title: Electronic Band Shapes Calculated with Optimally Tuned Range-Separated Hybrid Functionals.
abstract: Using a set of 20 organic molecules, we assess the accuracy of both the absorption and emission band shapes obtained by two optimally tuned range-separated hybrid functionals possessing 0% (LC-PBE*) and 25% (LC-PBE0*) of short-range exact exchange as well as by four other hybrid functionals including or not dispersion and long-range corrections (APF-D, PBE0-1/3, SOGGA11-X, and ωB97X-D). The band topologies are compared to experimental data and to previous time-dependent density functional theory calculations. It turns out that both optimally tuned functionals vastly improve the vibronic band shapes obtained with the non-tuned LC-PBE approach but, statistically, do not yield more accurate topologies than standard hybrid functionals. In other words, optimal tuning allows to obtain more accurate excited-state energies without degrading the description of band shapes. In addition, the LC-PBE0* 0-0 energies have been determined for a set of 40 compounds, and it is shown that the results are, on average, less accurate than those obtained by LC-PBE* for the same panel of molecules. The correlation between the optimal range-separation parameters determined for LC-PBE* and LC-PBE0* is discussed as well.
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York , 359 Natural Sciences Complex, Buffalo, New York 14260-3000, United States.
authors.forename: Barry
authors.initials: B
authors.lastname: Moore
authors.affiliation: Laboratoire CEISAM - UMR CNRS 6230, Université de Nantes , 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
authors.forename: Azzam
authors.initials: A
authors.lastname: Charaf-Eddin
authors.affiliation: Laboratoire CEISAM - UMR CNRS 6230, Université de Nantes , 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
authors.forename: Aurélien
authors.initials: A
authors.lastname: Planchat
authors.affiliation: Laboratoire LECIME - UMR CNRS 7575, Chimie-ParisTech , 11 rue P. et M. Curie, F-75231 Paris Cedex 05 France.|Institut Universitaire de France , 103, bd Saint-Michel, F-75005 Paris Cedex 05, France.
authors.forename: Carlo
authors.initials: C
authors.lastname: Adamo
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York , 359 Natural Sciences Complex, Buffalo, New York 14260-3000, United States.
authors.forename: Jochen
authors.initials: J
authors.lastname: Autschbach
authors.affiliation: Laboratoire CEISAM - UMR CNRS 6230, Université de Nantes , 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.|Institut Universitaire de France , 103, bd Saint-Michel, F-75005 Paris Cedex 05, France.
authors.forename: Denis
authors.initials: D
authors.lastname: Jacquemin