P 2 1 / c Postorthopyroxene γ-LiScGe 2 O 6 , a New Dense High-Pressure Polymorph and Its Direct Transformation from the Pbca Structure

• Published in: Inorganic chemistry 2020-12, Vol.59 (24), p.17981-17991
• Main Authors: Ende, Martin, Meusburger, Johannes M, Zeug, Manuela, Scheidl, Katharina S, Redhammer, Günther J, Miletich, Ronald
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.0c02284

Orthorhombic β-LiScGe O single crystals were compressed hydrostatically up to 10.35 GPa using a diamond anvil cell and investigated in situ by means of X-ray diffraction and Raman spectroscopy. Crystal-structure investigations at ambient conditions and at high pressure show a structural transition from an orthopyroxene-type structure ( ≈ 18.43 Å, ≈ 8.85 Å, and ≈ 5.34 Å at 8.6 ± 0.1 GPa) to a postorthopyroxene type 2 / structure of the new dense γ-LiScGe O ( ≈ 18.62 Å, ≈ 8.85 Å, ≈ 5.20 Å, and ≈ 93.1° at 9.5 ± 0.1 GPa). The structure refinements reveal displacive shifts of O atoms associated with a rotation of every other tetrahedral-chain unit from the O- to S-type position similar to the postorthopyroxene-type MgSiO . As a consequence of the oxygen displacement, the coordination number of Li atoms is changing from [5 + 1] to a proper 6-fold coordination. The transition around = 9.0 ± 0.1 GPa is associated with a volume discontinuity of Δ = -1.6%. This orthopyroxene (OEn- ) to postorthopyroxene (pOEn- 2 / ) transition is the second example of this type of transformation. Precise lattice parameters have been determined during isothermal compression. The fit of the unit-cell volumes of -LiScGe O , using a third-order Birch-Murnaghan equation of state, yields = 943.63 ± 0.11 Å , = 89.8 ± 0.6 GPa, and d /d = 4.75 ± 0.18 as parameters. Evaluation of the data points beyond the critical transition pressure using a second-order Birch-Murnaghan equation suggests = 940.6 ± 4.4 Å and = 82.4 ± 4.8 GPa. A series of high-pressure Raman spectra confirm the symmetry-related structural transition, with band positions shifting in a noncontinuous manner, thus confirming the proposed first-order transition.