(ArH2)+体系非绝热势能面的构建及相关动力学研究

(Ar+H2)+ and isotope reaction are typical three atomic ion-molecule reactions which contains prolific dynamical information. The non-adiabatic effects in the title reactions caused widespread concern.. The project study includes the following three aspects: Firstly, this project is to construct the non-adiabatic potential energy surface of the system on (ArH2)+ ion molecule reaction system by using all kinds of methods to improve the accuracy of the potential energy surface. Secondly, This rare gas molecular reaction process will be simulated on the new global non adiabatic potential energy surface by the time-dependent quantum wave packet and quasi classical trajectory methods. The collision reaction non- adiabatic process is studied on the state-state level, especially excited state process and the results are compared with the experiment. Combined with the potential energy surface and dynamical properties of the system, to comprehensive understand the information and the internal mechanism non adiabatic reaction process of the reaction dynamics. Thirdly, the Coriolis coupling is applied to the non-adiabatic reaction process to explore the influence of Coriolis effect on the reaction system, more attention is presented on the non-adiabatic process in the local of potential energy surface crossing and Coriolis coupling mechanism.

(ArH2)+体系是星际反应过程中重要的一个中间态，(Ar+)+H2及Ar+(H2+)反应是典型的三原子离子分子反应，动力学信息丰富，反应中的非绝热效应引起人们的广泛关注。. 本项目研究内容包括以下三个方面：①以(ArH2)+为研究对象，灵活运用各种拟合方法，提高势能面的精度，构建出该体系全维的非绝热势能面。②理论模拟该体系分子反应过程，运用构建出来的非绝热势能面，结合含时波包量子方法和准经典轨线方法，从态态层次上对碰撞反应非绝热过程进行研究，特别是激发态的过程，并与实验结果作比较，全面了解该反应的动力学信息，进而从势能面及动力学性质上来分析该体系非绝热反应过程的内在机制。③将科里奥利耦合应用到非绝热反应过程中，探究科里奥利效应对该反应体系的影响，关注非绝热过程中存在势能面交叉时，科里奥利耦合的作用机理。

势能面在分子反应动力学中起着无以替代的作用，对它的研究始终是物理化学领域的一个热点，构建高精度的势能面对于动力学研究来说非常的重要。科里奥利耦合和同位素效应在一些反应体系中影响很大。特别是对于一些小分子体系，科里奥利耦合和同位素效应不容忽视。该项目对ArH2+体系的势能面进行了研究，计算了NTe和PCl+分子的电子态结构和光谱数据，并采用含时量子波包方法对Li+HCl的动力学计算，部分研究成果和实验符合的很好，分析了相关的反应机理，并研究了科里奥利耦合和同位素效应对两个三原子体系反应过程的影响，对相关的激发态非绝热动力学进行了研究。