Deriving the vibronic coupling constants of the cyclopentadienyl radical with density functional theory and G(0)W(0)

摘要

The vibronic coupling constants of the cyclopentadienyl radical have been calculated with G(0)W(0), HF, and density functional theory (DFT) with various exchange-correlation functionals such as PBE, PBE0, LC-omega PBE, and the non-empirically tuned LC-omega PBE*. The vibronic coupling constants for HF and DFT were derived using the gradients of the eigenvalues of the degenerate HOMOs of the closed-shell cyclopentadienyl anion, while the gradients of the corresponding quasiparticle energy levels were used in the case of G(0)W(0). The differences between the linear vibronic constants obtained using HF and DFT were found to be small and reduced further when the G(0)W(0) correction is applied to HF and DFT. Finally, the linear vibronic coupling constants calculated with G(0)W(0) were found to agree well with the values obtained using high level wave function methods in the literature, which suggests that G(0)W(0) can be a useful tool toward the study of vibronic coupling.