Absorption and Fluorescence Signatures of 1,2,3-Triazole Based Regioisomers : Challenging Compounds for TD-DFT - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2014

Absorption and Fluorescence Signatures of 1,2,3-Triazole Based Regioisomers : Challenging Compounds for TD-DFT

Résumé

In the continuous quest for improving TD-DFT methodologies as a tool to predict the photophysical features of solvated chro- mophores, we herein investigate two model regioisomers based on the 1,2,3-triazole moiety. Starting from their experimental absorption and emission spectra, key energy differences highlighting the main trends between the two isomers are extracted and used to gauge the accuracy of several levels of theory. RI-CC2 and EOM-CCSD calculations allow us to ascertain that the low energy spectra is not linked to double excitations. In vacuum, neither these methods nor any of the implemented TD-DFT levels of theory, ranging from global hybrids (PBE0, B3LYP) to range-separated functionals without (CAM-B3LYP, ωB97X) or with dispersion corrections (ωB97X-D), is able to capture the key features that differentiate the two chromophores. Accounting for solvent within a specific PCM model allows to recover experimental trends, but the dramatic changes occurring when moving from toluene to THF and/or for different PCM approaches (LR, cLR, SS) suggest that this agreement is probably fortuitous. Even so the ωB97X-D functional combined to the SS-PCM scheme leads to quantitative agreement with experiment, TD-DFT results obtained for 1,2,3-triazole based chromophores need to be treated with caution. We also show that the SS-PCM approach may be useful to test current and novel exchange-correlation functionals against the charge transfer failure.
Fichier principal
Vignette du fichier
triazole-v5forHAL.pdf (459.15 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-00983146 , version 1 (06-06-2014)

Identifiants

Citer

Claudine Katan, Paul Savel, Bryan M. Wong, Thierry Roisnel, Vincent Dorcet, et al.. Absorption and Fluorescence Signatures of 1,2,3-Triazole Based Regioisomers : Challenging Compounds for TD-DFT. Physical Chemistry Chemical Physics, 2014, 16 (19), pp.9064-9073. ⟨10.1039/C4CP00478G⟩. ⟨hal-00983146⟩
263 Consultations
2210 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More