Photon energy dependence of the photoelectron spectra of the anthracene anion: On the influence of autodetaching states.

Vibrationally resolved photoelectron spectra of anthracene anions have been measured for photon energies between 1.13 and 4.96 eV. In this energy range, photoemission mostly occurs via autodetaching electronically excited states of the anion, which strongly modifies the vibrational excitation of the neutral molecule after electron emission. Based on the observed vibrational patterns, eight different excited states could be identified, seven of which are resonances known from absorption spectroscopy. Distinctly different photon energy dependencies of vibrational excitations have been obtained for different excited states, hinting at strongly different photoemission lifetimes. Unexpectedly, some resonances seem to exhibit bimodal distributions of emission lifetimes, possibly due to electronic relaxation processes induced by the excitation of specific vibrational modes.