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Nonadiabatic transitions, spin-orbit coupling, and prereactive complexes in polyatomic reaction dynamics

多原子反应动力学中的非绝热跃迁、自旋轨道耦合和预反应配合物

基本信息

批准号：
280121752
负责人：
Professor Dr. Uwe Manthe
金额：
--
依托单位：
Bereich Theoretischen Chemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2015
资助国家：
德国
起止时间：
2014-12-31 至 2018-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/280121752?language=en
关键词：
Nonadiabatic transitions spin orbit coupling

项目摘要

The project intends to contribute to the fundamental understanding of elementary chemical reaction processes in polyatomic systems. Transitions between electronic states which are induced by the approach of reactants will be investigated in detail for systems which consist of more than only three or four atoms. Vibronic and spin-orbit coupling will be explicitly included in the quantum dynamics simulations. Prereactive complexes and their importance for the reaction processes will be described in detail. As prototypical examples intensively studied by detailed experiment and theory, reactions of methane with fluorine and chlorine will be investigated.Atoms as fluorine or chlorine show degenerate electronic states which in reactions with molecules such as methane give rise to vibronic and spin-orbit coupling effects in the entrance channel of the reaction. In previous theoretical simulations, the reactions have been studied only on a single adiabatic potential energy surface and non-adiabatic transitions resulting from vibronic and spin-orbit coupling have not been accounted for. In the present project the non-adiabatic dynamics in the entrance channel of the reactions is investigated. The simulations employ coupled diabatic potential energy surfaces which accurately model the vibronic and spin-orbit coupling. Resonances caused by prereactive complexes are investigated by full-dimensional (12D) quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree approach and the effect of non-adiabatic transitions on the reaction process will be studied by trajectory surface hopping calculations. Results will be compared with recent transition state spectroscopy and crossed molecular beam experiments.

该项目旨在促进对多原子系统中基本化学反应过程的基本理解。对于由三个或四个以上原子组成的系统，将详细研究由反应物接近引起的电子态之间的跃迁。振动和自旋轨道耦合将明确包含在量子动力学模拟中。将详细描述预反应配合物及其对反应过程的重要性。作为通过详细的实验和理论深入研究的典型例子，将研究甲烷与氟和氯的反应。氟或氯等原子显示简并电子态，在与甲烷等分子的反应中，会在反应的入口通道中产生振动和自旋轨道耦合效应。在以前的理论模拟中，仅在单个绝热势能表面上研究了反应，并且没有考虑由电子振动和自旋轨道耦合引起的非绝热跃迁。在本项目中，研究了反应入口通道中的非绝热动力学。该模拟采用耦合非绝热势能面，可以准确地模拟电子振动和自旋轨道耦合。使用多层多构型时间相关 Hartree 方法通过全维（12D）量子动力学计算研究由预反应配合物引起的共振，并通过轨迹表面跳跃计算研究非绝热跃迁对反应过程的影响。结果将与最近的过渡态光谱和交叉分子束实验进行比较。