HOMO band dispersion of crystalline rubrene: Effects of self-energy corrections within the GW approximation

We investigate the band dispersion and relevant electronic properties of rubrene single crystals within the GW approximation. Due to the self-energy correction, the dispersion of the highest occupied molecular orbital (HOMO) band increases by 0.10 eV compared to the dispersion of the Kohn-Sham eigenvalues within the generalized gradient approximation, and the effective hole mass consequently decreases. The resulting value of 0.90 times the electron rest mass along the Γ-Y direction in the Brillouin zone is closer to experimental measurements than that obtained from density-functional theory. The enhanced bandwidth is explained in terms of the intermolecular hybridization of the HOMO(Y) wave function along the stacking direction of the molecules. Overall, our results support the bandlike interpretation of charge-carrier transport in rubrene.