Photosynthesis Research

, Volume 92, Issue 3, pp 289–303 | Cite as

Oxidation state changes of the Mn4Ca cluster in Photosystem II

Research Article


A detailed electronic structure of the Mn4Ca cluster is required before two key questions for understanding the mechanism of photosynthetic water oxidation can be addressed. They are whether all four oxidizing equivalents necessary to oxidize water to O2 accumulate on the four Mn ions of the oxygen-evolving complex, or do some ligand-centered oxidations take place before the formation and release of O2 during the S→ [S4] → S0 transition, and what are the oxidation state assignments for the Mn during S-state advancement. X-ray absorption and emission spectroscopy of Mn, including the newly introduced resonant inelastic X-ray scattering spectroscopy have been used to address these questions. The present state of understanding of the electronic structure and oxidation state changes of the Mn4Ca cluster in all the S-states, particularly in the S2 to S3 transition, derived from these techniques is described in this review.


Photosystem II Water oxidation Oxygen evolution Manganese cluster X-ray spectroscopy 



Photosystem II


oxygen-evolving complex


electron paramagnetic resonance


Electron-Nuclear Double Resonance


X-ray absorption spectroscopy


extended X-ray absorption fine structure


X-ray absorption near-edge spectroscopy


multiline EPR signal


near infra-red


Inflection point energy


X-ray emission spectroscopy


resonant inelastic X-ray scattering


constant incident energy


constant energy transfer



The research from our group presented in this review was supported by the NIH grant (GM 55302), and the DOE, Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, under Contract DE-AC02-05CH11231. Synchrotron radiation facilities were provided by SSRL, APS, and ALS, which are supported by DOE, Office of Basic Energy Sciences. The SSRL Biotechnology Program is supported by NIH, National Center of Research Resources, Biomedical Technology Program, and by DOE, Office of Health and Environmental Research. BioCAT at the APS is a NIH-supported Research Center RR-08630. We thank John Robblee, Johannes Messinger, Uwe Bergmann, Pieter Glatzel, Henk Visser, Carmen Fernandez, Shelly Pizarro, Elodie Anxolabéhère-Mallart, Wen Liang, Theo Roelofs, Yulia Pushkar, and Ken Sauer for contributing to much of the work presented in this review and for many helpful discussions over the years. We dedicate this review to the memory of Ron Guiles (1951–2005), who was a key person in the early development of X-ray spectroscopy techniques as applied to Photosystem II.


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Copyright information

© Springer Science+Business Media B.V. 2007

Authors and Affiliations

  1. 1.Melvin Calvin Laboratory, Physical Biosciences DivisionLawrence Berkeley National LaboratoryBerkeleyUSA

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