First-principles studies of Jahn-Teller effects in vanadium, niobium, and tantalum tetrafluoride molecules: electronic structure, vibronic spectra and radiationless decay dynamics

钒、铌和四氟化钽分子中 Jahn-Teller 效应的第一性原理研究：电子结构、电子振动谱和无辐射衰变动力学

基本信息

批准号：
328174852
负责人：
Professor Dr. Wolfgang Domcke
金额：
--
依托单位：
Ivanovo State University of Chemistry and Technology
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2017
资助国家：
德国
起止时间：
2016-12-31 至 2019-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/328174852?language=en
关键词：
First principles studies Jahn Teller

项目摘要

Transition-metal tetrahalides are a vast class of highly symmetric molecules for which very few spectroscopic data exist. Exploratory ab initio calculations of electronic potential-energy functions have provided evidence that the tetrafluorides of vanadium, niobium and tantalum exhibit exceptionally strong Jahn-Teller effects in their electronic ground state as well as in their first excited electronic state. In addition, there exist seams of conical intersection of the upper sheet of the ground-state surface with the lower sheet of the excited-state surface. The analytic representation of these multi-sheeted multi-dimensional potential-energy surfaces by Jahn-Teller Hamiltonians requires the development of the theory of the latter beyond the current state of the art. This project aims at the first-principles construction of advanced Jahn-Teller Hamiltonians for the title compounds, using multi-configuration Hartree-Fock and multireference configuration interaction methods with inclusion of spin-orbit coupling. Using these Jahn-Teller Hamiltonians, vibrational spectra of the electronic ground state and electronic spectra of the excited state will be calculated. The timescale of the radiationless deactivation of the excited state via pseudo-Jahn-Teller coupling with the ground state will be explored with time-dependent quantum dynamics methods. These detailed theoretical predictions may stimulate future experimental investigations of the spectroscopy and photophysics of transition-metal tetrahalides.

过渡金属四哈拉山脉是一类高度对称分子，很少有光谱数据。电子电位能量函数的探索性从头算计算提供了证据表明，钒，尼伯群和坦塔尔的四氟化体在其电子接地状态以及其第一个激发电子状态下表现出异常强大的Jahn-Teller效应。另外，存在地面表面上部片圆锥形相交的接缝与激发态表面的下部纸。 Jahn-Teller Hamiltonians对这些多页的多维电位 - 能量表面的分析表示，要求将后者理论的发展超过当前的最新状态。该项目的目的是使用多种配置Hartree-Fock和多差配置互动方法，将高级Jahn-Teller Hamiltonians的第一原理构建用于标题化合物。将使用这些Jahn-Teller Hamiltonians，将计算电子基态的振动光谱和激发态的电子光谱。通过时间依赖性的量子动力学方法，将探索激发态无辐射停用的时间尺度。这些详细的理论预测可能会刺激对过渡金属四分法的光谱和光体物理学的未来实验研究。