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

• Published in: Physical chemistry chemical physics : PCCP 2021-09, Vol.23 (34), p.1954-197
• Main Authors: Wong, Zi Cheng, Ungur, Liviu
• Format: Article
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d1cp02795f

The linear vibronic coupling constants of the benzene radical cation and anion have been obtained with different levels of the GW approximation, including G 0 W 0 , 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 G 0 W 0 with long-range corrected functionals were found to yield the best results on the whole. The linear vibronic coupling constants of the benzene radical cation and anion have been obtained with different levels of the GW approximation in conjunction with DFT with various exchange-correlation functionals.