Electronic Properties of Möbius Cyclacenes Studied by Thermally-Assisted-Occupation Density Functional Theory.

It has been extremely difficult for traditional theoretical methods to adequately predict the properties of systems possessing radical character (i.e., multi-reference systems), especially for multi-reference systems at the nanoscale. To circumvent this, we employ thermally-assisted-occupation density functional theory (TAO-DFT) to predict the electronic properties of Möbius cyclacenes, with the number of fused benzene rings (n) ranging from 8 to 100. In addition, to investigate the significance of Möbius topology, we also compare these properties with the respective properties of cyclacenes and acenes, containing the same number of fused benzene rings. From our TAO-DFT results, Möbius cyclacenes, cyclacenes, and acenes have singlet ground states for all the cases examined. However, unlike acenes, the electronic properties of Möbius cyclacenes and cyclacenes display clear oscillation patterns when n is small (e.g., n ≤ 10 for Möbius cyclacenes and n ≤ 23 for cyclacenes), and converge to the respective properties of acenes when n greatly exceeds 30. The polyradical character of the ground states of Möbius cyclacenes should increase with the molecular size, intimately correlated with the localization of active orbitals at the edges of molecules.