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Spin-orbit coupled diabatic potential energy surfaces for quantum dynamics

量子动力学的自旋轨道耦合非绝热势能面

基本信息

批准号：
251392548
负责人：
Professor Dr. Wolfgang Eisfeld
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：
2014
资助国家：
德国
起止时间：
2013-12-31 至 2021-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/251392548?language=en
关键词：
Spin orbit coupled diabatic potential

项目摘要

Vibronic and relativistic couplings among electronic states are the origin of nonadiabatic effects in molecular dynamics and often have a significant impact on reactions and spectra. Important examples are ultrafast radiationless processes in organic photochemistry, which are induced by conical intersections, or catalytic reactions with transition metals involving spin-forbidden mechanisms. The fundamental understanding and theoretical treatment of such nonadiabatic processes requires the correct handling of such couplings and the determination of fully coupled potential energy surfaces (PESs). The aim of the proposed project is the establishment of a method to generate full-dimensional diabatic PESs including relativistic (e. g. spin-orbit) couplings for medium sized molecules and to apply this new methodology to important benchmark systems. The method will treatall relevant coupling effects with high accuracy and will yield PESs in closed mathematical form to be used in quantum dynamics studies. To this end, our method called Effective Relativistic Coupling by symptotic Representation (ERCAR), which has been developed over the past few years, will be used. So far the method has been applied to the methyl iodide (CH 3 I) system, which has a particularly simple electronic structure within the methyl fragment. Next we want to apply the ERCAR methodology to iodobenzene (C6H5I) which has a more challenging electronic structure in the benzene fragment, presumably leading to new effects in the quantum dynamics. The goal of the proposed project is a thorough theoretical treatment of the photodissociationdynamics of iodobenzene in comparison to experiment and that of methyl iodide.

电子态之间的振动和相对论耦合是分子动力学中非绝热效应的起源，并且通常对反应和光谱产生重大影响。重要的例子是有机光化学中的超快无辐射过程，这是由圆锥形交叉引起的，或涉及自旋禁止机制的过渡金属催化反应。对此类非绝热过程的基本理解和理论处理需要正确处理此类耦合并确定完全耦合势能面（PES）。该项目的目标是建立一种方法来生成全维非绝热 PES，包括中等大小分子的相对论（例如自旋轨道）耦合，并将这种新方法应用于重要的基准系统。该方法将以高精度处理所有相关的耦合效应，并产生封闭数学形式的 PES，用于量子动力学研究。为此，我们将使用过去几年开发的称为渐近表示的有效相对论耦合（ERCAR）的方法。到目前为止，该方法已应用于甲基碘（CH 3 I）体系，该体系的甲基片段内具有特别简单的电子结构。接下来，我们希望将 ERCAR 方法应用于碘苯 (C6H5I)，其苯片段中具有更具挑战性的电子结构，可能会导致量子动力学中的新效应。该项目的目标是与实验和碘甲烷的光解离动力学进行比较，对碘苯的光解动力学进行彻底的理论处理。