Role of Kekul\'e and Non-Kekul\'e Structures in the Radical Character of Alternant Polycyclic Aromatic Hydrocarbons: A TAO-DFT Study

TL;DR

This study uses TAO-DFT to analyze how Kekulé and non-Kekulé structures influence the radical character of large alternant PAHs, highlighting structural effects and computational advantages.

Contribution

It demonstrates that Kekulé and non-Kekulé structures qualitatively explain radical character in PAHs, offering a cost-effective approach for large systems with static correlation.

Findings

Kekulé and non-Kekulé structures qualitatively describe radical character.

Radical character increases with system size.

Geometrical arrangements influence radical character.

Abstract

We investigate the role of Kekule and non-Kekule structures in the radical character of alternant polycyclic aromatic hydrocarbons (PAHs) using thermally-assisted-occupation density functional theory (TAO-DFT), an efficient electronic structure method for the study of large ground-state systems with strong static correlation effects. Our results reveal that the studies of Kekule and non-Kekule structures qualitatively describe the radical character of alternant PAHs, which could be useful when electronic structure calculations are infeasible due to the expensive computational cost. In addition, our results support previous findings on the increase in radical character with increasing system size. For alternant PAHs with the same number of aromatic rings, the geometrical arrangements of aromatic rings are responsible for their radical character.