title: TD-DFT Assessment of Functionals for Optical 0-0 Transitions in Solvated Dyes.
abstract: Using TD-DFT, we performed simulations of the adiabatic energies of 40 fluorescent molecules for which the experimental 0-0 energies in condensed phase are available. We used six hybrid functionals (B3LYP, PBE0, M06, M06-2X, CAM-B3LYP, and LC-PBE) that have been shown to provide accurate transition energies in previous TD-DFT assessments, selected two diffuse-containing basis sets, and applied the most recent models for estimating bulk solvation effects. In each case, the correction arising from the difference of zero-point vibrational energies between the ground and the excited states has been consistently determined. Basis set effects have also been carefully studied. It turned out that PBE0 and M06 are the most effective functionals in terms of average deviation (mean absolute error of 0.22-0.23 eV). However, both the M06-2X global hybrid that contains more exact exchange and the CAM-B3LYP range-separated hybrid significantly improve the consistency of the prediction for a relatively negligible degradation of the average error. In addition, we assessed (1) the cross-structure/spectra relationships, (2) the importance of solvent effects, and (3) the differences between adiabatic and vertical energies.
authors.affiliation: Laboratoire CEISAM-UMR CNR 6230, Université de Nantes , 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
authors.forename: Denis
authors.initials: D
authors.lastname: Jacquemin
authors.affiliation: Laboratoire CEISAM-UMR CNR 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, CNRS UMR-7575, Chimie-ParisTech , 11 rue Pierre et Marie 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 of Pisa , Via Risorgimento 35, 56126 Pisa, Italy.
authors.forename: Benedetta
authors.initials: B
authors.lastname: Mennucci