Aromatic stabilization energies in excited states at the multiconfigurational level: assessment in archetypal organic rings

Abstract

In this study, the excited state (anti)aromaticity of archetypal rings: benzene, cyclobutadiene, and cyclooctatetraene, was investigated using the energetic criterion by calculating aromatic stabilization energies. Calculations were performed at the multiconfigurational level, including dynamic correlation effect corrections using the N-electron valence state perturbation theory (NEVPT2) method. Results were compared with previously published data based on the magnetic and delocalization criteria. Aromaticity was assessed for the ground state, singlet excited states (S₁, S₂, and S₃), and triplet excited states (T₁, T₂, T₃, and T₄). (Anti)aromaticity assignments using the energetic criterion demonstrate both agreement and discrepancies with the other criteria, particularly for higher energy electronic states demonstrating the complexity of aromaticity assignment beyond the ground state. Finally, an approximate equation is proposed for the calculation of aromatic stabilization energies in excited states using experimental data such as formation enthalpies and well-resolved absorption spectra.