Some anions are known to exhibit excited states independent of external forces such as dipole moments and induced polarizabilities. Such States exist simply as a result of the stabilization of valence accepting orbitals whereby the binding energy of the extra electron is greater than the valence excitation energy. Closed-shell anions are interesting candidates for such transitions since their ground-state, spirt-paired nature makes the anions more,stable from the beginning. Consequently, this Work shows the point beyond which deprotonated, dosed-shell polycyclic aromatic hydrocarbons (PAHs) and those PAHs containing nitrogen :heteroatoms (PANHs) will exhibit valence-excited states. This behavior has already been demonstrated in some PANHs and for anistropically extended PAHs. This work establishes a general trend for PAHs/PANHs of arbitrary size and directional extension, whether in one dimension or two.. Once seven six-membered rings make up a PAH/PANH, valence excited states are present. For most classes of PAHs/PANHs, this number is closer to four. Even though most of these excited states are weak absorbers, the sheet number of PAHs present in various astronomical environments should make them significant, contributors to. astronomical spectra.