Theoretical and Computational Chemistry

Deriving the Vibronic Coupling Constants of the Cyclopentadienyl Radical with Density Functional Theory and G0W0

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Abstract

The vibronic coupling constants of the cyclopentadienyl radical have been calculated with G0W0, HF, and DFT with various exchange-correlation functionals. 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 G0W0. The differences between the linear vibronic constants obtained using HF and DFT were found to be small, and reduced further when the G0W0 correction is applied to HF and DFT. Finally, the linear vibronic coupling constants calculated with G0W0 were found to agree well with the values obtained using high level wave function methods in the literature, which suggests that G0W0 can be a useful tool towards the study of vibronic coupling.

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The following article has been accepted by the Journal of Chemical Physics

Content

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Supplementary material

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