The efficiency of energy transfer in ultrafast electronic relaxation of molecules depends strongly on the complex interplay between electronic and nuclear motion. In this study we use wavelength-selected XUV pulses to induce relaxation dynamics of highly excited cationic states of naphthalene. Surprisingly, the observed relaxation lifetimes increase with the cationic excitation energy. We propose that this is a manifestation of a quantum mechanical population trapping that leads to delayed relaxation of molecules in the regions with a high density of excited states.
