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arXiv · 2202.13208

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

Jiashu Liang·Xintian Feng·Diptarka Hait·Martin Head-Gordon
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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 performance and accuracy. The functionals $\omega$B97X-D and BMK are found to offer the best performance overall with a Root-Mean Square Error (RMSE) of 0.28 eV, better than the computationally more demanding CIS(D) wavefunction method with a RMSE of 0.36 eV. The results also suggest that Jacob's ladder still holds for TDDFT excitation energies, though hybrid 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.

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Jiashu Liang, Xintian Feng, Diptarka Hait, Martin Head-Gordon. 2022-02-26. 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. https://doi.org/10.1021/acs.jctc.2c00160

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