Knysh Iryna, Lipparini Filippo, Blondel Aymeric, Duchemin Ivan, Blase Xavier, Loos Pierre-François, Jacquemin Denis
Nantes Université, CNRS, CEISAM UMR 6230, F-44000 Nantes, France.
Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Moruzzi 3, 56124 Pisa, Italy.
J Chem Theory Comput. 2024 Sep 5. doi: 10.1021/acs.jctc.4c00906.
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 and ev 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 and 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 calculations based on Kohn-Sham starting points have been found to be particularly effective for singlet transitions, but much less for their triplet counterparts.
为了扩展高精度垂直跃迁能的QUEST数据库，我们考虑了染料化学中普遍存在的一系列大型有机发色团，如蒽醌、偶氮苯、BODIPY和萘酰亚胺。我们在CC3理论水平上计算了与低激发态相关的单重态和三重态垂直跃迁能。这产生了120多个新的高精度激发能。对于几个单重态跃迁，我们能够用紧凑基组确定CCSDT跃迁能，发现大多数态与CC3值的偏差最小。随后，我们使用这些参考值来评估一系列低阶波函数方法，包括流行的ADC(2)和CC2方案，以及含时密度泛函理论(TD-DFT)，无论是否应用Tamm-Dancoff近似(TDA)。在TD-DFT水平上，我们评估了大量的全局、范围分离、局域和双杂化泛函。此外，我们评估了基于从不同起点评估的 和 ev 准粒子能量的Bethe-Salpeter方程(BSE)形式的性能。结果表明，CC2和ADC(2.5)是在系统大小分别具有 和 标度的模型中最准确的模型。相比之下，CCSD的表现并不优于CC2。表现最佳的交换相关泛函包括BMK、M06-2X、M06-SX、CAM-B3LYP、ωB97X-D和LH20t，平均偏差约为0.20 eV或略低于此值。通过考虑双杂化可以进一步降低垂直激发能的误差。SOS-ωB88PP86和SOS-ωPBEPP86都表现出特别有吸引力的性能，整体质量与CC2相当，而PBE0-DH和PBE-QIDH的效率略低。基于Kohn-Sham起点的BSE/ev计算已被发现对单重态跃迁特别有效，但对三重态跃迁则效果差得多。
