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Modeling near-edge fine structure x-ray spectra of the manganese catalytic site for water oxidation in photosystem II
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
2012 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 134, no 41, 17157-17167 p.Article in journal (Refereed) Published
Abstract [en]

The Mn 1s near-edge absorption fine structure (NEXAFS) has been computed by means of transition-state gradient-corrected density functional theory (DFT) on four Mn 4Ca clusters modeling the successive S 0 to S 3 steps of the oxygen-evolving complex (OEC) in photosystem II (PSII). The model clusters were obtained from a previous theoretical study where they were determined by energy minimization. They are composed of Mn(III) and Mn(IV) atoms, progressing from Mn(III) 3Mn(IV) for S 0 to Mn(III) 2Mn(IV) 2 for S 1 to Mn(III)Mn(IV) 3 for S 2 to Mn(IV) 4 for S 3, implying an Mn-centered oxidation during each step of the photosynthetic oxygen evolution. The DFT simulations of the Mn 1s absorption edge reproduce the experimentally measured curves quite well. By the half-height method, the theoretical IPEs are shifted by 0.93 eV for the S 0 → S 1 transition, by 1.43 eV for the S 1 → S 2 transition, and by 0.63 eV for the S 2 → S 3 transition. The inflection point energy (IPE) shifts depend strongly on the method used to determine them, and the most interesting result is that the present clusters reproduce the shift in the S 2 → S 3 transition obtained by both the half-height and second-derivative methods, thus giving strong support to the previously suggested structures and assignments.

Place, publisher, year, edition, pages
2012. Vol. 134, no 41, 17157-17167 p.
Keyword [en]
Absorption edges, Absorption fine structure, Catalytic sites, Clusters modeling, Energy minimization, Fine structures, Gradient-corrected density functional theory, Inflection points, Oxygen evolution, Oxygen-evolving complexes, Photosystem II, Theoretical study, Transition-state, Water oxidation, X-ray spectra, Catalytic oxidation, Density functional theory, Manganese, oxygen, water, article, catalysis, chemical structure, energy, molecular model, oxidation, photosynthesis, roentgen spectroscopy
National Category
Natural Sciences
URN: urn:nbn:se:uu:diva-186074DOI: 10.1021/ja306794pISI: 000309854700042OAI: diva2:572519
Available from: 2012-11-28 Created: 2012-11-27 Last updated: 2013-03-13Bibliographically approved

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