Theoretical research on the spectroscopy and protonation energies of ionic species related to the neutral pyrrolo-aza-aromatic bases has been carried out, using Density Functional Theory (DFT) and its time dependent form (TDDFT). In the ionic species the skeleton localized (+) and (-) charge in the protonated and deprotonated species is shown to have a strong perturbation of the a-electronic states. The lowest electronic S-0 --> S-1 (pi,pi*) transitions are shown to have near-coincidence for each cation and anion for the whole homologous series, in agreement with the Valle-Kasha-Catalan rule previously stated. It is further demonstrated that simultaneous dramatic changes, upon electronic excitation, in acidity and basicity at the pyrrolo- and aza-positions of the molecular skeleton are the driving force for the biprotonic phototransfer processes in these bases. This constitutes confirmation of the proton-transfer rather than H-atom transfer as the reaction mechanism.