Capturing fingerprints of conical intersection: Complementary information of non-adiabatic dynamics from linear x-ray probes

Many recent experimental ultrafast spectroscopy studies have hinted at non-adiabatic dynamics indicating the existence of conical intersections, but their direct observation remains a challenge. The rapid change of the energy gap between the electronic states complicated their observation by requiring bandwidths of several electron volts. In this manuscript, we propose to use the combined information of different x-ray pump-probe techniques to identify the conical intersection. We theoretically study the conical intersection in pyrrole using transient x-ray absorption, time-resolved x-ray spontaneous emission, and linear off-resonant Raman spectroscopy to gather evidence of the curve crossing.