Amb motiu del tancament d'estiu, la validació de documents es reprendrà a partir del 28 d'agost de 2026. Disculpeu les molèsties.
Con motivo del cierre de verano, la validación de documentos se reanudará a partir del 28 de agosto de 2026. Disculpad las molestias
Due to the summer closure, document validation will resume starting August 28, 2026. We apologize for any inconvenience.

Files

260908.pdf (1.56 MB)

Document type

Article

Version

Accepted version

Publication date

2023-03-28

Publication license

cc-by-nc-nd (c) Elsevier B.V., 2023
Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/204983

Benchmarking DFT functionals for photophysics of pyranoflavylium cations

Journal Title

Authors

Director/Tutor

Journal ISSN

Volume Title

Related resource

https://doi.org/10.1016/j.jmgm.2023.108460

Abstract

An intense absorption, phosphorescence, a long triplet excited state lifetime and singlet oxygen generation capabilities are characteristics of pyranoflavylium cations, analogues to pyranoanthocyanidins originated in the maturation process of red wine. Such properties make these compounds potential photosensitizers to be applied in photodynamic therapy. In this context, the photophysical processes underlying that treatment critically depend on the electronic structure of the pyranoflavylium molecules. When employing density functional theory to describe the electronic structure of molecules, the choice of the most suitable functional is not trivial, and benchmark studies are needed to orient practitioners in the field. In this work, a benchmark of seven of the most commonly used density functionals in addressing the photophysical properties of a set of eight pyranoflavylium cations is reported. Ground and excited state geometries, molecular orbitals, and absorption, fluorescence and phosphorescence transition energies were calculated using density functional theory approaches, and evaluated and compared to experimental data and monoreferential wave function-based methodologies. Statistical analysis of the results indicates that global-hybrid functionals allow an excellent description of absorption and emission energies, with errors around 0.05 eV, while range-separated variants led to somewhat larger errors in the range 0.1-0.2 eV. In contrast, range-separated functionals display excellent phosphorescence energies with errors close to 0.05 eV, in this case global-hybrids showing increased discrepancies around 0.5-0.1 eV.

Subject

Fototeràpia, Química

Subject (English)

Phototherapy, Chemistry

Citation

Collections

Articles publicats en revistes (Farmàcia, Tecnologia Farmacèutica i Fisicoquímica)

Citation

SOUZA, Jhonathan R., et al. Benchmarking DFT functionals for photophysics of pyranoflavylium cations. Journal of Molecular Graphics & Modelling. 2023. Vol. 122, num. 108460. ISSN 1093-3263. [consulted: 7 of August of 2026]. Available at: https://hdl.handle.net/2445/204983

Export metadata

JSON - METS

Share record