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Experimental and calculated Raman spectra in Ca–Zn pyroxenes and a comparison between (CaxM2+1−x)M2+Si2O6 pyroxenes (M2+ = Mg, Co, Zn, Fe2+)

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Abstract

The Raman spectra of the end member pyroxenes CaZnSi2O6 and Zn2Si2O6 are calculated by quantum mechanical modeling and compared with the experimental ones measured in synthetic (CaxZn1−x)ZnSi2O6 pyroxenes with x = 0, 0.2, 0.3, 0.5, 0.7, 1. The calculated spectra correctly predict the intensity and peak positions of the spectra recorded on the end members. The model provides also useful hints for the mode assignment at the intermediate compositions. The experimental peak positions are compared in (CaxM2+1−x)M2+Si2O6 pyroxenes, with M2+ = Mg, Co, Zn, Fe2+. These pyroxenes share a common charge and different mass and ionic radius; the relative contributions of the mass and ionic radius in the experimental spectrum are discussed in four of the most intense peaks. We found that the positions of the strongest peaks are related to the average bond distances of the polyhedra which most affect a given mode. Ca–Zn pyroxenes provide an exception, whereas the CaZnSi2O6 end member fits quite well in the bond-distance/peak positions relations found in other pyroxenes, and the same does not occur as Zn exchanges for Ca. Peak broadening occurs in Zn pyroxenes in intermediate compositions; it is related to the presence of polyhedral local configurations around Zn and Ca atoms in the M2 polyhedron. The broadening is higher in the ~ 1010 cm−1 peak (ν19), which, among the strongest peaks, shows the highest difference in the Raman wavenumber between end members. The different behaviours of Zn pyroxenes with respect to Mg, Co, and Fe2+ ones are likely related to the partially covalent bonding in the M2 cavity shown by Zn pyroxenes.

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Acknowledgements

Helpful and constructive revisions by two anonymous reviewers significantly improved this paper and are acknowledged. This work was supported by MIUR funding PRIN2010-2011 (2010EARRRZ_005).

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Author notes

  1. Claudia Stangarone

    Present address: German Aerospace Center (DLR), Rutherfordstraße 2, 12489, Berlin, Germany

Authors and Affiliations

  1. Department of Chemistry, Life Sciences and Environmental Sustainability, University of Parma, Parco Area delle Scienze 157/A, 43124, Parma, Italy

    Mario Tribaudino, Claudia Stangarone, Claudia Gori & Luciana Mantovani

  2. Department of Mathematical, Physical and Computer Sciences, University of Parma, Parco Area delle Scienze 7/A, 43124, Parma, Italy

    Danilo Bersani & Pier Paolo Lottici

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  1. Mario Tribaudino
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  2. Claudia Stangarone
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Correspondence to Mario Tribaudino.

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Tribaudino, M., Stangarone, C., Gori, C. et al. Experimental and calculated Raman spectra in Ca–Zn pyroxenes and a comparison between (CaxM2+1−x)M2+Si2O6 pyroxenes (M2+ = Mg, Co, Zn, Fe2+). Phys Chem Minerals 46, 827–837 (2019). https://doi.org/10.1007/s00269-019-01043-z

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