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To expand the existing QUEST database of accurate vertical transitionenergies [\href{https://doi.org/10.1002/wcms.1517}{V\'eril et al.~\textit{WIREsComput.~Mol.~Sci.} \textbf{2021}, \textit{11}, e1517}], we have modeled morethan 100 electronic excited states of different natures (local,charge-transfer, Rydberg, singlet, and triplet) in a dozen of mono- anddi-substituted benzenes, including aniline, benzonitrile, chlorobenzene,fluorobenzene, nitrobenzene, among others. To establish theoretical bestestimates for these vertical excitation energies, we have employed advancedcoupled-cluster methods including iterative triples (CC3 and CCSDT) and, whentechnically possible, iterative quadruples (CC4). These high-levelcomputational approaches provide a robust foundation for benchmarking a seriesof popular wave function methods. The evaluated methods all includecontributions from double excitations (ADC(2), CC2, CCSD, CIS(D), EOM-MP2,STEOM-CCSD), along with schemes that also incorporate perturbative or iterativetriples (ADC(3), CCSDR(3), CCSD(T)(a)$^\star$, and CCSDT-3). This systematicexploration not only broadens the scope of the QUEST database but alsofacilitates a rigorous assessment of different theoretical approaches in theframework of a homologous chemical series, offering valuable insights into theaccuracy and reliability of these methods in such cases. We found that bothADC(2.5) and CCSDT-3 can provide consistent estimates, whereas among lessexpensive methods SCS-CC2 is likely the most effective approach. Importantly,we show that some lower order methods may offer reasonable trends in thehomologous series while providing quite large average errors, and \emph{viceversa}. Consequently, benchmarking the accuracy of a model based solely onabsolute transition energies may not be meaningful for applications involving aseries of similar compounds.

A Mountaineering Strategy to Excited States: Accurate Vertical Transition Energies and Benchmarks for Substituted Benzenes