Correlation vs. exchange competition drive the singlet-triplet excited-state inversion in non-alternant hydrocarbons

Please use this identifier to cite or link to this item:
Información del item - Informació de l'item - Item information
Title: Correlation vs. exchange competition drive the singlet-triplet excited-state inversion in non-alternant hydrocarbons
Authors: Sandoval-Salinas, María Eugenia | Ricci, Gaetano | Pérez-Jiménez, Ángel J. | Casanova, David | Olivier, Yoann | Sancho-Garcia, Juan-Carlos
Research Group/s: Química Cuántica
Center, Department or Service: Universidad de Alicante. Departamento de Química Física
Keywords: Singlet-triplet excited-state inversion | Driving force | Non-alternant hydrocarbons
Issue Date: 14-Jul-2023
Publisher: Royal Society of Chemistry
Citation: Physical Chemistry Chemical Physics. 2023, 25: 26417-26428.
Abstract: In this work, we focus on the understanding of the driving force behind the S1 - T1 excited-state energy inversion (which would thus violate the Hund’s rule, situating the S1 state lower in energy than the T1 state) of two non-benzenoid non-alternant hydrocarbons, composed of odd-membered rings. The molecules considered here have identical chemical composition but different atomic configuration in space. The delicate interplay between structural and electronic factors that might induce the inversion and its energy extension, only by few meV, are systematically investigated here by state-of-the-art calculations. Qualitative and quantitative accurate predictions are obtained employing post-HF methods, thanks to the balanced and careful inclusion of electron correlation effects. The obtained results might guide and rationalize new searches of molecules violating Hund’s rule, concomitantly advising the importance of key contributions from the theoretical method of choice.
Sponsor: The work in Alicante is supported by project PID2019-106114GB-I00 (“Ministerio de Ciencia e Innovación”). M.E.S.-S. acknowledges the funding by the United Kingdom Research and Innovation (U.K.R.I.) under the U.K. government’s Horizon Europe funding guarantee (grant number EP/X020908/1). Y.O. acknowledges the funding by the “Fonds de la Recherche Scientifique-FNRS” under Grant n. F.4534.21 (MIS-IMAGINE). 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. Computational resources were also provided by the “Consortium des Équipements de Calcul Intensif” (C´ECI), funded by the “Fonds de la Recherche Scientifiques de Belgique” (F.R.S.-F.N.R.S.) under Grant No. 2.5020.11. D.C. acknowledges funding by projects PID2019-109555GB-I00 and RED2018-102815-T (“Ministerio de Ciencia e Innovación”) and from project No. PIBA19-0004 (“Eusko Jaularitza”).
ISSN: 1463-9076 (Print) | 1463-9084 (Online)
DOI: 10.1039/D3CP02465B
Language: eng
Type: info:eu-repo/semantics/article
Rights: This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
Peer Review: si
Publisher version:
Appears in Collections:INV - QC - Artículos de Revistas

Files in This Item:
Files in This Item:
File Description SizeFormat 
ThumbnailSandoval-Salinas_etal_2023_PhysChemChemPhys.pdf2,55 MBAdobe PDFOpen Preview

This item is licensed under a Creative Commons License Creative Commons