Theoretical exploration of the relativistic Jahn-Teller effect

该项目是长期努力探索分子、团簇和配位络合物中的Jahn-Teller力的一部分，这些力来自自旋轨道算符，因此具有相对论性起源。Jahn-Teller哈密顿量包括新颖的相对论耦合项，将使用群论方法导出三角形，四面体，立方和八面体系统。除了通过Breit-Pauli算子对自旋-轨道耦合的微扰描述（适用于包含轻元素和中等重元素的系统）之外，还发展了一个系统的Jahn-Teller效应理论，该理论基于电子结构理论中相对论效应的变分处理，适用于包含非常重元素的系统。静电和相对论Jahn-Teller耦合参数将通过对选定的分子和簇群的从头计算电子结构计算来确定，例如过渡金属三氟化物和六氟化物以及第四和第五主族的簇阳离子。振动和电子的Jahn-Teller光谱将计算这些系统与从头计算的Jahn-Teller哈密顿量。

This project is part of a long-term effort to explore the Jahn-Teller forces in molecules, clusters and coordination complexes which arise from the spin-orbit operator and are, therefore, of relativistic origin. Jahn-Teller Hamiltonians including novel relativistic coupling terms will be derived for trigonal, tetragonal, cubic and octahedral systems using group-theoretical methods. In addition to the perturbative description of spin-orbit coupling via the Breit-Pauli operator, which is appropriate for systems containing light and moderately heavy elements, a systematic theory of the Jahn-Teller effect is developed which is based on a variational treatment of relativistic effects in electronic-structure theory and is appropriate for systems containing very heavy elements. Electrostatic and relativistic Jahn-Teller coupling parameters will be determined with ab initio electronic-structure calculations for selected groups of molecules and clusters, e.g. transition-metal trifluorides and hexafluorides as well as cluster cations of the fourth and fifth main group. Vibrational and electronic Jahn-Teller spectra will be computed for these systems with ab initio based Jahn-Teller Hamiltonians.