With the aim of investigating qualitatively and quantitatively the impact of using excited state relaxed or unrelaxed density for the estimation of nature and characteristic of electronic excited states, we analyzed the behavior of 52 exchange correlation functionals for the prediction of density‐based indexes such as those recently introduced in literature to evaluate the charge transfer distance (DCT) (Le Bahers et al. J. Chem. Theory Comput. 2011, 7, 2498) in the case of a prototype family of push–pull dyes. Our results show that while a qualitatively consistent assessment of the nature of the excited states is obtained using either the unrelaxed or the relaxed density, from a quantitative standpoint we observe large discrepancies in the charge transfer distance for electronic transitions having substantial CT character. This behavior is independent of nature of the exchange–correlation functional used. © 2018 Wiley Periodicals, Inc.

中文翻译：

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支撑电子密度的质量如何影响电荷转移描述符？

为了定性和定量地研究使用激发态松弛或未松弛密度对电子激发态的性质和特征估计的影响，我们分析了 52 个交换相关函数的行为，用于预测基于密度的指标，例如最近在文献中引入以评估推拉染料原型系列的电荷转移距离 (DCT)（Le Bahers 等人 J. Chem. Theory Comput. 2011, 7, 2498）。我们的结果表明，虽然使用未弛豫或弛豫密度获得了对激发态性质的定性一致评估，但从定量的角度来看，我们观察到具有实质性 CT 特征的电子跃迁的电荷转移距离存在很大差异。这种行为与所使用的交换相关函数的性质无关。© 2018 Wiley Periodicals, Inc.