TD-DFT Assessment of Functionals for Optical 0-0 Transitions in Solvated Dyes
TD-DFT Assessment of Functionals for Optical 0-0 Transitions in Solvated Dyes
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DOI：
10.1021/ct300326f
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发表时间：
2012-07-01
影响因子：
5.5
通讯作者：
Mennucci, Benedetta
中科院分区：
文献类型：
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作者：
Jacquemin, Denis;Planchat, Aurelien;Mennucci, Benedetta
利用TD-DFT，对40个荧光分子的绝热能进行了模拟，其中凝聚相的实验能量为0-0。我们使用了六个混合泛函（B3LYP、PBEO、M06、M06- 2x、CAM-B3LYP和LC-PBE），这些泛函在之前的TD-DFT评估中已经被证明可以提供准确的跃迁能量，我们选择了两个包含扩散的基集，并应用了最新的模型来估计体溶剂化效应。在每一种情况下，由基态和激发态之间的零点振动能量之差引起的修正都是一致确定的。基集效应也被仔细研究过。结果表明，在平均偏差方面，PBEO和M06是最有效的函数（平均绝对误差为0.22-0.23 eV）。然而，包含更精确交换的M06-2X全局混合模型和CAM-B3LYP距离分离混合模型都显著提高了预测的一致性，平均误差的退化相对可以忽略不计。此外，我们还评估了(1)交叉结构/光谱关系，(2)溶剂效应的重要性，以及(3)绝热能和垂直能之间的差异。
Using TD-DFT, we performed simulations of the adiabatic energies of 40 fluorescent molecules for which the experimental 0-0 energies in condensed phase are available. We used six hybrid functionals (B3LYP, PBEO, M06, M06-2X, CAM-B3LYP, and LC-PBE) that have been shown to provide accurate transition energies in previous TD-DFT assessments, selected two diffuse-containing basis sets, and applied the most recent models for estimating bulk solvation effects. In each case, the correction arising from the difference of zero-point vibrational energies between the ground and the excited states has been consistently determined. Basis set effects have also been carefully studied. It turned out that PBEO and M06 are the most effective functionals in terms of average deviation (mean absolute error of 0.22-0.23 eV). However, both the M06-2X global hybrid that contains more exact exchange and the CAM-B3LYP range-separated hybrid significantly improve the consistency of the prediction for a relatively negligible degradation of the average error. In addition, we assessed (1) the cross-structure/spectra relationships, (2) the importance of solvent effects, and (3) the differences between adiabatic and vertical energies.