Calculated proton affinities, polarizabilities, and some ionization energies and atomic and ring NBO charges are reported for 31 polycyclic aromatic nitrogen heterocyclics (PANHs) with 1-5 rings, calculated on the on the M06-2X/6-311+g**//B3LYP/6-31g* level of theory. The calculated proton affinities from 226 to 241 kcal mol(-1) for 3-5-ring compounds, predict well the relative experimental values. The proton affinities increase with increasing molecular size and show a linear correlation with polarizabilities. Linear geometry and nitrogen located in the central ring also favor increased proton affinity. These trends estimate a PA > 241 kcal mol-1 for an infinite linear chain, end-ring-N PANH molecule, and >261 kcal mol(-1) for an edge-N-doped graphene sheet, making it a superbase. NBO analysis shows that from pyridineH(+) to large 5-ring ions, the N-H nitrogen carries a constant q(N) = -0.46 +/- 0.1 charge, and the N-H hydrogen a constant q(H) = 0.43 +/- 0.01 positive charge, similar to the q(H) in NH4+. Overall, the NH group is nearly electrically neutral, and a nearly full positive charge is distributed on the aromatic hydrocarbon rings of the ions. When the nitrogen is in a central ring, that ring is negative, and the positive ionic charge is delocalized toward the end rings. When the nitrogen is in an end ring, the ionic charge is distributed more evenly. Increasing proton affinities with increasing polarizability result not from increasing charge transfer from the proton to the aromatic rings, but from increasing delocalization of the transferred charge in the aromatic hydrocarbon rings of the ions. In two-nitrogen compounds, interactions between the ring nitrogens decrease the proton affinities, but this effect decreases in larger ions.