Monitoring nonadiabatic coherence dynamics by time-resolved photoelectron spectroscopy

Time-resolved photoelectron spectroscopy (TRPES) is one of the most widely used techniques to study ultrafast molecular processes and nonadiabatic dynamics at conical intersections (CoIns). The molecular coherences emerging at CoIns contain key information about these nonadiabatic passages. However, the TRPES signal is dominated by background contributions due to state populations, and direct CoIn signatures due to molecular coherences could not be observed to date. Here, we simulate TRPES signals to monitor the relaxation of the RNA base uracil through a CoIn. We show that distinguishable signatures of coherence dynamics appear in the photoelectron signal. These could be accessed using existing ultrashort XUV and x-ray pulses, e.g., from free-electron lasers, providing most valuable information about nonadiabatic CoIn dynamics.