Aromaticity of aza aromatic molecules: prediction from Hückel theory with modified parameters

Hückel theory is a simple and powerful method for predicting the molecular orbital and the energy of conjugated molecules. However, the presence of nitrogen atoms in aza aromatic molecules alters the Coulomb and resonance integrals owing to the difference in electronegativity between nitrogen and carbon atoms. In this study, we focus on acridine and phenazine. Further correction is implemented based on the ring current model, thus revealing the change in resonance integral for the carbon-carbon bond along the bridge of the molecule. The Hamiltonian of the π-electron system in the Hückel method is solved using the HuLiS software. Various geometry-based aromaticity indices are used to obtain the aromaticity indices of the two non-equivalent rings. For further evaluation, the results for bond lengths are used to calculate the associated bond energy. Considering the carbon-hydrogen (CH) bonds, the total molecular energy is compared with the experimental heats of formation for a number of benzenoid hydrocarbons and aza aromatics, in addition to the two studied molecules. Finally, the correlation between the nitrogen atom on the aromaticity index and the ring energy content is evaluated to determine to which extent the Hückel model agrees with previous experimental and advanced computational studies.

Keywords:
Hückel theory; aza aromatic molecule; HuLiS software; geometry-based aromaticity; bond energy