Assessing the accuracy of TD-DFT excited-state geometries through optimal tuning with GW energy levels - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Chemical Physics Année : 2024

Assessing the accuracy of TD-DFT excited-state geometries through optimal tuning with GW energy levels

Résumé

We study the accuracy of excited state (ES) geometries using optimally tuned LC-PBE functionals with tuning based on GW quasiparticle energies. We compare the results obtained with the PBE, PBE0, non-tuned, and tuned LC-PBE functionals with available high-level CC reference values as well as experimental data. First, we compare ES geometrical parameters obtained for three different types of systems: molecules composed of a few atoms, 4-(dimethylamino)benzonitrile (DMABN), and conjugated dyes. To this end, we used wave-function results as benchmarks. Next, we evaluate the accuracy of the theoretically simulated spectra as compared to the experimental ones for five large dyes. Our results show that, besides small compact molecules for which tuning LC-PBE does not allow obtaining geometries more accurate than those computed with standard functionals, tuned range-separated functionals are clearly to be favored, not only for ES geometries but also for 0–0 energies, band shapes, and intensities for absorption and emission spectra. In particular, the results indicate that GW-tuned LC-PBE functionals provide improved matching with experimental spectra as compared to conventionally tuned functionals. It is an open question whether TD-DFT with GW-tuned functionals can qualitatively mimic the actual many-body Bethe–Salpeter (BSE/GW) formalism for which analytic ionic gradients remain to be developed.
Fichier principal
Vignette du fichier
JCP24-AR-00746.pdf (1.42 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-04542533 , version 1 (11-04-2024)

Identifiants

Citer

Iryna Knysh, Denez Raimbault, Ivan Duchemin, Xavier Blase, Denis Jacquemin. Assessing the accuracy of TD-DFT excited-state geometries through optimal tuning with GW energy levels. Journal of Chemical Physics, 2024, 160 (14), pp.144115. ⟨10.1063/5.0203818⟩. ⟨hal-04542533⟩
0 Consultations
0 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More