Jacquemin Denis, Perpète Eric A, Vydrov Oleg A, Scuseria Gustavo E, Adamo Carlo
Laboratoire de Chimie Théorique Appliquée, Groupe de Chimie-Physique Théorique et Structurale, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles 61, B-5000 Namur, Belgium.
J Chem Phys. 2007 Sep 7;127(9):094102. doi: 10.1063/1.2770700.
The first n-->pi* transitions of 18 nitroso and 16 thiocarbonyl dyes have been computed by time-dependent density functional theory (TD-DFT) using pure as well as global and range-separated hybrid functionals. It turns out that the accuracy of all hybrids is relatively similar, i.e., the inclusion of a growing fraction of exact exchange does neither worsen nor improve significantly the raw TD-DFT estimations. However, after a simple linear regression, it appears that the range-separated hybrids provide a better accuracy than global hybrids.
利用纯泛函以及全局和范围分离的杂化泛函，通过含时密度泛函理论（TD-DFT）计算了18种亚硝基染料和16种硫代羰基染料的首个n→π*跃迁。结果表明，所有杂化泛函的精度相对相似，即包含越来越多的精确交换成分，既不会显著恶化也不会显著改善原始TD-DFT估计值。然而，经过简单的线性回归后，似乎范围分离的杂化泛函比全局杂化泛函具有更高的精度。
