Transformation mechanism of the pressure-induced C2/c-to-P<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si1.svg"><mml:mrow><mml:mover accent="true"><mml:mn>1</mml:mn><mml:mo>¯</mml:mo></mml:mover></mml:mrow></mml:math>transition in ferrous sulfate monohydrate single crystals

Meusburger, Johannes M.; Ende, Martin; Talla, Dominik; Wildner, Manfred; Miletich, Ronald

doi:10.1016/j.jssc.2019.06.004

Cited by 16 publications

(52 citation statements)

References 60 publications

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“…This is in complete agreement what has been reported for the C2/cto-P1̅ transition from the ambient αto the high-p βpolymorph of FeSO 4 ·H 2 O. 27 In accordance with the displacive changes observed in this isostructural compound, a tendency of the framework to fold up can be anticipated for NiSO 4 ·H 2 O as well, as could be observed on the bond angles on the bridging oxygen atoms. There is a general decrease of Ni−O− Ni and Ni−O−S angles as a consequence of the compacting folding, together with the diversification of Ni−O2−S angles (126°vs 133°at 4.5 GPa) in the same manner as reported for FeSO 4 ·H 2 O upon exceeding the α-to-β transition point.…”

Section: ■ Materials and Methodssupporting

confidence: 91%

“…The values for the β-NiSO 4 ·H 2 O polymorph in the range 2.5 to 6.0 GPa correspond to K 0 = 44.5 ± 9.4 GPa and K′ = 8.2 ± 3.2, with a relatively high value for K′ due to obvious elastic softening effects as reported for the isostructural phases. 27,28 When the p range is restricted between 4.0 and 6.0 GPa, the fit yields a 500% error value for K 0 and K′ for BM- 3 Table 1) and might be indicative for the structural instability of the phase at even higher pressures beyond the maximum p within this experimental series. High-Pressure Crystal Structures.…”

Section: ■ Materials and Methodsmentioning

confidence: 73%

“…While the transformations do not cause virtually any changes with respect to the main structural units of the framework, with the exception of some polyhedral tilting leading to higher compaction, the hydrogen bonding system reveals notable changes at the critical transition points. Due to the loss of the local 2-fold axis (7) 1.459(7) S1−O1B 1.470 (7) 1.458(4) 1.461(4) S1−O2(A) 1.484 (2 27 the lattice distortion causes one of the O3···O1 distances to be drastically shortened (from 3.296(5) Å at 2.3(1) GPa to 2.851(6) Å at 8.4(1) GPa) thus becoming potentially involved in the hydrogen-bonding system ( Figure 10). These changes confirm the mechanism reported for the α-to-β transition in the analogous ferrous compound with the development of three short O3···O contacts suitable as relevant hydrogen bonds with O3 being the donator oxygen.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…16,25 Recent investigations on MgSO 4 ·H 2 O and FeSO 4 ·H 2 O under hydrostatic compression revealed a ferroelastic phase transition following the translationsgleiche C2/c-P1̅ group−subgroup relation and being apparently second order in its thermodynamic character. 27,28 Any of the symmetry changes follow a pattern of atom displacements related to the changes within the hydrogen bonding systems, whereas the topology of the heterodesmic frameworks remains unchanged, apart from distortion originating from symmetry breaking. In this context, synthetic NiSO 4 ·H 2 O single crystals are investigated in this study with respect to the occurrence of an equivalent structural polymorphism.…”

Section: ■ Introductionmentioning

confidence: 99%

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High-Pressure Behavior of Nickel Sulfate Monohydrate: Isothermal Compressibility, Structural Polymorphism, and Transition Pathway

et al. 2020

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Single crystals of synthetic nickel sulfate monohydrate, α-NiSO 4 ·H 2 O (space-group symmetry C2/c at ambient conditions), were subject to high-pressure behavior investigations in a diamond-anvil cell up to 10.8 GPa. By means of subtle spectral changes in Raman spectra recorded at 298 K on isothermal compression, two discontinuities were identified at 2.47(1) and 6.5(5) GPa. Both transitions turn out to be apparently second order in character, as deduced from the continuous evolution of unit-cell volumes determined from single-crystal X-ray diffraction. The first structural transition from αto β-NiSO 4 ·H 2 O is an obvious ferroelastic C2/c−P1̅ transition. It is purely displacive from a structural point of view, accompanied by symmetry changes in the hydrogen-bonding scheme. The second βto γ-NiSO 4 ·H 2 O transition, further splitting the O2 (hydrogen bridge acceptor) position and violating the P1̅ space-group symmetry, is also evident from the splitting of individual bands in the Raman spectra. It can be attributed to symmetry reduction through local violation of local centrosymmetry. Lattice elasticities were obtained by fitting second-order Birch−Murnaghan equations of state to the p-V data points yielding the following zero-pressure bulk moduli values: K 0 = 63.4 ± 1.0 GPa for α-NiSO 4 ·H 2 O, K 0 = 61.3 ± 1.9 GPa for β-NiSO 4 ·H 2 O, and K 0 = 68.8 ± 2.5 GPa for γ-NiSO 4 ·H 2 O.

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Section: ■ Materials and Methodssupporting

confidence: 91%

Section: ■ Materials and Methodsmentioning

confidence: 73%

Section: ■ Materials and Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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High-Pressure Behavior of Nickel Sulfate Monohydrate: Isothermal Compressibility, Structural Polymorphism, and Transition Pathway

et al. 2020

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“…However, it is known that high pressure (HP) could lead to interesting phenomena in minerals, including pressure-driven phase transitions [10]. In particular, HP studies have been performed in hydrated minerals related to chalcomenite, like FeSO4•H2O and MgSO4•H2O, leading to results relevant for Earth and Planetary Sciences [11,12]. However, nothing is known of the effects of HP in chalcomenite.…”

Section: Introductionmentioning

confidence: 99%

A High-pressure Investigation of the Synthetic Analogue of Chalcomenite, CuSeO<sub>3</sub>∙2H<sub>2</sub>O

González‐Platas¹,

Rodríguez‐Hernández²,

Múñoz³

et al. 2019

Preprint

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Synthetic chalcomenite-type cupric selenite CuSeO3•2H2O has been studied at room temperature under compression up to pressures of 8 GPa by means of single-crystal X-ray diffraction, Raman spectroscopy, and density-functional theory. According to X-ray diffraction, the orthorhombic phase undergoes an isostructural phase transition at 4.0(5) GPa with the thermodynamic character being first-order. This conclusion is supported by Raman spectroscopy studies which have detected the phase transition at 4.5(2) GPa and by the first-principles computing simulations. The structure solution at different pressures has provided information on the change with pressure of unit-cell parameters as well as on the bond and polyhedral compressibility. A Birch-Murnaghan equation of state has been fitted to the unit-cell volume data. We found that chalcomenite is highly compressible with a bulk modulus of 42 -49 GPa. The possible mechanism driving changes in the crystal structure is discussed, being the behavior of CuSeO3•2H2O mainly dominated by the large compressibility of the coordination polyhedron of Cu. On top of that, an assignation of Raman modes is proposed based upon density-functional theory and the pressure dependence of Raman modes discussed. Finally, the pressure dependence of phonon frequencies is also reported.

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Lattice dynamics, sound velocities, and atomic environments of szomolnokite at high pressure

Pardo,

Dobrosavljevic,

Sturhahn

et al. 2023

Phys Chem Minerals

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Complex mixtures of sulfates, silicates, and ice have been observed in a variety of planetary environments on Earth, Mars and the icy satellites of the solar system. Characterizing the properties of the corresponding compositional endmembers is important for understanding the interiors of a range of planetary bodies in which these phases are observed. To measure the electronic and vibrational properties of the iron endmember, szomolnokite, (FeSO 4 ⋅H 2 O), we have performed synchrotron 57 Fe nuclear resonant inelastic and forward scattering experiments in the diamond anvil cell up to 14.5 GPa. This pressure range covers depths within Earth's interior relevant to sulfur cycling in subduction zones and the range of pressures expected within icy satellites interiors. We nd evidence of crystal lattice softening, changes in elastic properties, and changes in the electric eld gradients of iron atoms associated with two structural transitions occurring within the experimental pressure range. We apply these ndings to icy satellite interiors, including discussion of elastic properties and implications for tidal observations.

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Transformation mechanism of the pressure-induced C2/c-to-P1¯transition in ferrous sulfate monohydrate single crystals

Cited by 16 publications

References 60 publications

High-Pressure Behavior of Nickel Sulfate Monohydrate: Isothermal Compressibility, Structural Polymorphism, and Transition Pathway

High-Pressure Behavior of Nickel Sulfate Monohydrate: Isothermal Compressibility, Structural Polymorphism, and Transition Pathway

A High-pressure Investigation of the Synthetic Analogue of Chalcomenite, CuSeO<sub>3</sub>∙2H<sub>2</sub>O

Lattice dynamics, sound velocities, and atomic environments of szomolnokite at high pressure

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