Vibronically coupled states: computational considerations and characterisation of vibronic and rovibronic spectroscopic parameters
Vibronically coupled states: computational considerations and characterisation of vibronic and rovibronic spectroscopic parameters
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DOI：
10.1080/0144235x.2021.1874118
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发表时间：
2021-04
影响因子：
6.1
通讯作者：
Ketan Sharma;T. Miller;J. Stanton
中科院分区：
文献类型：
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作者：
Ketan Sharma;T. Miller;J. Stanton
电子和核运动的相互作用-广义上被归类为“电子振动耦合”-在从分子动力学到电子光谱学的领域中发挥着许多作用。此外，这些现象对计算电子光谱学和量子化学都提出了重大挑战，因为通常的近似（Franck-Condon和Born-Oppenheimer）往往不能令人满意。在开始与振动耦合效应和一些计算策略的特点，他们的广泛概述后，审查讨论了这些影响是如何表现在各种类型的光谱。特别强调的是在Jahn-Teller系统的精细结构效应所产生的耦合，涉及旋转，轨道和自旋角动量。与理论上和实验上都得到了很好研究的整体电子振动能级结构不同，这些更微妙的效应只在高（旋转分辨）分辨率下才能看到，并且不太清楚。本文详细描述了这些分裂的量子力学起源，并提供了一些预测它们的计算策略。一个广泛的概述给出了家庭的Jahn-Teller活性分子，已被实验和理论研究。详细讨论了两个JT-活性自由基的理论和实验进行了比较，在低和高分辨率：甲氧基（CH）和甲氧基（CH O）。
The interaction of electronic and nuclear motion – broadly categorised as ‘vibronic coupling’ – plays a number of roles in areas that range from molecular dynamics to electronic spectroscopy. Additionally, these phenomena pose significant challenges to both computational electronic spectroscopy and quantum chemistry, as the usual approximations (Franck–Condon and Born–Oppenheimer) are often rendered unsatisfactory. After beginning with a broad overview of vibronic coupling effects and some computational strategies for characterising them, the review discusses how these effects are manifested in various types of spectra. Particular emphasis is given to fine-structure effects in Jahn–Teller systems that arise from couplings involving rotational, orbital and spin angular momenta. Unlike overall vibronic level structure, which has been quite well studied both theoretically and experimentally, these more subtle effects are seen only at high (rotationally-resolved) resolution, and are less well understood. The review gives a detailed description of the quantum-mechanical origin of these splittings and provides some computational strategies for predicting them. A broad overview is given of families of Jahn–Teller active molecules that have been investigated experimentally and theoretically. Detailed discussion is given for two JT-active radicals where theory and experiment are compared at both low and high resolution: cyclopentadienyl (C H ) and methoxy (CH O).