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  How Accurately Can Extended X-ray Absorption Spectra Be Predicted from First Principles? Implications for Modeling the Oxygen-Evolving Complex in Photosystem II

Beckwith, M. A., Ames, W., Vila, F. D., Krewald, V., Pantazis, D. A., Mantel, C., et al. (2015). How Accurately Can Extended X-ray Absorption Spectra Be Predicted from First Principles? Implications for Modeling the Oxygen-Evolving Complex in Photosystem II. Journal of the American Chemical Society, 137(40), 12815-12834. doi:10.1021/jacs.5b00783.

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 Creators:
Beckwith, Martha. A.1, 2, Author           
Ames, William1, Author           
Vila, Fernando D.3, Author
Krewald, Vera1, Author           
Pantazis, Dimitrios A.1, Author           
Mantel, Claire4, Author
Pécaut, Jacques5, Author
Gennari, Marcello4, Author
Duboc, Carole4, Author
Collomb, Marie-Noëlle4, Author
Yano, Junko6, Author
Rehr, John J.3, Author
Neese, Frank1, Author           
DeBeer, Serena1, 2, Author           
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States, ou_persistent22              
3Department of Physics, University of Washington, Seattle, Washington 98195, United States, ou_persistent22              
4Département de Chimie Moléculaire, Université Joseph Fourier Grenoble, CNRS, F-38000 Grenoble, France , ou_persistent22              
5Laboratoire de Reconnaissance Ionique et Chimie de Coordination, Service de Chimie Inorganique et Biologique, (UMR E-3 CEA/UJF, FRE3200 CNRS), CEA-Grenoble, INAC, 17 rue des Martyrs 38054 Grenoble cedex 9, France, ou_persistent22              
6Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, ou_persistent22              

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 Abstract: First principle calculations of extended X-ray absorption fine structure (EXAFS) data have seen widespread use in bioinorganic chemistry, perhaps most notably for modeling the Mn4Ca site in the oxygen evolving complex (OEC) of photosystem II (PSII). The logic implied by the calculations rests on the assumption that it is possible to a priori predict an accurate EXAFS spectrum provided that the underlying geometric structure is correct. The present study investigates the extent to which this is possible using state of the art EXAFS theory. The FEFF program is used to evaluate the ability of a multiple scattering-based approach to directly calculate the EXAFS spectrum of crystallographically defined model complexes. The results of these parameter free predictions are compared with the more traditional approach of fitting FEFF calculated spectra to experimental data. A series of seven crystallographically characterized Mn monomers and dimers is used as a test set. The largest deviations between the FEFF calculated EXAFS spectra and the experimental EXAFS spectra arise from the amplitudes. The amplitude errors result from a combination of errors in calculated S02 and Debye–Waller values as well as uncertainties in background subtraction. Additional errors may be attributed to structural parameters, particularly in cases where reliable high-resolution crystal structures are not available. Based on these investigations, the strengths and weaknesses of using first-principle EXAFS calculations as a predictive tool are discussed. We demonstrate that a range of DFT optimized structures of the OEC may all be considered consistent with experimental EXAFS data and that caution must be exercised when using EXAFS data to obtain topological arrangements of complex clusters.

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Language(s): eng - English
 Dates: 2015-01-232015-09-092015-10-14
 Publication Status: Published in print
 Pages: 20
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.5b00783
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 137 (40) Sequence Number: - Start / End Page: 12815 - 12834 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870