The recently developed method of frequency-, angle-, and time-resolved photoelectron imaging (FAT-PI) applied to the study of the dynamics of resonances of open-shell anions is reviewed. The basic principles of the method and its experimental realisation are outlined. The dynamics of a number of radical quinone anions is then considered. Firstly, we show for para-benzoquinone how frequency- and angle-resolved photoelectron imaging provides finger-prints of the dynamics of resonances and then how time-resolved photoelectron imaging yields deep mechanistic insight into the relaxation dynamics of the resonances. The effect of chemical substitutions of the para-quinone electrophore on the dynamics of resonances is discussed. Increasing the conjugation leads to a greatly enhanced ability for resonances to decay to the ground electronic state of the radical anion. Using time-resolved photoelectron spectroscopy, it is shown that the dynamics are facilitated by a bound valence state of the anion. The addition of electron donating methoxy groups leads to a reduced ability to access the ground state compared to para-benzoquinone. Both time-resolved dynamics and calculations provide a rationale for these observations. We consider the benefits and limitations of FAT-PI and its complementarity to 2D electron spectroscopy.

中文翻译：

---

通过光分离棱镜探测临时阴离子的超快动力学

综述了最近开发的用于研究开壳阴离子共振动力学的频率、角度和时间分辨光电子成像 (FAT-PI) 方法。概述了该方法的基本原理及其实验实现。然后考虑许多自由基醌阴离子的动力学。首先，我们展示了对苯醌的频率和角度分辨光电子成像如何提供共振动力学的指纹，然后时间分辨光电子成像如何产生对共振弛豫动力学的深入机械洞察。讨论了对醌电泳的化学取代对共振动力学的影响。增加共轭导致共振衰减到自由基阴离子的基电子态的能力大大增强。使用时间分辨光电子能谱，表明阴离子的束缚价态促进了动力学。与对苯醌相比，添加供电子甲氧基导致进入基态的能力降低。时间分辨动力学和计算都为这些观察提供了基本原理。我们考虑了 FAT-PI 的优点和局限性及其与 2D 电子光谱的互补性。与对苯醌相比，添加供电子甲氧基导致进入基态的能力降低。时间分辨动力学和计算都为这些观察提供了基本原理。我们考虑了 FAT-PI 的优点和局限性及其与 2D 电子光谱的互补性。与对苯醌相比，添加供电子甲氧基导致进入基态的能力降低。时间分辨动力学和计算都为这些观察提供了基本原理。我们考虑了 FAT-PI 的优点和局限性及其与 2D 电子光谱的互补性。