Prediction of Internal Reorganization Energy in Photoinduced Electron Transfer Processes of Molecular Dyads

A novel theoretical methodology is proposed to estimate the magnitude of internal reorganization energy for electron transfer and charge recombination processes in donor-bridge-acceptor (D-B-A) type molecular dyads. The potential energy surface for each process is plotted for the shortest path by assuming a displaced but slightly distorted harmonic oscillator model. Structural changes occurring upon photoexcitation and ionization were exploited to calculate the activation energies needed for electron transfer reactions with the aid of involved vibrational modes. D-B-A dyads consisting of octathiophene (T₈) paired with three (di)imide acceptors (naphthalene diimide (NDI), benzene diimide (BDI), and naphthalimide (NI)) were studied as model systems for theoretical calculations. It has been found that T₈NDI and T₈BDI possess very low activation energies for both forward electron transfer and charge recombination, and hence the rates for relevant processes should be very rapid. In contrast, the activation energies for such processes for T₈NI were found to be relatively large, and free energy estimations predict that the charge recombination mechanism in T₈NI falls into the inverted regime of Marcus semiclassical electron transfer theory. All of the calculated properties of the dyads are in very good agreement with the available experimental data, suggesting the suitability of the proposed theoretical approach in revealing the photoinduced electron transfer mechanisms of molecular dyads.