title: TD-DFT Performance for the Visible Absorption Spectra of Organic Dyes:  Conventional versus Long-Range Hybrids.
abstract: The π → π* transitions of more than 100 organic dyes from the major classes of chromophores (quinones, diazo, ...) have been investigated using a Time-Dependent Density Functional Theory (TD-DFT) procedure relying on large atomic basis sets and the systematic modeling of solvent effects. These calculations have been performed with pure (PBE) as well as conventional (PBE0) and long-range (LR) corrected hybrid functionals (LC-PBE, LC-ωPBE, and CAM-B3LYP). The computed wavelengths are systematically guided by the percentage of exact exchange included at intermediate interelectronic distance, i.e., the λmax value always follows the PBE > PBE0 > CAM-B3LYP > LC-PBE > LC-ωPBE > HF sequence. The functional giving the best estimates of the experimental transition energies may vary, but PBE0 and CAM-B3LYP tend to outperform all other approaches. The latter functional is shown to be especially adequate to treat molecules with delocalized excited states. The mean absolute error provided by PBE0 is 22 nm (0.14 eV) with no deviation exceeding 100 nm (0.50 eV):  PBE0 is able to deliver reasonable estimates of the color of most organic dyes of practical or industrial interest. By using a calibration curve, we found that the LR functionals systematically allow an even more consistent description of the low-lying excited-state energies than the conventional hybrids. Indeed, linearly corrected LR approaches yield an average error of 10 nm for each dye family. Therefore, when such statistical treatments can be designed for given sets of dyes, a simple and rapid theoretical procedure allows both a chemically sound and a numerically accurate description of the absorption wavelengths.
authors.affiliation: 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, Department of Chemistry, Rice University, Houston, Texas 77005, and Ecole Nationale Supérieure de Chimie de Paris, Laboratoire Electrochimie et Chimie Analytique, UMR CNRS-ENSCP no. 7575, 11, rue Pierre et Marie Curie, F-75321 Paris Cedex 05, France.
authors.forename: Denis
authors.initials: D
authors.lastname: Jacquemin
authors.affiliation: 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, Department of Chemistry, Rice University, Houston, Texas 77005, and Ecole Nationale Supérieure de Chimie de Paris, Laboratoire Electrochimie et Chimie Analytique, UMR CNRS-ENSCP no. 7575, 11, rue Pierre et Marie Curie, F-75321 Paris Cedex 05, France.
authors.forename: Eric A
authors.initials: EA
authors.lastname: Perpète
authors.affiliation: 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, Department of Chemistry, Rice University, Houston, Texas 77005, and Ecole Nationale Supérieure de Chimie de Paris, Laboratoire Electrochimie et Chimie Analytique, UMR CNRS-ENSCP no. 7575, 11, rue Pierre et Marie Curie, F-75321 Paris Cedex 05, France.
authors.forename: Gustavo E
authors.initials: GE
authors.lastname: Scuseria
authors.affiliation: 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, Department of Chemistry, Rice University, Houston, Texas 77005, and Ecole Nationale Supérieure de Chimie de Paris, Laboratoire Electrochimie et Chimie Analytique, UMR CNRS-ENSCP no. 7575, 11, rue Pierre et Marie Curie, F-75321 Paris Cedex 05, France.
authors.forename: Ilaria
authors.initials: I
authors.lastname: Ciofini
authors.affiliation: 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, Department of Chemistry, Rice University, Houston, Texas 77005, and Ecole Nationale Supérieure de Chimie de Paris, Laboratoire Electrochimie et Chimie Analytique, UMR CNRS-ENSCP no. 7575, 11, rue Pierre et Marie Curie, F-75321 Paris Cedex 05, France.
authors.forename: Carlo
authors.initials: C
authors.lastname: Adamo