Solvent-Induced Symmetry Breaking of the Photoinduced Charge Transfer Dynamics in the Bridged Perylene Dimer

The charge transfer dynamics of the bridged perylene dimer were investigated with the recently developed solvent coupling Redfield time propagation model. The results are compared with previous experimental findings to showcase the significance and applicability of the model. The charge transfer dynamics in vacuum showed that no breaking of the charge transfer direction symmetry occurred upon optical excitation, in perfect agreement with the experiment. Meanwhile, attractive solute-solvent interactions facilitated by the dipole moments of the polar solvents were observed to break the charge transfer direction symmetry. The conformational isomerism effect on the transfer dynamics manifested itself by promoting different transport channels upon solvation. Consequently, the solvent coupling Redfield time propagation model was indeed found to be able to quantitatively describe the charge transfer dynamics including exotic phenomena such as symmetry breaking of charge transfer direction.