Diabatic Decomposition Perspective on the Role of Charge Transfer and Local Excitations in Thermally Activated Delayed Fluorescence

Thermally activated delayed fluorescence (TADF) is a phenomenon that relies on the upconversion of triplet excitons to singlet excitons by means of reverse intersystem crossing (rISC). It has been shown both experimentally and theoretically that the TADF mechanism depends on the interplay between charge transfer and local excitations. However, the difference between the diabatic and adiabatic character of the involved excited states is rarely discussed in the literature. Here we develop a diabatization procedure to implement a four-state model Hamiltonian to a set of TADF molecules. We provide physical interpretations of the Hamiltonian elements and show their dependence on the electronic state of the equilibrium geometry. We also demonstrate how vibrations affect the TADF efficiency by modifying the diabatic decomposition of the molecule. Finally, we provide a simple model that connects the diabatic Hamiltonian to the electronic properties relevant to TADF and show how this relationship translates into different optimization strategies for rISC, fluorescence, and overall TADF performance.

Automated summary

This study develops a diabatization procedure to investigate TADF molecules. By analyzing the diabatic Hamiltonian of the molecules, we provide physical interpretations related to electronic states and molecular geometries. The study also finds the influence of vibrations on TADF efficiency and proposes different optimization strategies.