Key parameters that steer the efficiency of thermally
activated
delayed fluorescence (TADF) are the energetic splitting ΔE
ST between S1 and T1,
their mutual spin–orbit coupling (SOC) and the transition dipole
strength μ of the S1 emission. Small ΔE
ST values, resonable SOC and high values of
μ are difficult to achieve simultaneously. Using high-level
quantum chemical methods, we have investigated the course of these
parameters as functions of the donor–acceptor torsion angle
in a series of conformationally constrained triarylamine–terephthalonitrile
systems. Potential energy surface crossings between triplet states
of charge-transfer and local-excitation character close to 90°
indicate that a three-state model of the TADF kinetics might not be
appropriate. The smallest adiabatic ΔE
ST values are obtained for a hybrid solvent model comprising
two explicit toluene molecules in addition to a polarizable continuum
model of solvation. Due to the substantial geometrical displacements
of the S1 and T1 potentials in the torsion angle,
the adiabatic Hessian method does not provide meaningful rate constants
for reverse intersystem crossing. The recently developed vertical
Hessian approach remedies this problem.