Electronic Properties of Hexagonal Graphene Quantum Rings from TAO-DFT

The reliable prediction of electronic properties associated with graphene nanosystems can be challenging for conventional electronic structure methods, such as Kohn–Sham (KS) density functional theory (DFT), due to the presence of strong static correlation effects in these systems. To address this challenge, TAO (thermally assisted occupation) DFT has been recently proposed. In the present study, we employ TAO-DFT to predict the electronic properties of n-HGQRs (i.e., the hexagonal graphene quantum rings consisting of n aromatic rings fused together at each side). From TAO-DFT, the ground states of n-HGQRs are singlets for all the cases investigated (n = 3–15). As the system size increases, there should be a transition from the nonradical to polyradical nature of ground-state n-HGQR. The latter should be intimately related to the localization of active TAO-orbitals at the inner and outer edges of n-HGQR, which increases with increasing system size.