Delocalized radical cations having two nitrogen-centered charge bearing units bridged by pi systems may be considered Class III intervalence compounds. The transition energy of the longest wavelength band may therefore be equated with the E-op of Hush theory, which is twice the electronic interaction matrix element V. The optically estimated value of V (V-op = E-op/2) drops significantly (6.0 kcal/mol) when the methyl groups of tetramethyl-p-phenylenediamine radical cation (1(+), V-op = 23.3 kcal/mol) are replaced by phenyl groups in the tetraphenyl compound (3(+)) and detectably (0.6 kcal/mol) when they are replaced by bicyclic alkyl groups in bis(9-azabicyclo[3.3.1]non-9-yl)-p-phenylenediamine (4(+)). The V-op values observed for n bonds connecting the nitrogens follow the relationship V = V-o exp(-beta(n)(n-1)/2) rather well for dinitrogen (n = 3), p-phenylene (n = 5), and biphenylene (n = 9) bridges with beta(n) similar to 0.3. AM1-NCG calculations are fairly successful at predicting changes in E-op for these compounds and 1,5-dimethyl-1,5-dihydrophenazine radical cation (8(+)) but fail totally for methylviologen radical cation (10(+)). AM1 calculations predict [Me2N(CH=CH)(y)NMe2](+) to localize at y = 6 and [Me2N(C drop C)(y)NMe2](+) at y = 5, and in both cases calculated V drops below calculated lambda/2, as expected. V values for nitrogen-centered and transition metal-centered intervalence compounds are compared. Significantly larger V values for the nitrogen-centered examples cause charge delocalization to occur for larger pi systems than for transition metal-centered examples.