Accurate Treatment of Charge-Transfer Excitations and Thermally Activated Delayed Fluorescence Using the Particle–Particle Random Phase Approximation

Thermally activated delayed florescence (TADF) is a mechanism that increases the electroluminescence efficiency in organic light-emitting diodes by harnessing both singlet and triplet excitons. TADF is facilitated by a small energy difference between the first singlet (S1) and triplet (T1) excited states (ΔE(ST)), which is minimized by spatial separation of the donor and acceptor moieties. The resultant charge-transfer (CT) excited states are difficult to model using time-dependent density functional theory (TDDFT) because of the delocalization error present in standard density functional approximations to the exchange-correlation energy. In this work we explore the application of the particle–particle random phase approximation (pp-RPA) for the determination of both S1 and T1 excitation energies. We demonstrate that the accuracy of the pp-RPA is functional dependent and that, when combined with the hybrid functional B3LYP, the pp-RPA computed ΔE(ST) have a mean absolute deviation (MAD) of 0.12 eV for the...