title: Benchmark Study on the Triplet Excited-State Geometries and Phosphorescence Energies of Heterocyclic Compounds: Comparison Between TD-PBE0 and SAC-CI.
abstract: In this work, we investigated the properties of the triplet excited states of heterocyclic compounds including their geometries, electronic properties, and phosphorescence energies by using both the direct symmetry-adapted cluster-configuration interaction (SAC-CI) method and the TD-DFT approach with the PBE0 exchange-correlation functional (TD-PBE0). The target states are the ππ* and nπ* triplet states of furan, pyrrole, pyridine, p-benzoquinone, uracil, adenine, 9,10-anthraquinone, coumarin, and 1,8-naphthalimide as well as the Rydberg states. The present benchmark demonstrates that these two methods provide reasonably accurate geometries for the excited states of these heterocyclic compounds. The calculated Stokes shifts, which reflect geometry changes, were consistent for both these methods. The trends of agreement with experimental or reference values obtained for a panel of exchange-correlation functionals used to compute the absolute emission energies from the triplet states, differ from those found for the singlet excited states. Some of the low-lying triplet excited states were examined in detail for the first time, including vibrational analysis.
authors.affiliation: LECIME, Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie, UMR 7575 CNRS, Ecole Nationale Supérieure de Chimie de Paris, Chimie ParisTech , 11 rue P. et M. Curie, 75231 Paris Cedex 05, France.
authors.forename: Diane
authors.initials: D
authors.lastname: Bousquet
authors.affiliation: Institute for Molecular Science and Research Center for Computational Science , 38 Nishigo-naka, Myodaiji, Okazaki, 444-8585, Japan.|Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University , Nishikyo-ku, Kyoto 615-8520, Japan.
authors.forename: Ryoichi
authors.initials: R
authors.lastname: Fukuda
authors.affiliation: CEISAM, UMR CNRS 6230, BP 92208, Université de Nantes , 2 Rue de la Houssinière, 44322 Nantes, France.|Institut Universitaire de France , 103 Boulevard Saint Michel, F-75005 Paris, France.
authors.forename: Denis
authors.initials: D
authors.lastname: Jacquemin
authors.affiliation: LECIME, Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie, UMR 7575 CNRS, Ecole Nationale Supérieure de Chimie de Paris, Chimie ParisTech , 11 rue P. et M. Curie, 75231 Paris Cedex 05, France.
authors.forename: Ilaria
authors.initials: I
authors.lastname: Ciofini
authors.affiliation: LECIME, Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie, UMR 7575 CNRS, Ecole Nationale Supérieure de Chimie de Paris, Chimie ParisTech , 11 rue P. et M. Curie, 75231 Paris Cedex 05, France.|Institut Universitaire de France , 103 Boulevard Saint Michel, F-75005 Paris, France.
authors.forename: Carlo
authors.initials: C
authors.lastname: Adamo
authors.affiliation: Institute for Molecular Science and Research Center for Computational Science , 38 Nishigo-naka, Myodaiji, Okazaki, 444-8585, Japan.|Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University , Nishikyo-ku, Kyoto 615-8520, Japan.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Ehara