Liang Jiashu, Feng Xintian, Hait Diptarka, Head-Gordon Martin
Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California at Berkeley, Berkeley, California 94720, United States.
Q-Chem Inc., Pleasanton, California 94588, United States.
J Chem Theory Comput. 2022 Jun 14;18(6):3460-3473. doi: 10.1021/acs.jctc.2c00160. Epub 2022 May 9.
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.
在本文中，针对463个垂直激发能的计算，评估了40多种常用或最近开发的密度泛函的性能，所依据的是庞大且精确的QuestDB基准集。为此，Tamm-Dancoff近似在计算效率和准确性之间提供了良好的平衡。发现泛函ωB97X-D和BMK总体表现最佳，均方根误差（RMSE）约为0.27 eV，优于计算要求更高的CIS(D)波函数方法，后者的RMSE为0.36 eV。结果还表明，对于含时密度泛函理论激发能而言，雅各布天梯仍然成立，尽管杂化元广义梯度近似（meta-GGAs）通常并不比杂化广义梯度近似（GGAs）更好。还研究了基组收敛的影响、对meta-GGAs的规范不变性校正以及非局域相关（VV10），并给出了实用的基组建议。
