Reference CC3 Excitation Energies for Organic Chromophores: Benchmarking TD-DFT, BSE/GW, and Wave Function Methods,Journal of Chemical Theory and Computation

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Reference CC3 Excitation Energies for Organic Chromophores: Benchmarking TD-DFT, BSE/GW, and Wave Function Methods
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2024-09-05 , DOI: 10.1021/acs.jctc.4c00906
Iryna Knysh ₁ , Filippo Lipparini ₂ , Aymeric Blondel ₁ , Ivan Duchemin ₃ , Xavier Blase ₄ , Pierre-François Loos ₅ , Denis Jacquemin _{1,

6}

Affiliation

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 G₀W₀ and evGW 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

O (N^{5})

$O (N^{5})$ and

O (N^{6})

$O (N^{6})$ 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/evGW calculations based on Kohn–Sham starting points have been found to be particularly effective for singlet transitions, but much less for their triplet counterparts.

中文翻译：

有机发色团的参考 CC3 激发能量：TD-DFT、BSE/GW 和波函数方法的基准测试

为了扩展高精度垂直跃迁能量的 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，例如蒽醌、偶氮苯、BODIPY 和萘二甲酰亚胺。我们在 CC3 理论水平上计算与低激发态相关的单线态和三线态垂直跃迁能量。这导致收集了 120 多种新的高精度激发能量。对于几个单重态跃迁，我们已经能够使用紧凑的基组确定 CCSDT 跃迁能量，找到大多数状态与 CC3 值的最小偏差。随后，我们使用这些参考值来对一系列低阶波函数方法进行基准测试，包括流行的 ADC(2) 和 CC2 方案，以及瞬态密度泛函理论 (TD-DFT)，无论有无应用 Tamm–Dancoff 近似 (TDA)。在 TD-DFT 级别，我们评估了大量全局泛函、范围分离泛函、局部泛函和双混合泛函。此外，我们还依赖于从不同起点评估的G ₀ W ₀和 ev GW准粒子能量来评估 Bethe-Salpeter 方程 (BSE) 形式的性能。事实证明，CC2 和 ADC(2.5) 是各自具有最准确的模型

O (N^{5})

$O (N^{5})$ 和

O (N^{6})

$O (N^{6})$
随系统大小缩放。相比之下，CCSD 的性能并不优于 CC2。性能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。通过考虑双混合可以进一步减少垂直激发能量的误差。 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 的效率仅稍低。人们发现，基于 Kohn-Sham 起点的 BSE/ev GW计算对于单线态跃迁特别有效，但对于三线态跃迁则效果较差。

更新日期：2024-09-05

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