Exciton maps for thermally activated delayed fluorescence active/inactive carbazole benzonitrile derivatives

The all-electron first-principles GW+Bethe-Salpeter method was applied to six carbazole benzonitrile (CzBN) derivatives, which were recently reported to be both thermally activated delayed fluorescence (TADF) active and inactive despite their singlet-triplet splittings being commonly around 0.2 eV. The present method successfully reproduced very similar photoabsorption spectra as experiments from the viewpoint of the peak positions and relative peak heights. We also performed exciton analysis with the exciton wave functions for several lowest singlet and triplet exciton states to reveal the details of the optical properties. We applied this to not only the present six CzBN derivatives but also 18 other TADF molecules and proposed a new exciton map to classify the molecules as the TADF active/inactive by using the exciton binding energy in the vertical axis and the ratio of electron and hole delocalization in the horizontal axis. Our results suggest two possible TADF mechanisms: spatially less localized hole states than the electron states where the exciton binding energy is proportional to the ratio of hole and electron delocalization and spatially more localized hole states than the electron states where the exciton binding energy should be large.