Applying Marcus theory to describe the carrier transports in organic semiconductors: Limitations and beyond

Marcus theory has been successfully applied to molecular design for organic semiconductors with the aid of quantum chemistry calculations for the molecular parameters: the intermolecular electronic coupling V and the intramolecular charge reorganization energy lambda. The assumption behind this is the localized nature of the electronic state for representing the charge carriers, being holes or electrons. As far as the quantitative description of carrier mobility is concerned, the direct application of Marcus semiclassical theory usually led to underestimation of the experimental data. A number of effects going beyond such a semiclassical description will be introduced here, including the quantum nuclear effect, dynamic disorder, and delocalization effects. The recently developed quantum dynamics simulation at the time-dependent density matrix renormalization group theory is briefly discussed. The latter was shown to be a quickly emerging efficient quantum dynamics method for the complex system.