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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.

过渡金属四卤化物是一大类高度对称的分子，其光谱数据很少。电子势能函数的探索性从头计算提供了证据，证明钒、铌和钽的四氟化物在其电子基态和第一激发态中表现出异常强烈的扬-泰勒效应。此外，基态表面的上片与激发态表面的下片存在锥形相交的接缝。要用扬-泰勒哈密顿算子解析表示这些多层多维势能面，需要后者的理论发展到目前的水平。本项目旨在利用包含自旋轨道耦合的多构型Hartree-Fock和多参考构型相互作用方法，对标题化合物的先进Jahn-Teller hamilton算符进行第一性原理构建。利用这些杨-泰勒哈密顿量，计算电子基态的振动谱和激发态的电子谱。通过与基态的伪jahn - teller耦合来探索激发态无辐射失活的时间尺度。这些详细的理论预测可能会刺激过渡金属四卤化物的光谱和光物理的未来实验研究。