Singlet‐Triplet Excited‐State Inversion in Heptazine and Related Molecules: Assessment of TD‐DFT and ab initio Methods
Por favor, use este identificador para citar o enlazar este ítem:
http://hdl.handle.net/10045/113742
Título: | Singlet‐Triplet Excited‐State Inversion in Heptazine and Related Molecules: Assessment of TD‐DFT and ab initio Methods |
---|---|
Autor/es: | Ricci, Gaetano | San-Fabián, Emilio | Olivier, Yoann | Sancho-Garcia, Juan-Carlos |
Grupo/s de investigación o GITE: | Química Cuántica |
Centro, Departamento o Servicio: | Universidad de Alicante. Departamento de Química Física |
Palabras clave: | Ab initio calculations | Electron correlation effects | Exchange interaction | Heptazine derivatives | Singlet-triplet energy gap |
Área/s de conocimiento: | Química Física |
Fecha de publicación: | 17-mar-2021 |
Editor: | Wiley-VCH GmbH |
Cita bibliográfica: | ChemPhysChem. 2021, 22(6): 553-560. https://doi.org/10.1002/cphc.202000926 |
Resumen: | We have investigated the origin of the S1-T1 energy levels inversion for heptazine, and other N-doped π-conjugated hydrocarbons, leading thus to an unusually negative singlet-triplet energy gap (DEST < 0). Since this inversion might rely on substantial doubly-excited configurations to the S1 and/or T1 wavefunctions, we have systematically applied multi-configurational SA-CASSCF and SC-NEVPT2 methods, SCS-corrected CC2 and ADC(2) approaches, and linear-response TD-DFT, to analyse if the latter method could also face this challenging issue. We have also extended the study to B-doped π-conjugated systems, to see the effect of chemical composition on the results. For all the systems studied, an intricate interplay between the singlet-triplet exchange interaction, the influence of doubly-excited configurations, and the impact of dynamic correlation effects, serves to explain the DEST < 0 values found for most of the compounds, which is not predicted by TD-DFT. |
Patrocinador/es: | The work in Alicante is supported by “Ministerio de Ciencia e Innovación” of Spain (Grant No. PID2019-106114GB–I00). Computational resources in Namur are provided by the “Consortium des Équipements de Calcul Intensif” (CÉCI), funded by the “Fonds de la Recherche Scientifiques de Belgique” (F.R.S.-F.N.R.S.) under Grant No. 2.5020.11. G.R. acknowledges a grant from the “Fonds pour la formation a la Recherche dans l’Industrie et dans l’Agriculture” (F.R.I.A.) of the F.R.S.-F.N.R.S. |
URI: | http://hdl.handle.net/10045/113742 |
ISSN: | 1439-4235 (Print) | 1439-7641 (Online) |
DOI: | 10.1002/cphc.202000926 |
Idioma: | eng |
Tipo: | info:eu-repo/semantics/article |
Derechos: | © 2020 Wiley-VCH GmbH |
Revisión científica: | si |
Versión del editor: | https://doi.org/10.1002/cphc.202000926 |
Aparece en las colecciones: | INV - QC - Artículos de Revistas |
Archivos en este ítem:
Archivo | Descripción | Tamaño | Formato | |
---|---|---|---|---|
Ricci_etal_2021_ChemPhysChem_final.pdf | Versión final (acceso restringido) | 1,11 MB | Adobe PDF | Abrir Solicitar una copia |
Ricci_etal_2021_ChemPhysChem_accepted.pdf | Accepted Manuscript (acceso abierto) | 1,61 MB | Adobe PDF | Abrir Vista previa |
Todos los documentos en RUA están protegidos por derechos de autor. Algunos derechos reservados.