We compare different response schemes for coupling continuum solvation models to time-dependent density functional theory (TD-DFT) for the determination of solvent effects on the excited state dipole moments of solvated molecules. In particular, linear-response (LR) and state-specific (SS) formalisms are compared. Using 20 low-lying electronic excitations, displaying both localized and charge-transfer character, this study highlights the importance of applying a SS model not only for the calculation of energies, as previously reported ( J. Chem. Theory Comput., 2015, 11, 5782, DOI: 10.1021/acs.jctc.5b00679), but also for the prediction of excited state properties. Generally, when a range-separated exchange–correlation functional is used, both LR and SS schemes provide very similar dipole moments for local transitions, whereas differences of a few Debye units with respect to LR values are observed for CT transitions. The delicate interplay between the response scheme and the exchange–correlation functional is discussed as well, and we show that using an inadequate functional in a SS framework can yield to dramatic overestimations of the dipole moments.

中文翻译：

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解决方案中的激发态偶极矩：状态特定和线性响应TD-DFT值之间的比较

我们比较了耦合连续溶剂化模型与时变密度泛函理论（TD-DFT）的不同响应方案，以确定溶剂对溶剂化分子的激发态偶极矩的影响。特别是，比较了线性响应（LR）和状态特定（SS）形式主义。用20低洼电子激发，同时显示本地化和电荷转移性质，本研究的亮点，施加SS模型不仅对能量的计算如先前报道（的重要性J.化学理论COMPUT。 ，2015年，11，5782，DOI：10.1021 / acs.jctc.5b00679），也用于预测激发态性质。通常，当使用距离分隔的交换相关函数时，LR和SS方案都为局部跃迁提供了非常相似的偶极矩，而对于CT跃迁，观察到了几个德拜单位相对于LR值的差异。还讨论了响应方案和交换相关函数之间的微妙相互作用，并且我们表明，在SS框架中使用不充分的函数会导致偶极矩的急剧高估。