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1. Strong enhancement of magnetic ordering temperature and structural/valence transitions in EuPd 3 S 4 under high pressure

   https://doi.org/10.1073/pnas.2310779120  

   Huyan, Shuyuan ; Ryan, Dominic H. ; Slade, Tyler J. ; Lavina, Barbara ; Jose, Greeshma ; Wang, Haozhe ; Wilde, John M. ; Ribeiro, Raquel A. ; Zhao, Jiyong ; Xie, Weiwei ; et al ( December 2023 , Proceedings of the National Academy of Sciences)

   We present a comprehensive study of the inhomogeneous mixed-valence compound, EuPd₃S₄, by electrical transport, X-ray diffraction, time-domain¹⁵¹Eu synchrotron Mössbauer spectroscopy, and X-ray absorption spectroscopy measurements under high pressure. Electrical transport measurements show that the antiferromagnetic ordering temperature,T_N, increases rapidly from 2.8 K at ambient pressure to 23.5 K at ~19 GPa and plateaus between ~19 and ~29 GPa after which no anomaly associated withT_Nis detected. A pressure-induced first-order structural transition from cubic to tetragonal is observed, with a rather broad coexistence region (~20 GPa to ~30 GPa) that corresponds to theT_Nplateau. Mössbauer spectroscopy measurements show a clear valence transition from approximately 50:50 Eu²⁺:Eu³⁺to fully Eu³⁺at ~28 GPa, consistent with the vanishing of the magnetic order at the same pressure. X-ray absorption data show a transition to a fully trivalent state at a similar pressure. Our results show that pressure first greatly enhancesT_N, most likely via enhanced hybridization between the Eu 4fstates and the conduction band, and then, second, causes a structural phase transition that coincides with the conversion of the europium to a fully trivalent state.

    

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2. Structural Behavior of C2/m Tremolite to 40 GPa: A High-Pressure Single-Crystal X-ray Diffraction Study

   https://doi.org/10.2138/am-2022-8278  

   Ott, Jason N. ; Kalkan, Bora ; Kunz, Martin ; Berlanga, Genesis ; Yuvali, Ali F. ; Williams, Quentin ( October 2022 , American Mineralogist)

   The high-pressure structure and stability of the calcic amphibole tremolite (Ca2Mg5Si8O22(OH)2) was investigated to ~40 GPa at 300 K by single-crystal X-ray diffraction using synchrotron radiation. C2/m symmetry tremolite displays a broader metastability range than previously studied clinoamphiboles, exhibiting no first-order phase transition up to 40 GPa. Axial parameter ratios a/b and a/c, in conjunction with finite strain versus normalized pressure trends, indicate that changes in compressional behavior occur at pressures of ~5 and ~20 GPa. An analysis of the finite strain trends, using third-order Birch-Murnaghan equations of state, resulted in bulk moduli (𝐾) of 72(7), 77(2), and 61(1) GPa for the compressional regimes from 0-5 GPa (regime I), 5-20 GPa (II), and above 20 GPa (III), respectively, and accompanying pressure-derivatives of the bulk moduli (𝐾′) of 8.6(42), 6.0(3), and 10.0(2). The results are consistent with first-principle theoretical calculations of tremolite elasticity. The axial compressibility ratios of tremolite, determined as 𝛽a : 𝛽b : 𝛽c = 2.22:1.0:0.78 (regime I), 2.12:1.0:0.96 (II), and 1.03:1.0:0.75 (III), demonstrate a substantial reduction of the compressional anisotropy of tremolite at high pressures, which is a notable contrast with the increasingly anisotropic compressibility observed in the high-pressure polymorphs of the clinoamphibole grunerite. The shift in compression-regime at 5 GPa (I-II) transition is ascribed to stiffening along the crystallographic a-axis corresponding to closure of the vacant A-site in the structure, and a shift in the topology of the a-oriented surfaces of the structural I-beam from concave to convex. The II-III regime shift at 20 GPa corresponds to an increasing rate of compaction of the Ca-polyhedra and increased distortion of the Mg-octahedral sites, processes which dictate compaction in both high-pressure compression-regimes. Bond-valence analyses of the tremolite structure under pressure show dramatic overbonding of the Ca-cations (75% at 30 GPa), with significant Mg-cation overbonding as well (40%). These imply that tremolite’s notable metastability range hinges on the calcium cation’s bonding environment. The 8-fold coordinated Ca-polyhedron accommodates significant compaction under pressure, while the geometry of the Ca-O polyhedron becomes increasingly regular and inhibits the reorientation of the tetrahedral chains that generate phase transitions observed in other clinoamphiboles. Peak/background ratio of diffraction data collected above 40 GPa and our equation of state determination of bulk moduli and compressibilities of tremolite in regime III, in concert with the results of our previous Raman study, suggest that C2/m tremolite may be approaching the limit of its metastability above 40 GPa. Our results have relevance for both the metastable compaction of tremolite during impact events, and for possible metastable persistence of tremolite within cold subduction zones within the Earth. 

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3. High pressure raman spectroscopy and X-ray diffraction of K2Ca(CO3)2 bütschliite: multiple pressure-induced phase transitions in a double carbonate

   https://doi.org/10.1007/s00269-023-01262-5  

   Zeff, G. ; Kalkan, B. ; Armstrong, K. ; Kunz, M. ; Williams, Q. ( January 2024 , Physics and Chemistry of Minerals)

   The crystal structure and bonding environment of K₂Ca(CO₃)₂bütschliite were probed under isothermal compression via Raman spectroscopy to 95 GPa and single crystal and powder X-ray diffraction to 12 and 68 GPa, respectively. A second order Birch-Murnaghan equation of state fit to the X-ray data yields a bulk modulus,$${K}_{0}=46.9$$$K_0=46.9$GPa with an imposed value of$${K}_{0}^{\prime}= 4$$$K_0^{\prime }=4$for the ambient pressure phase. Compression of bütschliite is highly anisotropic, with contraction along thec-axis accounting for most of the volume change. Bütschliite undergoes a phase transition to a monoclinicC2/mstructure at around 6 GPa, mirroring polymorphism within isostructural borates. A fit to the compression data of the monoclinic phase yields$${V}_{0}=322.2$$$V_0=322.2$ Å³$$,$$$,$$${K}_{0}=24.8$$$K_0=24.8$GPa and$${K}_{0}^{\prime}=4.0$$$K_0^{\prime }=4.0$using a third order fit; the ability to access different compression mechanisms gives rise to a more compressible material than the low-pressure phase. In particular, compression of theC2/mphase involves interlayer displacement and twisting of the [CO₃] units, and an increase in coordination number of the K⁺ion. Three more phase transitions, at ~ 28, 34, and 37 GPa occur based on the Raman spectra and powder diffraction data: these give rise to new [CO₃] bonding environments within the structure.

    

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4. X-ray diffraction reveals two structural transitions in szomolnokite

   https://doi.org/10.2138/am-2022-8147  

   Pardo, Olivia S. ; Dobrosavljevic, Vasilije V. ; Perez, Tyler ; Sturhahn, Wolfgang ; Liu, Zhenxian ; Rossman, George R. ; Jackson, Jennifer M. ( March 2023 , American Mineralogist)

   Abstract Hydrated sulfates have been identified and studied in a wide variety of environments on Earth, Mars, and the icy satellites of the solar system. The subsurface presence of hydrous sulfur-bearing phases to any extent necessitates a better understanding of their thermodynamic and elastic properties at pressure. End-member experimental and computational data are lacking and are needed to accurately model hydrous, sulfur-bearing planetary interiors. In this work, high-pressure X-ray diffraction (XRD) and synchrotron Fourier-transform infrared (FTIR) measurements were conducted on szomolnokite (FeSO4·H2O) up to ~83 and 24 GPa, respectively. This study finds a monoclinic-triclinic (C2/c to P1) structural phase transition occurring in szomolnokite between 5.0(1) and 6.6(1) GPa and a previously unknown triclinic-monoclinic (P1 to P21) structural transition occurring between 12.7(3) and 16.8(3) GPa. The high-pressure transition was identified by the appearance of distinct reflections in the XRD patterns that cannot be attributed to a second phase related to the dissociation of the P1 phase, and it is further characterized by increased H2O bonding within the structure. We fit third-order Birch-Murnaghan equations of state for each of the three phases identified in our data and refit published data to compare the elastic parameters of szomolnokite, kieserite (MgSO4·H2O), and blödite (Na2Mg(SO4)2·4H2O). At ambient pressure, szomolnokite is less compressible than blödite and more than kieserite, but by 7 GPa both szomolnokite and kieserite have approximately the same bulk modulus, while blödite’s remains lower than both phases up to 20 GPa. These results indicate the stability of szomolnokite’s high-pressure monoclinic phase and the retention of water within the structure up to pressures found in planetary deep interiors. 

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5. Metastable phase formation in europium hexaboride on compression to 187 GPa

   https://doi.org/10.1063/5.0173376  

   Sereika, Raimundas ; Clay, Matthew P. ; Zhu, Li ; Rosa, Priscila F. ; Bi, Wenli ; Vohra, Yogesh K. ( October 2023 , Journal of Applied Physics)

   Transition-metal and rare-earth borides are of considerable interest due to their electronic, mechanical, and magnetic properties as well as their structural stability under extreme conditions. Here, we report on a series of high-pressure Raman and x-ray diffraction experiments on the cubic rare-earth hexaboride EuB6 to an ultrahigh pressure of 187 GPa in a diamond anvil cell. In EuB6, divalent europium ions occupy the corners of the cubic structure, which encloses a rigid boron-bonded cage. So far, no structural phase transitions have been reported, while the nanoindentation studies indicate amorphization in nanoscale shear bands during plastic deformation. Our x-ray diffraction studies have revealed that the ambient cubic phase of EuB6 shows broadening and splitting of diffraction peaks starting at 72 GPa and the broadening continuing to 187 GPa. The high-pressure phase is recovered on decompression, and the Raman spectroscopy of the recovered sample from 187 GPa shows a downward frequency shift and broadening of T2g, Eg, and A1g modes of boron octahedron. The density functional theory simulations of EuB6 at 100 GPa have identified five possible lowest energy crystal structures. The experimental x-ray diffraction data at high pressures is compared with the theoretical predictions and the role of structural distortions induced by shear stresses is also discussed.

    

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