Modeling near-edge fine structure x-ray spectra of the manganese catalytic site for water oxidation in photosystem II
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
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.
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
IdentifiersURN: urn:nbn:se:uu:diva-186074DOI: 10.1021/ja306794pISI: 000309854700042OAI: oai:DiVA.org:uu-186074DiVA: diva2:572519