The "nonbonding" or n-orbitals of two tetraazanaphthalenes cannot be satisfactorily analyzed using the conventional model of through-space and through-bond interactions between nitrogen lone pairs, as this approach does not adequately explain the energy ordering of the n-orbitals in molecules such as 1,4,5,8-tetraazanaphthalene and 2,3,6,7-tetraazanaphthalene. An alternative computational approach is presented, in which the electronic structure of these molecules is viewed as arising from substitution-induced perturbations to the parent molecule, naphthalene. Semiempirical calculations at the CNDO/S level show that the n-orbitals can be understood in terms of perturbed naphthalene-like a-orbitals, often with significant contributions from sigma*-orbitals. This approach has been found to be instructive and quantitative, with potential applications to a wide range of related molecules.