Optical Dynamics of Exciton and Polaron Formation in Molecular Aggregates

Results of femtosecond accumulated photon echo, picosecond pump-probe and fluorescence lifetime measurements are reported on aggregates of the dyes pseudoisocyanine (PIC) and substituted thiapyrylium (TPY), embedded in a polycarbonate matrix. It is concluded that in the PIC aggregate, delocalized excitations (excitons) are formed, which are weakly coupled to the aggregate’s nuclear frame. In the TPY aggregate, excitons are also initially formed, but through strong local electron-phonon coupling these excitons are not stable and decay into polarons, which become trapped. It is suggested that the nature of the excitations in aggregates crucially depends on the change of electron density distribution upon optical excitation. When this change is large, as revealed by a large change of dipole moment, polarons will be formed. In the other limit of a small change of dipole moment on optical excitation, excitons with an enhanced radiative lifetime are formed, which coherently propagate over that part of the aggregate where the molecules are electronically strongly coupled. The relevance of these findings towards energy transport in photo-biological systems is also discussed.