Reference CC3 Excitation Energies for Organic Chromophores: Benchmarking TD-DFT, BSE/ GW , and Wave Function Methods
Year: 2024
Type: article
Abstract: To expand the QUEST database of highly accurate vertical transition energies, we consider a series of large organic chromogens ubiquitous in dye chemistry, such as anthraquinone, azobenzene, BODIPY, and naphthalimide. We compute, at the CC3 level of theory, the singlet and triplet vertical transition energies associated with the low-lying excited states. This leads to a collection of more than 120 new highly accurate excitation energies. For several singlet transitions, we have been able to determine CCSDT transition energies with a compact basis set, finding minimal deviations from the CC3 values for most states. Subsequently, we employ these reference values to benchmark a series of lower-order wave function approaches, including the popular ADC(2) and CC2 schemes, as well as time-dependent density-functional theory (TD-DFT), both with and without applying the Tamm–Dancoff approximation (TDA). At the TD-DFT level, we evaluate a large panel of global, range-separated, local, and double hybrid functionals. Additionally, we assess the performance of the Bethe–Salpeter equation (BSE) formalism relying on both G 0 W 0 and ev GW quasiparticle energies evaluated from various starting points. It turns out that CC2 and ADC(2.5) are the most accurate models among those with respective O ( N 5 ) and O ( N 6 ) scalings with system size. In contrast, CCSD does not outperform CC2. The best performing exchange–correlation functionals include BMK, M06–2X, M06-SX, CAM-B3LYP, ωB97X-D, and LH20t, with average deviations of approximately 0.20 eV or slightly below. Errors on vertical excitation energies can be further reduced by considering double hybrids. Both SOS-ωB88PP86 and SOS-ωPBEPP86 exhibit particularly attractive performances with overall quality on par with CC2, whereas PBE0-DH and PBE-QIDH are only slightly less efficient. BSE/ev GW calculations based on Kohn–Sham starting points have been found to be particularly effective for singlet transitions, but much less for their triplet counterparts.
Institutions: Centre National de la Recherche Scientifique, Chimie et Interdisciplinarité, Synthèse, Analyse, Modélisation, Nantes Université, University of Pisa, Commissariat à l'Énergie Atomique et aux Énergies Alternatives, CEA Grenoble, Institut de Recherche Interdisciplinaire de Grenoble, Université Grenoble Alpes, Institut Néel, Université Toulouse III - Paul Sabatier, Laboratoire de Chimie et Physique Quantiques, Université de Toulouse, Institut Universitaire de France
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W4402320187