title: Verdict: Time-Dependent Density Functional Theory "Not Guilty" of Large Errors for Cyanines.
abstract: We assess the accuracy of eight Minnesota density functionals (M05 through M08-SO) and two others (PBE and PBE0) for the prediction of electronic excitation energies of a family of four cyanine dyes. We find that time-dependent density functional theory (TDDFT) with the five most recent of these functionals (from M06-HF through M08-SO) is able to predict excitation energies for cyanine dyes within 0.10-0.36 eV accuracy with respect to the most accurate available Quantum Monte Carlo calculations, providing a comparable accuracy to the latest generation of CASPT2 calculations, which have errors of 0.16-0.34 eV. Therefore previous conclusions that TDDFT cannot treat cyanine dyes reasonably accurately must be revised.
authors.affiliation: Laboratoire CEISAM - UMR CNRS 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: Commercial Printing Engine Lab, HP Laboratories, Hewlett-Packard Co. , 1501 Page Mill Road, Palo Alto, California 94304, United States.
authors.forename: Yan
authors.initials: Y
authors.lastname: Zhao
authors.affiliation: Department of Chemistry, University of Coimbra , 3004-535 Coimbra, Portugal.
authors.forename: Rosendo
authors.initials: R
authors.lastname: Valero
authors.affiliation: École Nationale Supérieure de Chimie de Paris - Chimie ParisTech , LECIME, UMR 7575 CNRS, 11 rue Pierre et Marie Curie, 75005 Paris, France.
authors.forename: Carlo
authors.initials: C
authors.lastname: Adamo
authors.affiliation: École Nationale Supérieure de Chimie de Paris - Chimie ParisTech , LECIME, UMR 7575 CNRS, 11 rue Pierre et Marie Curie, 75005 Paris, France.
authors.forename: Ilaria
authors.initials: I
authors.lastname: Ciofini
authors.affiliation: Department of Chemistry and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455-0431, United States.
authors.forename: Donald G
authors.initials: DG
authors.lastname: Truhlar