Low-pressure ferroelastic phase transition in rutile-type AX2 minerals: cassiterite (SnO2), pyrolusite (MnO2) and sellaite (MgF2)

  • Nadia Curetti
  • Marcello Merli
  • Silvana Capella
  • Piera Benna
  • Alessandro PaveseEmail author
Original Paper


The structural behaviour of cassiterite (SnO2), pyrolusite (MnO2) and sellaite (MgF2), i.e. AX2-minerals, has been investigated at room temperature by in situ high-pressure single-crystal diffraction, up to 14 GPa, using a diamond anvil cell. Such minerals undergo a ferroelastic phase transition, from rutile-like structure (SG: P42/mnm) to CaCl2-like structure (SG: Pnnm), at ≈ 10.25, 4.05 and 4.80 GPa, respectively. The structural evolution under pressure has been described by the trends of some structure parameters that are other than zero in the region of the low-symmetry phase’s stability. In particular, three tilting-angles (ω, ω′, ABS) and the metric distortion of the cation-centred octahedron (quantified via the difference between apical-anion and equatorial-anion distances Δ|Xax−Xeq|) are used to express the atoms’ readjustment, i.e. relaxation, taking place in the CaCl2-like structures under pressure. The crystallographic investigation presented is complemented with an analysis of the energy involved in the phase transition using the Landau formalism and adopting the following definition for the order parameter: Q = η11η22, ηij being the spontaneous strain tensor. The dependence of ω, ω′, ABS and Δ|Xax−Xeq| on Q allows determination of a correlation between geometrical deformation parameter and energy. Lastly, the relaxation mechanisms that exploits ω, ω′, ABS and Δ|Xax−Xeq| may be related to the ionic degree of bonding, the latter modelled via quantum mechanics and Bader theory. Sellaite, the mineral exhibiting the highest degree of ionic bonding among those investigated, tends to accomplish relaxation through pure rotation of the octahedron, rather than a metric distortion (Δ|Xax−Xeq|), which would shorten inter-atomic distances thus increasing repulsion between anions.


High-pressure diffraction Ferroelastic phase transition Cassiterite Pyrolusite Sellaite 



The authors are very grateful to Marco Ciriotti (President of AMI, “Associazione Micromineralogica Italiana”) for supplying the natural samples and precise information about their geographic occurrences. Reviews from two anonymous referees greatly improved the manuscript; we are grateful to them for critical reading and useful suggestions. We sincerely thank Laurie Jayne Kurilla for giving valuable advice on the English language. The CrisDi and G Scansetti Interdepartmental Centers of University of Torino are acknowledged. The present investigation was partly funded by the Italian Ministry for Education, University and Research through the MIUR-Project PRIN 2017 (2017L83S77).

Supplementary material

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Supplementary material 1 (CIF 180 kb)
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Supplementary material 2 (CIF 135 kb)
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Supplementary material 3 (CIF 119 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Earth Sciences DepartmentUniversity of TorinoTurinItaly
  2. 2.CrisDi Interdepartmental Center for CrystallographyTurinItaly
  3. 3.Earth and Sea DepartmentUniversity of PalermoPalermoItaly

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