Crossings of electronic potential energy surfaces in nuclear configuration space, known as conical intersections, determine the rates and outcomes of a large class of photochemical molecular processes. Much theoretical progress has been made in computing strongly coupled electronic and nuclear motions at different levels, but how to incorporate them in different spectroscopic signals and the approximations involved are less established. This will be the focus of the present review. We survey a wide range of time-resolved spectroscopic techniques which span from the infrared to the X-ray regimes and can be used for probing the nonadiabatic dynamics in the vicinity of conical intersections. Transient electronic and vibrational probes and their theoretical signal calculations are classified by their information content. This includes transient vibrational spectroscopic methods (transient infrared and femtosecond off-resonant stimulated Raman), resonant electronic probes (transient absorption and photoelectron spectroscopy), and novel stimulated X-ray Raman techniques. Along with the precise definition of what to calculate for predicting the various signals, we outline a toolbox of protocols for their simulation.

中文翻译：

---

模拟非绝热分子过程的相干多维光谱：从红外到X射线体制。

核构型空间中电子势能表面的交叉（称为圆锥形交叉）决定了一大类光化学分子过程的速率和结果。在计算不同级别的强耦合电子运动和核运动方面，已经取得了许多理论上的进展，但是如何将它们合并到不同的光谱信号中以及所涉及的近似方法却很少。这将是本次审查的重点。我们调查了范围广泛的时间分辨光谱技术，这些技术涵盖了从红外到X射线的范围，可用于探测圆锥形交叉点附近的非绝热动力学。瞬态电子和振动探头及其理论信号计算按其信息内容分类。这包括瞬态振动光谱法（瞬态红外和飞秒非共振激发拉曼），共振电子探针（瞬态吸收和光电子能谱）以及新颖的激发X射线拉曼技术。除了精确地定义预测各种信号所要计算的内容之外，我们还概述了用于仿真的协议工具箱。