Resonantly enhanced multiphoton ionization and zero kinetic energy photoelectron spectroscopy of benzo[e]pyrene

► REMPI of benzo[e]pyrene shows extensive vibronic coupling. ► DFT simulation with vibronic coupling is successful in reproducing the REMPI spectrum. ► ZEKE demonstrates propensity in preserving the vibrational excitation of the intermediate state. ► Remarkable structural stability of BeP during ionization.