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Electron density distribution and bond critical point properties for forsterite, Mg2 SiO4, determined with synchrotron single crystal X-ray diffraction data

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Abstract

A generalized X-ray scattering factor model experimental electron density distribution has been generated for the orthosilicate forsterite, using an essentially extinction and absorption free set of single crystal diffraction data recorded with intense, high energy synchrotron X-ray radiation (E=100.6 keV). A refinement of the model converged with an R(F)=0.0061. An evaluation of the bond critical point, bcp, properties of the distribution at the (3, −1) stationary points for the SiO and MgO bonded interactions, yielded values that agree typically within ~5%, on average, with theoretical values generated with quantum chemical computational strategies, using relatively robust basis sets. On the basis of this result, the modeling of the experimental distribution is considered to be adequate. As the bcp properties increase in magnitude, the MgO and SiO bonds decrease in length as calculated for a number of rock forming silicates. As asserted by Coppens (X-ray charge densities and chemical bonding. Oxford University Press, Oxford, 1997), large negative ∇2ρ(r c ) values, characteristic of shared interactions involving first row atoms, may not be characteristic of closed shell covalent bonded interactions involving second row Si, P and S atoms bonded to O. This study adds new evidence to the overall relatively good agreement between theoretical bcp properties generated with computational quantum strategies, on the one hand, and experimental properties generated with single crystal high energy synchrotron diffraction data on the other. The similarity of results not only provides a basis for using computational strategies for studying and modeling structures, defects and the reactivity of representative structures, but it also provides a basis for improving our understanding of the crystal chemistry of earth materials and the character of the SiO bonded interaction.

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Acknowledgments

The National Science Foundation and the U. S. Department of Energy are thanked for supporting this study in part with Grants EAR-9627458 (GVG, MB Boisen, Jr.), EAR-0229472 (NL Ross, GVG), DE-FG02-03ER15389 (JD Rimstidt, GVG), and DE-FG02-97ER14751 (DFC). This study was also generously supported by the National Computation Sciences Alliance under a SURA Block Grant (Project ndg), utilizing the IBM p690 at the National Center of Supercomputing Applications. A. Kirfel and T. Lippmann gratefully acknowledge financial support by the Bundesminister für Bildung und Forschung, contract No. 05 KS1PDA, under which the experimental study of forsterite, measurements, refinements and topological analyses were completed. With the exceptions of the sections on the experimental and data collection and the refinement strategies, much of this paper was written in large part by GVG when he was a Visiting Scholar at the University of Arizona in 2005. Bob Downs and the University Distinguished Professors Foundation at Virginia Tech are thanked for generously supporting the visit. Bob Downs, Charlie Prewitt, Marcus Oligero and Sue Robison are also thanked for making the visit a very worthwhile and profitable experience.

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Authors and Affiliations

  1. Mineralogisch-Petrologisches Institut, Universität Bonn, Poppelsdorfer Schloss, 53115, Bonn, Germany

    A. Kirfel

  2. GKSS, Max-Planck-Strasse, 21502, Geesthacht, Germany

    T. Lippmann

  3. Institut für Materialchemie, Technische Universität Wien, Getreidemarkt 9/156-TC, 1060, Wien, Austria

    P. Blaha & K. Schwarz

  4. Department of Chemical Engineering, Virginia Tech, Blacksburg, 24061, VA, USA

    D. F. Cox

  5. W.R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, PO Box 999, KB-96, Richland, 99352, WA, USA

    K. M. Rosso

  6. Departments of Geosciences, Materials Science and Engineering and Mathematics, Virginia Tech, Blacksburg, VA, 24061, USA

    G. V. Gibbs

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  1. A. Kirfel
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Kirfel, A., Lippmann, T., Blaha, P. et al. Electron density distribution and bond critical point properties for forsterite, Mg2 SiO4, determined with synchrotron single crystal X-ray diffraction data. Phys Chem Minerals 32, 301–313 (2005). https://doi.org/10.1007/s00269-005-0468-5

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