Jacquemin Denis, Wathelet Valérie, Perpète Eric A
Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, rue de Bruxelles, 61, B-5000 Namur, Belgium.
J Phys Chem A. 2006 Jul 27;110(29):9145-52. doi: 10.1021/jp062580d.
The n --> pi* transitions in more than 100 thiocarbonyl dyes have been calculated with an ab initio procedure relying on the combination of time-dependent density functional theory (TD-DFT) for evaluating excited states and the polarizable continuum model (PCM) for modeling the bulk solvent effects on both the geometrical and electronic structures. Two hybrid functionals (B3LYP and PBE0) and several basis sets, some including f polarization functions, have been used. B3LYP provides the most accurate raw estimates, but once simple linear regression is performed, both functionals give similar results with a small advantage for PBE0. By use of the latter, the mean absolute deviation with respect to experiment is limited to 0.06 eV whereas less than 20% of the estimates differ from absorption data by more than 0.10 eV. To assess the validity limits of our model, compounds containing multiple C=S chromophores have also been considered.
已采用一种从头算程序对100多种硫代羰基染料中的n→π*跃迁进行了计算，该程序依赖于将用于评估激发态的含时密度泛函理论（TD-DFT）与用于模拟本体溶剂对几何结构和电子结构影响的极化连续介质模型（PCM）相结合。使用了两种杂化泛函（B3LYP和PBE0）以及几个基组，其中一些基组包含f极化函数。B3LYP提供了最准确的原始估计值，但一旦进行简单的线性回归，两种泛函给出的结果相似，PBE0略有优势。使用后者时，相对于实验的平均绝对偏差限制在0.06 eV，而估计值与吸收数据的差异超过0.10 eV的不到20%。为了评估我们模型的有效性极限，还考虑了含有多个C=S发色团的化合物。
