Effects of Solvent Dielectric on Thermally Activated Delayed Fluorescence: A Predictive Computational Polarization...

We study computationally thermally activated delayed fluorescence (TADF) in donor-acceptor compounds. The relevant electronic excited states that are strongly affected by the dielectric environment are treated by a polarization consistent framework. The high fidelity potential energy surfaces are used following a quantum-mechanical Fermi's golden rule (FGR) picture to calculate rates of intersystem crossing (ISC) and reverse intersystem crossing (RISC). To demonstrate the potency of the approach, we consider isomers of benzonitrile functionalized tert-butyl-substituted dimethylacridine (DMAC-BN), which were recently found to perform well as TADF emitters. The calculated excited state energies that appear to reproduce well measured spectral trends with respect to the dielectric constant are used to parametrize ISC/RISC FGR rates. The calculated rates reproduce well measured rates, whereas semiclassical based rates are grossly underestimated. In particular, we find in agreement with the recent experimental study [Phys. Rev. Appl.2019, 12, 044021] that the ortho and meta isomers are significantly more effective as TADF emitters. The computational framework provides valuable insight at the molecular level into RISC rates and therefore can contribute to the design of materials of increased TADF efficiency.