Tuning UV Pump X-ray Probe Spectroscopy on the Nitrogen K Edge Reveals the Radiationless Relaxation of Pyrazine: Ab Initio Simulations Using the Quasiclassical Doorway-Window Approximation

Abstract

Transient absorption UV pump X-ray probe spectroscopy has been established as a versatile technique for the exploration of ultrafast photoinduced dynamics in valence-excited states. In this work, an ab initio theoretical framework for the simulation of time-resolved UV pump X-ray probe spectra is presented. The method is based on the description of the radiation-matter interaction in the classical doorway-window approximation and a surface-hopping algorithm for the nonadiabatic nuclear excited-state dynamics. Using the second-order algebraic-diagrammatic construction scheme for excited states, UV pump X-ray probe signals were simulated for the carbon and nitrogen K edges of pyrazine, assuming a duration of 5 fs of the UV pump and X-ray probe pulses. It is predicted that spectra measured at the nitrogen K edge carry much richer information about the ultrafast nonadiabatic dynamics in the valence-excited states of pyrazine than those measured at the carbon K edge.