Multidimensional vibrational coherence spectroscopy has been part of laser spectroscopy since the 1990s and its role in several areas of science has continuously been increasing. In this contribution, after introducing the principals of vibrational coherence spectroscopy (VCS), we review the three most widespread experimental methods for multidimensional VCS (multi-VCS), namely femtosecond stimulated Raman spectroscopy, pump-impulsive vibrational spectroscopy, and pump-degenerate four wave-mixing. Focus is given to the generation and typical analysis of the respective signals in the time and spectral domains. Critical aspects of all multidimensional techniques are the challenges in the data interpretation due to the existence of several possible contributions to the observed signals or to optical interferences and how to overcome the corresponding difficulties by exploiting experimental parameters including higher-order nonlinear effects. We overview how multidimensional vibrational coherence spectroscopy can assist a chemist in understanding how molecular structural changes and eventually photochemical reactions take place. In order to illustrate the application of the techniques described in this chapter, two molecular systems are discussed in more detail in regard to the vibrational dynamics in the electronic excited states: (1) carotenoids as a non-reactive system and (2) stilbene derivatives as a reactive system.

自1990年代以来，多维振动相干光谱学已成为激光光谱学的一部分，并且它在科学的几个领域中的作用不断提高。在此贡献中，在介绍了振动相干光谱法（VCS）的原理之后，我们回顾了三种最广泛的用于多维VCS（multi-VCS）的实验方法，即飞秒激发拉曼光谱，泵浦脉冲振动光谱法和泵浦简并的四种方法。混波。重点放在时域和频谱域中各个信号的生成和典型分析上。所有多维技术的关键方面是数据解​​释中的挑战，这归因于对观察到的信号或光学干扰存在多种可能的贡献，以及如何通过利用包括高阶非线性效应的实验参数来克服相应的困难。我们概述了多维振动相干光谱法如何帮助化学家理解分子结构变化以及最终的光化学反应的发生方式。为了说明本章中描述的技术的应用，就电子激发态下的振动动力学，更详细地讨论了两个分子系统：（1）类胡萝卜素作为非反应性系统和（2）lb衍生物作为反应系统。