Intriguing Electronic Structures of C8 and C12 Carbon Rings

Abstract

We report on the ground and numerous excited electronic states. In the ground state the C4n rings are closed-shell systems possessing polyynic structures and can be classified as double anti-aromatic molecules. In their energetically lowest lying triplet state the rings exhibit aromatic cumulenic structures. The overall change in the electronic structures is rather dramatic upon the found moderate geometric changes from polyynic to cumulenic structure. Among others, Hund's rule is violated in both C8 and C12 in their cumulenic structures. We mention that until now, graphene is the only carbon allotrope reported to violate Hund's rule. The reasons for the violation are analyzed. Much effort has been invested to understand the relaxation pathways of the low-lying states leading the C8 from polyynic to cumulenic geometry and vice versa. On its minimum energy path, the first singlet excited state changes from open-shell character in the polyynic structure to a closed-shell state in the cumulenic structure. The cumulenic state lowest in energy is an open-shell singlet which relaxes to the closed-shell polyynic ground state.