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Tunneling in PSII

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Abstract

With available high resolution structures of PSII and a collection of reported redox midpoint potentials for most of the cofactors, it is possible to compare the expected electron tunneling rates with experimental rates to determine which electron transfer reactions are likely to reflect simply engineered electron tunneling, and which are more sophisticated and associated with large product rearrangements or the making and breaking of bonds. Reliable reorganization energies are largely lacking in this photosystem compared to PSI and purple bacteria and contribute about an order of magnitude uncertainty in tunneling rate estimates. Nevertheless it seems clear that as in purple bacterial reaction centers and PSI, with the notable exception of the oxygen evolving center, the majority of electron transfers within PSII are electron-tunneling limited at room temperature. Tunneling simulations also suggest that the short circuit between pheophytin and the adjacent chlorophyll cation may be fast enough to challenge triplet decay as the principle means of charge recombination from QA− at room temperature.

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Authors and Affiliations

  1. Department of Biochemistry and Biophysics, University of Pennsylvania, Philadelphia, PA, 19104-6059, USA

    Christopher C. Moser, Christopher C. Page & P. Leslie Dutton

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  1. Christopher C. Moser
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  2. Christopher C. Page
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  3. P. Leslie Dutton
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Correspondence to Christopher C. Moser.

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Dedicated to Professor James Barber on the occasion of his 65th birthday.

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Moser, C.C., Page, C.C. & Dutton, P.L. Tunneling in PSII. Photochem Photobiol Sci 4, 933–939 (2005). https://doi.org/10.1039/b507352a

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