title: Assessment of Functionals for TD-DFT Calculations of Singlet-Triplet Transitions.
abstract: The calculation of transition energies for electronically excited states remains a challenge in quantum chemistry, for which time-dependent density functional theory (TD-DFT) is often viewed as a balanced (computational effort/obtained accuracy) technique. In this study, we benchmark 34 DFT functionals in the specific framework of TD-DFT calculations for singlet-triplet transitions. The results are compared to accurate wave function data reported for the same set of 63 excited-states, and it turns out that, within the selected TD-DFT framework, BMK and M06-2X emerge as the most efficient hybrids. This investigation clearly illustrates that the conclusions drawn for singlet excited states do not necessarily hold for triplet states, even for similar molecular structures.
authors.affiliation: Groupe de Chimie-Physique Théorique et Structurale, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles, 61, B-5000 Namur, Belgium, 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: Groupe de Chimie-Physique Théorique et Structurale, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles, 61, B-5000 Namur, Belgium, 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: Groupe de Chimie-Physique Théorique et Structurale, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles, 61, B-5000 Namur, Belgium, 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: Groupe de Chimie-Physique Théorique et Structurale, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles, 61, B-5000 Namur, Belgium, 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