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Trapping Dynamics in Photosystem I-Light Harvesting Complex I of Higher Plants Is Governed by the Competition Between Excited State Diffusion from Low Energy States and Photochemical Charge Separation

Molotokaite, Egle, Remelli, William, Casazza, Anna Paola, Zucchelli, Giuseppe, Polli, Dario, Cerullo, Giulio, Santabarbara, Stefano
The Journal of physical chemistry 2017 v.121 no.42 pp. 9816-9830
absorption, chlorophyll, electron transfer, energy, fluorescence, harvesting, light harvesting complex, models, photochemistry, spinach, trapping, wavelengths
The dynamics of excited state equilibration and primary photochemical trapping have been investigated in the photosystem I-light harvesting complex I isolated from spinach, by the complementary time-resolved fluorescence and transient absorption approaches. The combined analysis of the experimental data indicates that the excited state decay is described by lifetimes in the ranges of 12–16 ps, 32–36 ps, and 64–77 ps, for both detection methods, whereas faster components, having lifetimes of 550–780 fs and 4.2–5.2 ps, are resolved only by transient absorption. A unified model capable of describing both the fluorescence and the absorption dynamics has been developed. From this model it appears that the majority of excited state equilibration between the bulk of the antenna pigments and the reaction center occurs in less than 2 ps, that the primary charge separated state is populated in ∼4 ps, and that the charge stabilization by electron transfer is completed in ∼70 ps. Energy equilibration dynamics associated with the long wavelength absorbing/emitting forms harbored by the PSI external antenna are also characterized by a time mean lifetime of ∼75 ps, thus overlapping with radical pair charge stabilization reactions. Even in the presence of a kinetic bottleneck for energy equilibration, the excited state dynamics are shown to be principally trap-limited. However, direct excitation of the low energy chlorophyll forms is predicted to lengthen significantly (∼2-folds) the average trapping time.