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

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 delta E-ST (i.e., the energy difference between the lowest singlet S-1 and triplet T-1 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 delta E(ST )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 S-1 energies as compared to SCS-CC2 while T(1 )energies remain similar, leading to very large delta E-ST, 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 LET2T1 for the majority of emitters, while pi-electron extension emerges as the best strategy to minimize delta E-ST. We also employed SCS-CC2 to evaluate donor-acceptor systems that contain a MRTADF 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 (S-2). This work highlights the importance of using wavefunction methods in relation to MR-TADF emitter design and associated photophysics.