We have evaluated the performance of various density functionals, covering generalized gradient approximation (GGA), global hybrid (GH) and range‐separated hybrid (RSH), using time dependent density functional theory (TDDFT) for computing vertical excitation energies against experimental absorption maximum (λmax) for a set of 10 different core‐substituted naphthalene diimides (cNDI) recorded in dichloromethane. The computed excitation in case of GH PBE0 is most accurate while the trend is most systematic with RSH LCY‐BLYP compared to λmax. We highlight the importance of including solvent effects for optimal agreement with the λmax. Increasing the basis set size from TZ2P to QZ4P has a negligible influence on the computed excitation energies. Notably, RSH CAMY‐B3LYP gave the least error for charge‐transfer excitation. The poorest agreement with λmax is obtained with semi‐local GGA functionals. Use of the optimally‐tuned RSH LCY‐BLYP* is not recommended because of the high computational cost and marginal improvement in results.

中文翻译：

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核取代萘二酰亚胺的 TDDFT 垂直激发能性能

我们评估了各种密度泛函的性能，包括广义梯度近似 (GGA)、全局混合 (GH) 和范围分离混合 (RSH)，使用时间相关密度泛函理论 (TDDFT) 计算垂直激发能量与实验吸收最大值(λmax) 用于在二氯甲烷中记录的一组 10 种不同的核取代萘二亚胺 (cNDI)。GH PBE0 的计算激发最准确，而与 λmax 相比，RSH LCY-BLYP 的趋势最系统。我们强调了包括溶剂效应以获得与 λmax 最佳一致的重要性。将基组大小从 TZ2P 增加到 QZ4P 对计算的激发能量的影响可以忽略不计。值得注意的是，RSH CAMY-B3LYP 对电荷转移激发的误差最小。与 λmax 最差的一致性是通过半局部 GGA 泛函获得的。不推荐使用优化调整的 RSH LCY-BLYP*，因为计算成本高且结果略有改善。