Prof. SUN XiangNew York University Shanghai
ROOM 9004, Hefei National Laboratory Building
Abstract: Photoinduced charge transfer plays a key role in the conversion of solar energy. In this work, we introduce a hierarchy of post-Marcus methods based on the linearized semiclassical (LSC) method for calculating the charge transfer rates in organic photovoltaic material. The LSC approximation provides a flexible, rigorous and self-consistent framework for developing computationally feasible methods, capable of capturing important quantum effects in complex many-body systems. We derived the LSC-based photoinduced charge transfer rates within the framework of equilibrium and nonequilibrium Fermi’s golden rule. The LSC-based methods are compared with fully quantum-mechanical charge transfer rates in benchmarking spin-boson systems. We also showcase the feasibility, accuracy, and robustness of these methods within the context of a realistic molecular application to the carotenoid-porphyrin-fullerene molecular triad in polar organic solvent described in terms of anharmonic force fields. From the charge transfer rate calculations on different levels of approximations, we are able to resolve the photoinduced charge transfer mechanism and test the validity of classic Marcus assumptions, such as parabolic potential surfaces, Condon approximation, and neglecting nuclear dynamical effects.
Address: University of Science and Technology of China, No.96, JinZhai Road Baohe District, Hefei, Anhui, 230026, P.R.China.