Exploring vibronic coupling in the benzene radical cation and anion with different levels of the GW approximation

Abstract

The linear vibronic coupling constants of the benzene radical cation and anion have been obtained with different levels of the GW approximation, including G₀W₀, eigenvalue self-consistent GW, and quasiparticle self-consistent GW, as well as DFT with the following exchange–correlation functionals: BLYP, B3LYP, CAM-B3LYP, tuned CAM-B3LYP, and an IP-tuned CAM-B3LYP functional. The vibronic coupling constants were calculated numerically using the gradients of the eigenvalues of the degenerate HOMOs and LUMOs of the neutral benzene molecule for DFT, while the numerical gradients of the quasiparticle energies were used in the case of GW. The results were evaluated against those of high level wave function methods in the literature, and the approximate self-consistent GW methods and G₀W₀ with long-range corrected functionals were found to yield the best results on the whole.