Following the Nonadiabatic Ultrafast Dynamics of Uracil via Simulated X-ray Absorption Spectra.

Abstract

The nucleobase uracil exhibits high photostability due to ultrafast relaxation processes mediated by conical intersections (CoIns), where the interplay between nuclear and electron dynamics becomes crucial. In our previous study, we observed seemingly long-lived traces of electronic coherence for the relaxation process through the S2/S1 CoIn by applying our ansatz for coupled nuclear and electron dynamics in molecules (NEMol). In this work, we theoretically investigate how time-dependent transient X-ray absorption spectroscopy can be used to observe this ultrafast dynamics. Therefore, we calculated X-ray absorption spectra (XAS) for the oxygen K-edge, using a multireference protocol in combination with NEMol dynamics. Thus, we have access to both the transient XAS based on the nuclear wavepacket dynamics and the modulation of the signals caused by the electronic coherence induced by the excitation process and the presence of a CoIn seam. In both cases, we were able to qualitatively predict its influence on the resulting XAS.