Theoretical exploration of the relativistic Jahn-Teller effect

相对论性Jahn-Teller效应的理论探索

• 批准号: 192356176
• 负责人: Professor Dr. Wolfgang Domcke
• 金额: --
• 依托单位: Lehrstuhl für Theoretische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2010
• 资助国家: 德国
• 起止时间: 2009-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/192356176?language=en
• 关键词: Theoretical; exploration; relativistic; Jahn; Teller

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.

该项目是探索分子、团簇和配位复合物中 Jahn-Teller 力的长期努力的一部分，这些力源自自旋轨道算符，因此具有相对论起源。将使用群论方法导出三角、四方、立方和八面体系统的 Jahn-Teller 哈密顿量，包括新颖的相对论耦合项。除了通过 Breit-Pauli 算子对自旋轨道耦合进行微扰描述（适用于含有轻元素和中重元素的系统）之外，还开发了基于相对论变分处理的 Jahn-Teller 效应系统理论。电子结构理论中的影响，适用于含有非常重元素的系统。静电和相对论 Jahn-Teller 耦合参数将通过对选定的分子和团簇的从头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。将使用基于 Jahn-Teller 哈密顿量的从头计算这些系统的振动和电子 Jahn-Teller 谱。

项目成果

Quantum dynamics on a three-sheeted six-dimensional ab initio potential-energy surface of the phosphine cation: Simulation of the photoelectron spectrum and the ultrafast radiationless decay dynamics.

膦阳离子的三层六维从头算势能表面上的量子动力学：光电子能谱和超快无辐射衰变动力学的模拟

• DOI: 10.1063/1.4935601
• 发表时间: 2015
• 期刊: The Journal of chemical physics
• 作者: S. Bhattacharyya;Z. Dai;W. Domcke
• 通讯作者: W. Domcke

The (E + A) × (e + a) Jahn-Teller and pseudo-Jahn-Teller Hamiltonian including spin-orbit coupling for trigonal systems.

(E A) à (e a) Jahn-Teller 和伪 Jahn-Teller 哈密顿量，包括三角系统的自旋轨道耦合

• DOI: 10.1021/jp506793z
• 发表时间: 2014
• 期刊: The journal of physical chemistry. A
• 作者: S. Bhattacharyya;D. Opalka;L. V. Poluyanov;W. Domcke
• 通讯作者: W. Domcke

Relativistic Jahn-Teller effects in the photoelectron spectra of tetrahedral P4, As4, Sb4, and Bi4.

四面体 P4、As4、Sb4 和 Bi4 光电子能谱中的相对论 Jahn-Teller 效应

• DOI: 10.1063/1.3629779
• 发表时间: 2011
• 期刊: The Journal of chemical physics
• 作者: D. Opalka;L. V. Poluyanov;W. Domcke
• 通讯作者: W. Domcke

Relativistic theory of the Jahn-Teller effect: p-orbitals in tetrahedral and trigonal systems.

• DOI: 10.1063/1.4943863
• 发表时间: 2016-03
• 期刊: The Journal of chemical physics
• 作者: W. Domcke;Daniel Opalka;L. V. Poluyanov

Quasi-classical nonadiabatic transition probability for G3/2 × (t2 + e) Jahn–Teller systems

G3/2 × (t2 e) JahnâTeller 系统的准经典非绝热转移概率

• DOI: 10.1016/j.chemphys.2015.09.008
• 发表时间: 2015
• 期刊: Chemical Physics
• 影响因子: 2.3
• 作者: L. V.Poluyanov;V. Volokhov;W. Domcke
• 通讯作者: W. Domcke