Electronic coherences in nonadiabatic molecular photophysics revealed by time-resolved photoelectron spectroscopy

Abstract

Time-resolved photoelectron spectroscopy (TRPES) signals that monitor the relaxation of the RNA base uracil upon optical excitation are simulated. Distinguishable signatures of coherence dynamics at conical intersections are identified, with temporal and spectral resolutions determined by the duration of the ionizing probe pulse. The frequency resolution of the technique, either directly provided by the signal or retrieved at the data-processing stage, can magnify the contribution from molecular coherences, enabling the extraction of most valuable information about the nonadiabatic molecular dynamics. The predicted coherence signatures in TRPES could be experimentally observed with existing ultrashort pulses from high-order harmonic generation or free-electron lasers.