ΔDFT Predicts Inverted Singlet-Triplet Gaps with Chemical Accuracy at a Fraction of the Cost of Wave Function-Based Approaches.

Efficient OLEDs need to quickly convert singlet and triplet excitons into photons. Molecules with an inverted singlet-triplet energy gap (INVEST) are promising candidates for this task. However, typical INVEST molecules have drawbacks like too low oscillator strengths and excitation energies. High-throughput screening could identify suitable INVEST molecules, but existing methods are problematic: The workhorse method TD-DFT cannot reproduce gap inversion, while wave function-based methods are too slow. This study proposes a state-specific method based on unrestricted Kohn-Sham DFT with common hybrid functionals. Tuned on the new INVEST15 benchmark set, this method achieves an error of less than 1 kcal/mol, which is traced back to error cancellation between spin contamination and dynamic correlation. Applied to the larger and structurally diverse NAH159 set in a black-box fashion, the method maintains a small error (1.2 kcal/mol) and accurately predicts gap signs in 83% of cases, confirming its robustness and suitability for screening workflows.

Benchmarking Charge-Transfer Excited States in TADF Emitters: ΔDFT Outperforms TD-DFT for Emission Energies.

Charge-transfer (CT) excited states are crucial to organic light-emitting diodes (OLEDs), particularly to those based on thermally activated delayed fluorescence (TADF). However, accurately modeling CT states remains challenging, even with modern implementations of (time-dependent) density functional theory [(TD-)DFT], especially in a dielectric environment. To identify shortcomings and improve the methodology, we previously established the STGABS27 benchmark set with highly accurate experimental references for the adiabatic energy gap between the lowest singlet and triplet excited states (ΔEST). Here, we diversify this set to the STGABS27-EMS benchmark by including experimental emission energies (Eem) and use this new set to (re)-evaluate various DFT-based approaches. Surprisingly, these tests demonstrate that a state-specific (un)restricted open-shell Kohn-Sham (U/ROKS) DFT coupled with a polarizable continuum model for perturbative state-specific nonequilibrium solvation (ptSS-PCM) provides exceptional accuracy for predicting Eem over a wide range of density functionals. In contrast, the main workhorse of the field, Tamm-Dancoff-approximated TD-DFT (TDA-DFT) paired with the same ptSS-PCM, is distinctly less accurate and strongly functional-dependent. More importantly, while TDA-DFT requires the choice of two very different density functionals for good performance on either ΔEST or Eem, the time-independent U/ROKS/PCM approaches deliver excellent accuracy for both quantities with a wide variety of functionals.

NBN- and BNB-Phenalenyls: the Yin and Yang of Heteroatom-doped π Systems.

NBN- and BNB-doped phenalenyls are isoelectronic to phenalenyl anions and cations, respectively. They represent a pair of complementary molecules that have essentially identical structures but opposite properties as electron donors and acceptors. The NBN-phenalenyls 1-4 considered here were prepared from N,N'-dimethyl-1,8-diaminonaphthalene and readily available boron-containing building blocks (i. e., BH3⋅SMe2 (1), p-CF3-C6H4B(OH)2 (2), C6H5B(OH)2 (3), or MesBCl2/iPr2NEt (4)). Treatment of 1 with 4-Me2N-2,6-Me2-C6H2Li gave the corresponding NBN derivative 5. The BNB-phenalenyl 6 was synthesized from 1,8-naphthalenediyl-bridged diborane(6), PhNH2, and MesMgBr. A computational study reveals that the photoemission of 1, 4, and 5 originates from locally excited (LE) states at the NBN-phenalenyl fragments, while that of 2 is dominated by charge transfer (CT) from the NBN-phenalenyl to the p-CF3-C6H4 fragment. Depending on the dihedral angle θ between its Ph and NBN planes, compound 3 emits mainly from a less polar LE (θ >55°) or more polar CT state (θ <55°). In turn, the energetic preference for either state is governed by the polarity of the solvent used. An equimolar aggregate of the NBN- and BNB-phenalenyls 3 and 6 (in THF/H2O) shows a distinct red-shifted emission compared to that of the individual components, which originates from an intermolecular CT state.

Either Accurate Singlet-Triplet Gaps or Excited-State Structures: Testing and Understanding the Performance of TD-DFT for TADF Emitters.

The energy gap between the lowest singlet and triplet excited states (ΔEST) is a key property of thermally activated delayed fluorescence (TADF) emitters, where these states are dominated by charge-transfer (CT) character. Despite its well-known shortcomings concerning CT states, time-dependent density functional theory (TD-DFT) is widely used to predict this gap and study TADF. Moreover, polar CT states exhibit a strong interaction with their molecular environment, which further complicates their computational description. Addressing these two major challenges, this work studies the performance of Tamm-Dancoff-approximated TD-DFT (TDA-DFT) on the recent STGABS27 benchmark set,1 exploring different strategies to include orbital and structural relaxation, as well as dielectric embedding. The results show that the best-performing strategy is to calculate ΔEST at the ground-state structure using functionals with a surprisingly small amount of Fock exchange of ≈10% and without a (complete) solvent model. However, as this approach heavily relies on error cancellation to mimic dielectric relaxation, it is not robust and exhibits large systematic deviations in excited state energies, state characters, and structures. More rigorous approaches, including state-specific solvation, do not share these systematic deviations, but their predicted ΔEST values exhibit larger statistical errors. We thus conclude that for the description of CT states in dielectric environments, none of the tested TDA-DFT methods is competitive with the recently presented ROKS/PCM approach regarding robustness, accuracy, and computational efficiency.