Quantum simulations of thermally activated delayed fluorescence in an all-organic emitter

We investigate the prototypical NAI-DMAC thermally activated delayed fluorescence (TADF) emitter in the gas phase- and high-packing fraction limits at finite temperature, by combining first principles molecular dynamics with a quantum thermostat to account for nuclear quantum effects (NQE). We find a weak dependence of the singlet–triplet energy gap (ΔEST) on temperature in both the solid and the molecule, and a substantial effect of packing. While the ΔEST vanishes in the perfect crystal, it is of the order of ∼0.3 eV in the molecule, with fluctuations ranging from 0.1 to 0.4 eV at 300 K. The transition probability between the HOMOs and LUMOs has a stronger dependence on temperature than the singlet–triplet gap, with a desirable effect for thermally activated fluorescence; such temperature effect is weaker in the condensed phase than in the molecule. Our results on ΔEST and oscillator strengths, together with our estimates of direct and reverse intersystem crossing rates, show that optimization of packing and geometrical conformation is critical to increase the efficiency of TADF compounds. Our findings highlight the importance of considering thermal fluctuations and NQE to obtain robust predictions of the electronic properties of NAI-DMAC.