Benchmarking DFT Functionals for Excited-State Calculations of Donor-Acceptor TADF Emitters: Insights on the Key Parameters Determining Reverse Inter-System Crossing.

The importance of intermediate triplet states and the nature of excited states has gained interest in recent years for the thermally activated delayed fluorescence (TADF) mechanism. It is widely accepted that simple conversion between charge transfer (CT) triplet and singlet excited states is too crude, and a more complex route involving higher-lying locally excited triplet excited states has to be invoked to witness the magnitude of the rate of reverse inter-system crossing (RISC) rates. The increased complexity has challenged the reliability of computational methods to accurately predict the relative energy between excited states as well as their nature. Here, we compare the results of widely used density functional theory (DFT) functionals, CAM-B3LYP, LC-ωPBE, LC-ω*PBE, LC-ω*HPBE, B3LYP, PBE0, and M06-2X, against a wavefunction-based reference method, Spin-Component Scaling second-order approximate Coupled Cluster (SCS-CC2), in 14 known TADF emitters possessing a diversity of chemical structures. Overall, the use of the Tamm-Dancoff Approximation (TDA) together with CAM-B3LYP, M06-2X, and the two ω-tuned range-separated functionals LC-ω*PBE and LC-ω*HPBE demonstrated the best agreement with SCS-CC2 calculations in predicting the absolute energy of the singlet S 1 , and triplet T 1 and T 2 excited states and their energy differences. However, consistently across the series and irrespective of the functional or the use of TDA, the nature of T 1 and T 2 is not as accurately captured as compared to S 1 . We also investigated the impact of the optimization of S 1 and T 1 excited states on Δ E ST and the nature of these states for three different functionals (PBE0, CAM-B3LYP, and M06-2X). We observed large changes in Δ E ST using CAM-B3LYP and PBE0 functionals associated with a large stabilization of T 1 with CAM-B3LYP and a large stabilization of S 1 with PBE0, while Δ E ST is much less affected considering the M06-2X functional. The nature of the S 1 state barely evolves after geometry optimization essentially because this state is CT by nature for the three functionals tested. However, the prediction of the T 1 nature is more problematic since these functionals for some compounds interpret the nature of T 1 very differently. SCS-CC2 calculations on top of the TDA-DFT optimized geometries lead to a large variation in terms of Δ E ST and the excited-state nature depending on the chosen functionals, further stressing the large dependence of the excited-state features on the excited-state geometries. The presented work highlights that despite good agreement of energies, the description of the exact nature of the triplet states should be undertaken with caution.