Extended theoretical modeling of reverse intersystem crossing for thermally activated delayed fluorescence materials.

Hagai, Masaya; Inai, Naoto; Yasuda, Takuma; Fujimoto, Kazuhiro J; Yanai, Takeshi · Sci Adv · 2024

basic_science · Level V

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Abstract

Thermally activated delayed fluorescence (TADF) materials and multi-resonant (MR) variants are promising organic emitters that can achieve an internal electroluminescence quantum efficiency of ~100%. The reverse intersystem crossing (RISC) is key for harnessing triplet energies for fluorescence. Theoretical modeling is thus crucial to estimate its rate constant (<i>k</i><sub>RISC</sub>) for material development. Here, we present a comprehensive assessment of the theory for simulating the RISC of MR-TADF molecules within a perturbative excited-state dynamics framework. Our extended rate formula reveals the importance of the concerted effects of nonadiabatic spin-vibronic coupling and vibrationally induced spin-orbital couplings in reliably determining <i>k</i><sub>RISC</sub> of MR-TADF molecules. The excited singlet-triplet energy gap is another factor influencing <i>k</i><sub>RISC</sub>. We present a scheme for gap estimation using experimental Arrhenius plots of <i>k</i><sub>RISC</sub>. Erroneous behavior caused by approximations in Marcus theory is elucidated by testing 121 MR-TADF molecules. Our extended modeling offers in-depth descriptions of <i>k</i><sub>RISC</sub>.