Exciton Self-Trapping in sp² Carbon Nanostructures Induced by Edge Ether Groups

Recent experiments have suggested that exciton self-trapping plays an important role in governing the optical properties of graphene quantum dots (GQDs) and carbon dots (CDs), while the molecular structures related to this phenomenon remain unclear. This theoretical study reports exciton self-trapping induced by edge-bonded ether (C-O-C) groups in graphene nanosheets. Density functional theory (DFT) and time-dependent DFT calculations show that the initially delocalized electron and hole are trapped in the vicinity of the edge ether groups on graphene nanosheets upon excited-state (S1) relaxation, accompanied by structural planarization of the seven-membered cyclic ether rings in the same region. The resulted significant structural deformation leads to large Stokes shift energies, which are comparable to the magnitudes of the notably large emission shift observed in experiments. This study provides a feasible explanation of the origin of exciton self-trapping and offers guidance for experiments to investigate and engineer exciton self-trapping in relevant materials.