Figure 1: Schematic of the experiment.

(a) Schematic of the XUV-induced dynamics in PAH molecules studied in this paper. Excited states are created in the valence shell of the cation through one of two possibilities, namely the formation of a single-hole configuration or the formation of a 2hole-1particle configuration (involving a shake-up process) (left) (IP stands for Ionization potential). The cation can be further ionized by the IR probe laser, provided that non-adiabatic relaxation has not taken place yet (middle). After relaxation, the IR probe cannot ionize the cation anymore (right). (b) Two-colour XUV+IR ion signals measured in the case of anthracene, as a function of the detected mass-to-charge ratio and the XUV-IR delay. XUV-only and IR-only signals have been subtracted. The XUV pump and IR probe pulses overlap at zero delay (black dashed line). A red colour corresponds to a signal increase, while a blue colour signifies depletion. For positive XUV-IR delays, a very fast dynamics is observed for the doubly charged anthracene ion (A²⁺, m/q=89). As explained in the text, the measurement reflects non-adiabatic relaxation in the anthracene cation (A⁺). The dynamics observed in the first fragment (A-C₂H₂⁺) is not discussed in this article.