Perpète Eric A, Preat Julien, André Jean-Marie, Jacquemin Denis
Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, Namur, Belgium.
J Phys Chem A. 2006 May 4;110(17):5629-35. doi: 10.1021/jp060069e.
The UV/visible spectra of a series of indirubin, isoindigo, and other indigo/thioindigo related dyes have been evaluated in various solvent environments by using the time-dependent density functional theory in conjunction with the polarizable continuum model. Even for molecules of the same family, significant differences in the excitation processes have been noted. Two hybrid functionals have been selected: B3LYP and PBE0. For a set of the 50 selected molecular cases, both functionals provide accurate lambda(max), with mean absolute deviations limited to 0.1 eV. Actually, isoindigo is the main challenging series, with systematically underestimated excitation energies, due to the different nature of the excitation process. In most cases, we found that PBE0 is more efficient in reproducing the experimental values than B3LYP for sulfur-containing dyes not featuring internal hydrogen bonds, the reverse assertion being also true. In addition, the spectra of a series of unknown dyes have been predicted.
通过使用含时密度泛函理论并结合极化连续介质模型，在各种溶剂环境中评估了一系列靛玉红、异靛蓝及其他靛蓝/硫靛蓝相关染料的紫外/可见光谱。即使对于同一家族的分子，也已注意到激发过程存在显著差异。选择了两种杂化泛函：B3LYP和PBE0。对于一组选定的50个分子实例，两种泛函都能提供准确的最大波长（λmax），平均绝对偏差限制在0.1 eV以内。实际上，异靛蓝是主要具有挑战性的系列，由于激发过程的性质不同，其激发能被系统地低估。在大多数情况下，我们发现对于不含内部氢键的含硫染料，PBE0在重现实验值方面比B3LYP更有效，反之亦然。此外，还预测了一系列未知染料的光谱。
