Computational insights into the O2-evolving complex of photosystem II

Eduardo M. Sproviero, James P. McEvoy, José A. Gascón, Gary W. Brudvig, Victor S. Batista

Research output: Contribution to journalReview articlepeer-review

50 Citations (Scopus)


Mechanistic investigations of the water-splitting reaction of the oxygen-evolving complex (OEC) of photosystem II (PSII) are fundamentally informed by structural studies. Many physical techniques have provided important insights into the OEC structure and function, including X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy as well as mass spectrometry (MS), electron paramagnetic resonance (EPR) spectroscopy, and Fourier transform infrared spectroscopy applied in conjunction with mutagenesis studies. However, experimental studies have yet to yield consensus as to the exact configuration of the catalytic metal cluster and its ligation scheme. Computational modeling studies, including density functional (DFT) theory combined with quantum mechanics/molecular mechanics (QM/MM) hybrid methods for explicitly including the influence of the surrounding protein, have proposed chemically satisfactory models of the fully ligated OEC within PSII that are maximally consistent with experimental results. The inorganic core of these models is similar to the crystallographic model upon which they were based, but comprises important modifications due to structural refinement, hydration, and proteinaceous ligation which improve agreement with a wide range of experimental data. The computational models are useful for rationalizing spectroscopic and crystallographic results and for building a complete structure-based mechanism of water-splitting in PSII as described by the intermediate oxidation states of the OEC. This review summarizes these recent advances in QM/MM modeling of PSII within the context of recent experimental studies.

Original languageEnglish
Pages (from-to)91-114
Number of pages24
JournalPhotosynthesis Research
Issue number1
Publication statusPublished - Jul 2008


  • Density functional theory (DFT)
  • Oxomanganese complexes
  • Oxygen evolution
  • Oxygen evolving center
  • Photosynthesis
  • Photosystem II
  • Quantum mechanics/molecular mechanics (QM/MM)
  • Water oxidation

ASJC Scopus subject areas

  • Biochemistry
  • Plant Science
  • Cell Biology

Fingerprint Dive into the research topics of 'Computational insights into the O<sub>2</sub>-evolving complex of photosystem II'. Together they form a unique fingerprint.

Cite this