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${}_5$H${}_5$) and methoxy (CH${}_3$O).

电子运动与核运动的相互作用-广泛归类为“振动耦合”-在从分子动力学到电子光谱学的各个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，因为通常的近似值（弗朗克-康登和博恩-奥本海默）常常令人不满意。在对电磁耦合效应进行了概述并介绍了表征这些特征的一些计算策略后，本文讨论了这些效应如何在各种类型的光谱中体现出来。特别强调在Jahn-Teller系统中的精细结构效应，该效应是由涉及旋转，轨道和自旋角动量的耦合引起的。与整体振动水平结构不同，在理论和实验上都进行了很好的研究，这些更微妙的效果只有在高分辨率（旋转分辨率）下才能看到，并且了解得很少。审查提供了这些分裂的量子力学起源的详细描述，并提供了一些预测它们的计算策略。本文对Jahn–Teller活性分子家族进行了广泛的概述，这些家族已通过实验和理论进行了研究。给出了两个JT活性基团的详细讨论，其中在低分辨率和高分辨率下都对理论和实验进行了比较：环戊二烯基（C 审查提供了这些分裂的量子力学起源的详细描述，并提供了一些预测它们的计算策略。本文对Jahn–Teller活性分子家族进行了广泛的概述，这些家族已通过实验和理论进行了研究。给出了两个JT活性基团的详细讨论，其中在低分辨率和高分辨率下都对理论和实验进行了比较：环戊二烯基（C 审查提供了这些分裂的量子力学起源的详细描述，并提供了一些预测它们的计算策略。本文对Jahn–Teller活性分子家族进行了广泛的概述，这些家族已通过实验和理论进行了研究。给出了两个JT活性基团的详细讨论，其中在低分辨率和高分辨率下都对理论和实验进行了比较：环戊二烯基（C${}_5$H${}_5$）和甲氧基（CH${}_3$O）。