本项目的研究结果将具有重要的理论和学术价值；而且对于深入了解所涉反应的微观机理，合理解释实验现象，正确理解大气化学等领域中的反应机制具有重要的意义。

中文关键词： 旋轨耦合；锥形交叉；高精度势能面；反应动力学；雷诺-泰勒效应

英文摘要： Spin-orbit coupling and conical intersections can induce couplings among multiple electronic states in molecular reactions, in which case dynamical studies at the quantum state level depend on the construction of multiple coupled potential energy surfaces(PESs). Aiming at important scientific issues related to multiple electronic-state couplings, we will conduct theoretical studies at the level of highly accurate coupled PESs and quantum dynamics on the reaction dynamics of prototype reactive systems, such as CH3Cl and C+H2. These prototype reactions are very improtant in atmospheric chemistry and astrophysics. Our studies will reveal the important effects of the multiple electronic-state couplings on molecular reactions, identify new reaction mechanisms, and understand the relationship between the spin-orbit coupling and conical intersections and molecular vibrational structures and reactivity. It is expected that the research results of this program are not only of great theoretical and academic value, but also important for undestanding the detailed reaction mechanisms, for explaining many special experimental phenomena, and for understanding the basic mechanisms in such fields as atmospheric chemistry.

英文关键词： spin-orbit coupling;conical intersection;highly accurate potential energy surface;reaction dynamics;Renner-Teller effects