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On Electron Spin Polarization Created in the Excited Triplet State of Accessory Chlorophyll via Photoinduced Charge-Recombination of the Photosystem II Reaction Center

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Abstract

We present a theoretical approach to investigate the electron spin polarization (ESP) of the excited triplet state that has been detected using the time-resolved electron paramagnetic resonance (TREPR) method in the photosystem II center of the plants. We show, using the stochastic Liouville equation, that the ESP pattern created in the accessory chlorophyll (ChlaccD1) which reside near the PD1 chlorophyll of the active branch is explained by one-step, concerted double electron transfer model, initiating from the singlet–triplet conversion of the light-induced charge-separated state composed of PD1 radical cation and pheophytin radical anion. We also considered the sequential ESP transfer model via the triplet charge-recombination (CR) and the triplet–triplet energy transfer processes. It has been clearly shown that the ESP created in the 3ChlaccD1* is dependent on the rate constant (k TT) of the triplet–triplet energy transfer from the intermediate triplet state created by the CR. Also we show that the relative orientation of the principal axes of the spin dipolar interaction in the intermediate triplet state (3PD1*, as an example) may play a role in the ESP pattern, when the k TT is smaller than the angular frequency of the Zeeman energy. We have theoretically shown that the TREPR measurement of the ESP is very powerful to investigate the primary chemical process and to characterize the intermediate as a signature of the stepwise ESP transfer.

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Acknowledgments

We thank Professor Hiroyuki Mino (Nagoya University) for valuable discussions concerning the kinetics and the mechanism of the charge separation and the triplet formation in the PS II systems.

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  1. Department of Chemistry, Faculty of Science, Shizuoka University, 836 Ohya Surugaku, Shizuoka, 422-8529, Japan

    Shusuke Katagiri & Yasuhiro Kobori

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  1. Shusuke Katagiri
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  2. Yasuhiro Kobori
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Correspondence to Yasuhiro Kobori.

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Katagiri, S., Kobori, Y. On Electron Spin Polarization Created in the Excited Triplet State of Accessory Chlorophyll via Photoinduced Charge-Recombination of the Photosystem II Reaction Center. Appl Magn Reson 37, 177–189 (2010). https://doi.org/10.1007/s00723-009-0049-8

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  • DOI: https://doi.org/10.1007/s00723-009-0049-8

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