In an effort to expand the existing QUEST database of accurate vertical transition energies [Véril et al. WIREs Comput. Mol. Sci. 2021, 11, e1517], we have modeled more than 100 electronic excited states of different natures (local, charge‐transfer, Rydberg, singlet, and triplet) in a dozen of mono‐ and di‐substituted benzenes, including aniline, benzonitrile, chlorobenzene, fluorobenzene, nitrobenzene, among others. To establish theoretical best estimates for these vertical excitation energies, we have employed advanced coupled‐cluster methods including iterative triples (CC3 and CCSDT) and, when technically possible, iterative quadruples (CC4). These high‐level computational approaches provide a robust foundation for benchmarking a series of popular wave function methods. The evaluated methods all include contributions from double excitations (ADC(2), CC2, CCSD, CIS(D), EOM‐MP2, STEOM‐CCSD), along with schemes that also incorporate perturbative or iterative triples (ADC(3), CCSDR(3), CCSD(T)(a), and CCSDT‐3). This systematic exploration not only broadens the scope of the QUEST database but also facilitates a rigorous assessment of different theoretical approaches in the framework of a homologous chemical series, offering valuable insights into the accuracy and reliability of these methods in such cases. We found that both ADC(2.5) and CCSDT‐3 can provide very consistent estimates, whereas among less expensive methods SCS‐CC2 is likely the most effective approach. Importantly, we show that some lower order methods may offer reasonable trends in the homologous series while providing quite large average errors, and vice versa. Consequently, benchmarking the accuracy of a model based solely on absolute transition energies may not be meaningful for applications involving a series of similar compounds.

中文翻译：

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激发态的登山策略：准确的垂直跃迁能量和取代苯的基准

为了扩展现有的精确垂直跃迁能量 QUEST 数据库 [Véril 等人。电线计算。摩尔。科学。2021年，11，e1517]，我们在十几种单取代和二取代苯中模拟了 100 多种不同性质的电子激发态（局域、电荷转移、里德伯、单线态和三线态），包括苯胺、苯甲腈、氯苯、氟苯、硝基苯等。为了对这些垂直激发能建立理论上的最佳估计，我们采用了先进的耦合簇方法，包括迭代三元组（CC3和CCSDT），以及技术上可行的迭代四元组（CC4）。这些高级计算方法为一系列流行的波函数方法的基准测试提供了坚实的基础。评估的方法均包括双激励（ADC(2)、CC2、CCSD、CIS(D)、EOM-MP2、STEOM-CCSD）的贡献，以及还包含微扰或迭代三元组的方案（ADC(3)、CCSDR） (3)、CCSD(T)(a) 和 CCSDT-3)。这种系统性探索不仅扩大了 QUEST 数据库的范围，而且促进了在同源化学系列框架内对不同理论方法的严格评估，为这些方法在这种情况下的准确性和可靠性提供了宝贵的见解。我们发现 ADC(2.5) 和 CCSDT-3 都可以提供非常一致的估计，而在较便宜的方法中，SCS-CC2 可能是最有效的方法。重要的是，我们表明一些低阶方法可以在同系序列中提供合理的趋势，同时提供相当大的平均误差，并且反之亦然。因此，仅基于绝对跃迁能量对模型的准确性进行基准测试对于涉及一系列相似化合物的应用可能没有意义。