title: Bethe-Salpeter study of cationic dyes: Comparisons with ADC(2) and TD-DFT.
abstract: We present a theoretical investigation of the excited-state properties of a large series of structurally diverse arylcarbonium derivatives that are known to be challenging for theoretical models. More specifically, we compare the pros and cons of TD-DFT (TD-M06-2X), ADC(2), and BSE/GW approaches for a large panel of compounds, using two different solvent models. Both 0-0 and vertical transition energies are considered and compared to the experimental values. All approaches reasonably reproduce the auxochromic and acidochromic shifts, although in most cases both TD-DFT and BSE/GW return larger correlation with experimental values than ADC(2) for these shifts. In contrast, the absolute transition energies obtained with ADC(2) tend to be closer to the measurements, TD-DFT using the M06-2X functional largely overestimating the experimental references (by ca. 0.5 eV), and BSE/GW providing intermediate values. In addition, we show that the selected solvent model has a significant impact on the results, the corrected linear-response approach providing larger transition energies than its linear-response counterpart.
authors.affiliation: CEISAM, UMR CNRS 6230, BP 92208, Université de Nantes, 2, Rue de la Houssinière, 44322 Nantes Cedex 3, France.
authors.forename: Cloé
authors.initials: C
authors.lastname: Azarias
authors.affiliation: INAC, SP2M/L_Sim, CEA/UJF Cedex 09, 38054 Grenoble, France.
authors.forename: Ivan
authors.initials: I
authors.lastname: Duchemin
authors.affiliation: Univ. Grenoble Alpes, Inst NEEL, F-38042 Grenoble, France.
authors.forename: Xavier
authors.identifier: 0000000202019093
authors.initials: X
authors.lastname: Blase
authors.affiliation: CEISAM, UMR CNRS 6230, BP 92208, Université de Nantes, 2, Rue de la Houssinière, 44322 Nantes Cedex 3, France.
authors.forename: Denis
authors.initials: D
authors.lastname: Jacquemin