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Mixed quantum-classical approach to the simulation and assignment of the time-resolved photoelectron spectra

Time-resolved photoelectron spectroscopy (TRPES) has proven to be one of the most convenient pump- probe techniques for monitoring the coupled nuclear and electronic molecular dynamics. [1] In this work we present an efficient procedure for the calculation of valence-ionization TRPES signal based on classical doorway-window (DW) [2] formalism and apply it on the case of pyrazine molecule excited to 1B2u(ππ*) state by the pump pulse, for which the experimental TRPES has been recorded. [3] The evaluation of DW expression for TRPES signal is done by combining ADC(2)-based surface hopping trajectories, [4] multireference (XMS-CASPT2) treatment of ionization channels and B-spline static-exchange DFT description of ionization continuum. [5] The method yielded excellent agreement with the experiment (Figure 1). Finally, to assign the spectrum, we apply a simple spectral decomposition scheme based on the diabatization procedure.

Pump-probe spectroscopy ; Photoelectron spectroscopy ; Pyrazine ; Surface Hopping

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