Université de Paris, ITODYS, CNRS, Paris, F-75006, France.
Chimie ParisTech, PSL Research University, CNRS, Institute of Chemistry for Life and Health Sciences (i-CLeHS, Paris, France.
J Comput Chem. 2021 May 30;42(14):970-981. doi: 10.1002/jcc.26517. Epub 2021 Mar 21.
We investigate the performance of a set of recently introduced range-separated double-hybrid functionals, namely ωB2-PLYP, ωB2GP-PLYP, RSX-0DH, and RSX-QIDH models for hard-to-calculate excitation energies. We compare with the parent (B2-PLYP, B2GP-PLYP, PBE0-DH, and PBE-QIDH) and other (DSD-PBEP86) double-hybrid models as well as with some of the most widely employed hybrid functionals (B3LYP, PBE0, M06-2X, and ωB97X). For this purpose, we select a number of medium-sized intra- and inter-molecular charge-transfer excitations, which are known to be challenging to calculate using time-dependent density-functional theory (TD-DFT) and for which accurate reference values are available. We assess whether the high accuracy shown by the newest double-hybrid models is also confirmed for those cases too. We find that asymptotically corrected double-hybrid models yield a superior performance, especially for the inter-molecular charge-transfer excitation energies, as compared to standard double-hybrid models. Overall, the PBE-QIDH and its corresponding range-separated RSX-QIDH functional are recommended for general-purpose TD-DFT applications, depending on whether long-range effects are expected to play a significant role.
我们研究了一组最近引入的范围分离双杂交泛函的性能，即 ωB2-PLYP、ωB2GP-PLYP、RSX-0DH 和 RSX-QIDH 模型，用于计算难以计算的激发能。我们将其与母体（B2-PLYP、B2GP-PLYP、PBE0-DH 和 PBE-QIDH）和其他（DSD-PBEP86）双杂交模型以及一些最广泛使用的混合泛函（B3LYP、PBE0、M06-2X 和 ωB97X）进行了比较。为此，我们选择了一些中等大小的分子内和分子间电荷转移激发态，这些激发态已知使用时间依赖密度泛函理论（TD-DFT）计算具有挑战性，并且有准确的参考值。我们评估了最新的双杂交模型的高精度是否也适用于这些情况。我们发现，与标准双杂交模型相比，渐近校正的双杂交模型表现出更好的性能，特别是对于分子间电荷转移激发能。总体而言，PBE-QIDH 及其对应的范围分离 RSX-QIDH 泛函推荐用于一般用途的 TD-DFT 应用，具体取决于是否预计远程效应会发挥重要作用。
