Hall, David, Sancho-Garcia, Juan-Carlos, Pershin, Anton, Ricci, Gaetano, Beljonne, David, Zysman-Colman, Eli, Olivier, Yoann
Modeling of Multiresonant Thermally Activated Delayed Fluorescence Emitters─Properly Accounting for Electron Correlation Is Key!
Journal of Chemical Theory and Computation. 2022, 18(8): 4903-4918. https://doi.org/10.1021/acs.jctc.2c00141
URI: http://hdl.handle.net/10045/125014
DOI: 10.1021/acs.jctc.2c00141
ISSN: 1549-9618 (Print)
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.
Keywords:Multiresonant thermally activated delayed fluorescent, Spin-component scaling second-order approximate coupled-cluster, ΔEST, Wavefunction methods, Electron correlation
American Chemical Society
info:eu-repo/semantics/article