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ChemRxiv-Triad-NEFGR.pdf (2.64 MB)
Photoinduced Charge Transfer Dynamics in Carotenoid-Porphyrin-C60 Triad via the Linearized Semiclassical Nonequilibrium Fermi's Golden Rule
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submitted on 20.06.2020 and posted on 23.06.2020by Zhengqing Tong, Margaret S. Cheung, Barry D. Dunietz, Eitan Geva, Xiang Sun
The nonequilibrium Fermi’s golden rule (NE-FGR) describes the time-dependent rate coefficient for electronic transitions, when the nuclear degrees of freedom start out in a nonequilibrium state. In this letter, the linearized semiclassical (LSC) approximation of the NE-FGR is used to calculate the photoinduced charge transfer rates in the carotenoid-porphyrin-C60 molecular triad dissolved in explicit tetrahydrofuran. The initial nonequilibrium state corresponds to impulsive photoexcitation from the equilibrated ground-state to the ππ* state, and the porphyrin-to-C60 and the carotenoid-to-C60 charge transfer rates are calculated. Our results show that accounting for the nonequilibrium nature of the initial state significantly enhances the transition rate of the porphyrin-to-C60 CT process. We also derive the instantaneous Marcus theory (IMT) from LSC NE-FGR, which casts the CT rate coefficients in terms of a Marcus-like expression, with explicitly time-dependent reorganization energy and reaction free energy. IMT is found to reproduce the CT rates in the system under consideration remarkably well.