title: Application of recent double-hybrid density functionals to low-lying singlet-singlet excitation energies of large organic compounds.
abstract: The present work assesses some recently developed double-hybrid density functionals (B2π-PLYP, PBE0-DH, and PBE0-2) using linear-response Tamm-Dancoff Time-Dependent Density Functional Theory. This assessment is achieved against experimentally derived low-lying excitation energies of large organic dyes of recent interest, including some excitations dominated by charge-transfer transitions. Comparisons are made with some of the best-performing methods established from the literature, such as PBE0 or B3LYP hybrid or the recently proposed B2-PLYP and B2GP-PLYP double-hybrid models, to ascertain their quality and robustness on equal footing. The accuracy of parameter-free or empirical forms of double-hybrid functionals is also briefly discussed. Generally speaking, it turns out that double-hybrid expressions always provide more accurate estimates than corresponding hybrid methods. Double-hybrid functionals actually reach averaged accuracies of 0.2 eV, that can be admittedly considered close to any intended accuracy limit within the present theoretical framework.
authors.affiliation: INSERM UMR-S850 - Faculté de Pharmacie, Université de Limoges, 87025 Limoges, France.
authors.forename: F
authors.initials: F
authors.lastname: Di Meo
authors.forename: P
authors.initials: P
authors.lastname: Trouillas
authors.forename: C
authors.initials: C
authors.lastname: Adamo
authors.forename: J C
authors.initials: JC
authors.lastname: Sancho-García
mesh_terms: D008958:Models, Molecular; D008968:Molecular Conformation; D009930:Organic Chemicals / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics; D013997:Time Factors
chemical_list: D009930:Organic Chemicals