Ultrafast reorganization of the hole charge created upon outer-valence ionization of porphyrins

► Ultrafast electron dynamics following ionization of porphyrins is studied. ► Ionization spectra of the free-base porphyrin and Mg(II) porphyrin are analyzed. ► Hole charge created upon ionization spreads over the molecule in only few femtoseconds. ► This redistribution of the charge may predetermine the nuclear dynamics that follow.