Modeling of Multiresonant Thermally Activated Delayed Fluorescence Emitters─Properly Accounting for Electron Correlation Is Key!

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Title: Modeling of Multiresonant Thermally Activated Delayed Fluorescence Emitters─Properly Accounting for Electron Correlation Is Key!
Authors: Hall, David | Sancho-Garcia, Juan-Carlos | Pershin, Anton | Ricci, Gaetano | Beljonne, David | Zysman-Colman, Eli | Olivier, Yoann
Research Group/s: Química Cuántica
Center, Department or Service: Universidad de Alicante. Departamento de Química Física
Keywords: Multiresonant thermally activated delayed fluorescent | Spin-component scaling second-order approximate coupled-cluster | ΔEST | Wavefunction methods | Electron correlation
Knowledge Area: Química Física
Issue Date: 5-Jul-2022
Publisher: American Chemical Society
Citation: Journal of Chemical Theory and Computation. 2022, 18(8): 4903-4918.
Abstract: With the surge of interest in multiresonant thermally activated delayed fluorescent (MR-TADF) materials, it is important that there exist computational methods to accurately model their excited states. Here, building on our previous work, we demonstrate how the spin-component scaling second-order approximate coupled-cluster (SCS-CC2), a wavefunction-based method, is robust at predicting the ΔEST (i.e., the energy difference between the lowest singlet S1 and triplet T1 excited states) of a large number of MR-TADF materials, with a mean average deviation (MAD) of 0.04 eV compared to experimental data. Time-dependent density functional theory calculations with the most common DFT functionals as well as the consideration of the Tamm-Dancoff approximation (TDA) consistently predict a much larger ΔEST as a result of a poorer account of Coulomb correlation as compared to SCS-CC2. Very interestingly, the use of a metric to assess the importance of higher order excitations in the SCS-CC2 wavefunctions shows that Coulomb correlation effects are substantially larger in the lowest singlet compared to the corresponding triplet and need to be accounted for a balanced description of the relevant electronic excited states. This is further highlighted with coupled cluster singles-only calculations, which predict very different S1 energies as compared to SCS-CC2 while T1 energies remain similar, leading to very large ΔEST, in complete disagreement with the experiments. We compared our SCS-CC2/cc-pVDZ with other wavefunction approaches, namely, CC2/cc-pVDZ and SOS-CC2/cc-pVDZ leading to similar performances. Using SCS-CC2, we investigate the excited-state properties of MR-TADF emitters showcasing large ΔET2T1 for the majority of emitters, while π-electron extension emerges as the best strategy to minimize ΔEST. We also employed SCS-CC2 to evaluate donor–acceptor systems that contain a MR-TADF moiety acting as the acceptor and show that the broad emission observed for some of these compounds arises from the solvent-promoted stabilization of a higher-lying charge-transfer singlet state (S2). This work highlights the importance of using wavefunction methods in relation to MR-TADF emitter design and associated photophysics.
Sponsor: The St Andrews team would like to thank the Leverhulme Trust (RPG-2016-047) for financial support. E.Z.C. is a Royal Society Leverhulme Trust Senior Research fellow (SRF\R1\201089). Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F.R.S.-FNRS) under Grant no. 2.5020.11, as well as the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under the grant agreement n1117545. G.R. acknowledges a grant from the “Fonds pour la formation à la Recherche dans l’Industrie et dans l’Agriculture” (F.R.I.A.) of the F.R.S.-F.N.R.S. Y.O. acknowledges funding by the Fonds de la Recherche Scientifique-FNRS under Grant n° F.4534.21 (MIS-IMAGINE). D.B. is a FNRS Research Director. J.C.S.G. acknowledges “Ministerio de Ciecia e Innovación” of Spain (PID2019-106114GB-I00).
ISSN: 1549-9618 (Print) | 1549-9626 (Online)
DOI: 10.1021/acs.jctc.2c00141
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2022 American Chemical Society
Peer Review: si
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Appears in Collections:INV - QC - Artículos de Revistas

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