Time-resolved photoelectron spectroscopy measurements combined with quantum chemistry and dynamics calculations allow unprecedented insight into the electronic relaxation mechanisms of photoexcited molecules in the gas-phase. In this Tutorial Review, we explain the essential concepts linking photoelectron spectroscopy measurements with electronic structure and how key features on the potential energy landscape are identified using quantum chemistry and quantum dynamics calculations. We illustrate how time-resolved photoelectron spectroscopy and theory work together using examples ranging in complexity from the prototypical organic molecule benzene to a pyrrole dimer bound by a weak N–H⋯π interaction and the green fluorescent protein chromophore.

中文翻译：

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使用时间分辨光电子能谱揭示光激发分子的电子弛豫动力学

时间分辨光电子能谱测量与量子化学和动力学计算相结合，使人们对气相中光激发分子的电子弛豫机理有了前所未有的了解。在本教程审查中，我们解释了将光电子能谱测量与电子结构联系起来的基本概念，以及如何使用量子化学和量子动力学计算来识别势能图景上的关键特征。我们使用复杂的例子说明了时间分辨的光电子光谱学和理论是如何协同工作的，这些例子的范围很广，从典型的有机分子苯到被弱N-H⋯π相互作用和绿色荧光蛋白发色团束缚的吡咯二聚体。