Photosynthesis Research

, Volume 98, Issue 1–3, pp 53–80 | Cite as

Photosystem II: The machinery of photosynthetic water splitting

  • Gernot Renger
  • Thomas Renger


This review summarizes our current state of knowledge on the structural organization and functional pattern of photosynthetic water splitting in the multimeric Photosystem II (PS II) complex, which acts as a light-driven water: plastoquinone-oxidoreductase. The overall process comprises three types of reaction sequences: (1) photon absorption and excited singlet state trapping by charge separation leading to the ion radical pair \( {\text{P}}680^{ + \bullet } {\text{Q}}_{\text{A}}^{ - \bullet } \left( { \overset{\wedge}{=}{\text{P}}_{\text{D1}}^{ + \bullet } {\text{Q}}_{\text{A}}^{ - \bullet } } \right) \) formation, (2) oxidative water splitting into four protons and molecular dioxygen at the water oxidizing complex (WOC) with \( {\text{P}}680^{ + \bullet } \) as driving force and tyrosine YZ as intermediary redox carrier, and (3) reduction of plastoquinone to plastoquinol at the special QB binding site with \( {\text{Q}}_{\text{A}}^{ - \bullet } \) acting as reductant. Based on recent progress in structure analysis and using new theoretical approaches the mechanism of reaction sequence (1) is discussed with special emphasis on the excited energy transfer pathways and the sequence of charge transfer steps: \( ^{1} \left( {\text{RC-PC}} \right)^{ *} {\text{Q}}_{\text{A}} \to {\text{P}}_{{{\text{D}}2}} {\text{P}}_{{{\text{D}}1}} {\text{Chl}}_{{{\text{D}}1}}^{ + \bullet } {\text{Pheo}}_{{{\text{D}}1}}^{ - \bullet } {\text{Q}}_{\text{A}} \to {\text{P}}_{{{\text{D}}2}} {\text{P}}_{{{\text{D}}1}}^{ + \bullet } {\text{Chl}}_{{{\text{D}}1}} {\text{Pheo}}_{{{\text{D}}1}}^{ - \bullet } {\text{Q}}_{\text{A}} \to {\text{P}}_{{{\text{D}}2}} {\text{P}}_{{{\text{D}}1}}^{ + \bullet } {\text{Chl}}_{\text{D1}} {\text{Pheo}}_{\text{D1}} {\text{Q}}_{\text{A}}^{ - \bullet } , \) where 1(RC-PC)* denotes the excited singlet state 1P680* of the reaction centre pigment complex. The structure of the catalytic Mn4O X Ca cluster of the WOC and the four step reaction sequence leading to oxidative water splitting are described and problems arising for the electronic configuration, in particular for the nature of redox state S3, are discussed. The unravelling of the mode of O–O bond formation is of key relevance for understanding the mechanism of the process. This problem is not yet solved. A multistate model is proposed for S3 and the functional role of proton shifts and hydrogen bond network(s) is emphasized. Analogously, the structure of the QB site for PQ reduction to PQH2 and the energetic and kinetics of the two step redox reaction sequence are described. Furthermore, the relevance of the protein dynamics and the role of water molecules for its flexibility are briefly outlined. We end this review by presenting future perspectives on the water oxidation process.


Photosystem II Charge separation Oxidative water splitting Reductive plastoquinol formation Mechanisms 

List of abbreviations


Antenna complexes







ChlD1, ChlD2

“accessory” Chlorophylls of the D1- and D2-branches, respectively of the RC


Chlorophyll binding proteins

CP43, CP47

Core antenna subunits of PS II


Density functional theory




Excitation energy transfer


Midpoint redox potential


Electron paramagnetic resonance


Electron transfer


Extended X-ray absorption fine structure


Fourier transform infrared


Light harvesting complex II


Detailed symbol for redox states S i of the WOC


Multiple site electron and proton transfer


Nonadiabatic electron transfer


Photosystem II


RC of purple bacteria



\( {\text{P}}680^{ + \bullet } \)

Oxidized state of the RC pigments

PD1, PD2

“special pair” Chlorophylls of the D1- and D2-branches, respectively, of the RC

PheoD1, PheoD2

Pheophytins of the D1- and D2-branches, respectively, of the RC




Proton transfer


Plastoquinones of the RC


Quasielastic neutron scattering


Reaction center

1(RC-PC)*, 1P680*

Excited singlet state of the RC pigments




Water oxidizing complex

Yz, YD

Redox active tyrosines of the D1- and D2-branches, respectively


X-ray diffraction crystallography



We thank Govindjee for critical reading and many helpful comments to improve the manuscript, Yulia Pushkar and Vittal Yachandra for providing the data for Fig. 6c, Jan Kern for Figs. 1, 6a and b, Philipp Kühn for the electronic versions of Figs. 4, 5 and 7 and Jörg Pieper for Fig. 9. The financial support by Deutsche Forschungsgemeinschaft (Sfb 429 TP A1 (G.R.) and TP A9 (T.R.)) is gratefully acknowledged. T.R. acknowledges support from the Cluster of Excellence “Unified Concepts in Catalysis” coordinated by the Technische Universität Berlin and funded by the Deutsche Forschungsgemeinschaft.


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© Springer Science+Business Media B.V. 2008

Authors and Affiliations

  1. 1.Max Volmer Laboratory for Biophysical ChemistryBerlin Institute of TechnologyBerlinGermany
  2. 2.Institute for Chemistry and BiochemistryFree University BerlinBerlinGermany

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