Photoinduced charge transfer plays a key role in the conversion of solar energy. In this work, we investigate the charge transfer rates of a bio-inspired organic photovoltaic (OPV) material via a hierarchy of post-Marcus methods based on the linearized semiclassical (LSC) method. 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 developed a hierarchy of LSC-based approaches for calculating the photoinduced charge transfer rates within the framework of equilibrium and nonequilibrium Fermi’s golden rule. These LSC-based methods allow one to account for quantum effects based on classical-like inputs. We showcase the feasibility, accuracy, and robustness of these methods within the context of a realistic molecular application to the carotenoid-porphyrin-C<sub>60</sub> molecular triad in polar organic solvent described in terms of anharmonic force fields. Multistate charge transfer between the spectroscopic bright π-π*, partially charge-separated, and fully charge-separated states of two typical triad confirmations are investigated. 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.

Photoinduced charge transfer rates in light-harvesting carotenoid-porphyrin-C<sub>60</sub> molecular triad

253rd National Meeting (2017)

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Photoinduced charge transfer rates in light-harvesting carotenoid-porphyrin-C60 molecular triad

Photoinduced charge transfer rates in light-harvesting carotenoid-porphyrin-C₆₀ molecular triad