cid 247275928c3f812dababf98881032c5fbd7af20b741b3e0df26b3674796c7ebe · original · open access · via openalex
Title: Revisiting the Performance of Time-Dependent Density Functional Theory for Electronic Excitations: Assessment of 43 Popular and Recently Developed Functionals from Rungs One to Four Authors: Jiashu Liang; Xintian Feng; Diptarka Hait; Martin Head‐Gordon Venue: Journal of Chemical Theory and Computation Year: 2022 Canonical: doi:10.1021/acs.jctc.2c00160 URL: https://doi.org/10.1021/acs.jctc.2c00160 Collector: openalex OA: true ABSTRACT In this paper, the performance of more than 40 popular or recently developed density functionals is assessed for the calculation of 463 vertical excitation energies against the large and accurate QuestDB benchmark set. For this purpose, the Tamm-Dancoff approximation offers a good balance between computational efficiency and accuracy. The functionals ωB97X-D and BMK are found to offer the best performance overall with a root-mean square error (RMSE) of around 0.27 eV, better than the computationally more demanding CIS(D) wave function method with a RMSE of 0.36 eV. The results also suggest that Jacob's ladder still holds for time-dependent density functional theory excitation energies, though hybrid meta generalized-gradient approximations (meta-GGAs) are not generally better than hybrid GGAs. Effects of basis set convergence, gauge invariance correction to meta-GGAs, and nonlocal correlation (VV10) are also studied, and practical basis set recommendations are provided.