Time-resolved photoelectron spectroscopy: the continuing evolution of a mature technique

Time-resolved photoelectron spectroscopy (TRPES) has become one of the most widespread techniques for probing nonadiabatic dynamics in the excited electronic states of molecules. Furthermore, the complementary development of ab initio approaches for the simulation of TRPES signals has enabled the interpretation of these transient spectra in terms of underlying coupled electronic-nuclear dynamics. In this perspective, we discuss the current state-of-the-art approaches, including efforts to push femtosecond pulses into vacuum ultraviolet and soft X-ray regimes as well as the utilization of novel polarizations to use time-resolved optical activity as a probe of nonadiabatic dynamics. We close this perspective with a forward-looking prospectus on the new areas of application for this technique. In this perspective, we discuss the current state of the art of time-resolved photoelectron spectroscopy to probe nonadiabatic dynamics, including ab initio approaches for its simulation and new experimental efforts.