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Multipole-refined charge density study of diopside at ambient conditions

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Abstract

The experimental multipole electron density, ρ(r), of diopside was derived from high-resolution single-crystal diffraction at room temperature. Its topological analysis revealed predominantly ionic Si–O bonding, as found in electron density studies of other silicates. In particular, the non-bridging Si–O bonds are slightly less ionic in character than the bridging Si–O bonds. The Ca–O and Mg–O bonds are classified as pure closed-shell ionic interactions. An analysis of –∇2ρ(r) showed the presence of maxima around the oxygen atoms, associated to lone pairs domains that are involved in bonds with the surrounding ions. Calculation of atomic basins gave net charges of –1.56(12), 3.11(17), 1.79(13) and 1.88(18) e for O (averaged), Si, Ca and Mg atoms, respectively. O···O interactions between the O atoms at the vertices of the SiO4 tetrahedron were also detected from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. All these results were also confirmed by periodic restricted Hartree–Fock (RHF) calculations.

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Acknowledgment

We gratefully thank Prof. J. Gibbs for a stimulating discussion about the Espinosa classification of the atomic interactions.

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Authors and Affiliations

  1. CNR-Istituto di Scienze e Tecnologie Molecolari, via Golgi 19, 20133, Milano, Italy

    R. Bianchi & A. Forni

  2. CNR-Istituto di Geoscienze e Georisorse (Sezione di Pavia), via Ferrata 1, 27100, Pavia, Italy

    R. Oberti

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  1. R. Bianchi
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  2. A. Forni
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  3. R. Oberti
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Correspondence to R. Bianchi.

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Bianchi, R., Forni, A. & Oberti, R. Multipole-refined charge density study of diopside at ambient conditions. Phys Chem Minerals 32, 638–645 (2005). https://doi.org/10.1007/s00269-005-0039-9

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