scholarly journals Strong hydrogen bonding in a dense hydrous magnesium silicate discovered by neutron Laue diffraction

IUCrJ ◽  
2020 ◽  
Vol 7 (3) ◽  
pp. 370-374
Author(s):  
Narangoo Purevjav ◽  
Takuo Okuchi ◽  
Christina Hoffmann

A large amount of hydrogen circulates inside the Earth, which affects the long-term evolution of the planet. The majority of this hydrogen is stored in deep Earth within the crystal structures of dense minerals that are thermodynamically stable at high pressures and temperatures. To understand the reason for their stability under such extreme conditions, the chemical bonding geometry and cation exchange mechanism for including hydrogen were analyzed in a representative structure of such minerals (i.e. phase E of dense hydrous magnesium silicate) by using time-of-flight single-crystal neutron Laue diffraction. Phase E has a layered structure belonging to the space group R 3 m and a very large hydrogen capacity (up to 18% H2O weight fraction). It is stable at pressures of 13–18 GPa and temperatures of up to at least 1573 K. Deuterated high-quality crystals with the chemical formula Mg2.28Si1.32D2.15O6 were synthesized under the relevant high-pressure and high-temperature conditions. The nuclear density distribution obtained by neutron diffraction indicated that the O—D dipoles were directed towards neighboring O2− ions to form strong interlayer hydrogen bonds. This bonding plays a crucial role in stabilizing hydrogen within the mineral structure under such high-pressure and high-temperature conditions. It is considered that cation exchange occurs among Mg2+, D+ and Si4+ within this structure, making the hydrogen capacity flexible.

2021 ◽  
Author(s):  
Taehyun Kim ◽  
Stella Chariton ◽  
Vitali Prakapenka ◽  
Anna Pakhomova ◽  
Hanns-Peter Liermann ◽  
...  

<p>Astrophysical surveys so far have suggested that water-rich planets could be common [1] (including Uranus and Neptune in our Solar System). In the conventional interior model of water-rich planets, it has been assumed to have separate layers of atmosphere, ice/fluid, rocky mantle and metallic core [2]. However, recent studies have proposed the existence of heavy elements in the ice/fluid layer of Uranus, challenging the conventional view [3]. In addition, chemical interaction and thermodynamic processes of major rock-forming minerals at the H<sub>2</sub>O–rock interface conditions of the water-rich planetary interiors have been scarcely explored.</p> <p>We have performed laser-heated diamond-anvil cell experiments on two rock-forming minerals, olivine ((Mg<sub>0.9</sub>,Fe<sub>0.1</sub>)<sub>2</sub>SiO<sub>4</sub>) and ferropericlase ((Mg<sub>0.9</sub>,Fe<sub>0.1</sub>)O), in water at the pressure and temperature conditions expected for the water-rich planets. During laser-heating, we collected X-ray diffraction (XRD) data at beamlines 13-IDD of GSECARS at APS and P02.2, the ECB of PETRA III at DESY. Our dataset covers pressures between 20 and 80 GPa. After high-pressure and high-temperature experiments, we conducted chemical and textural analysis using focused ion beam (FIB) and scanning electron microscope (SEM) at Yonsei University.</p> <p>During laser-heating, Si-rich high-pressure phases were formed, such as bridgmanite ((Mg,Fe)SiO<sub>3</sub>) and stishovite (SiO<sub>2</sub>), from the high Mg/Si ratio of starting composition (olivine). The formation of Si-rich phases from Mg-rich starting composition suggests dissolve of MgO into H<sub>2</sub>O-liquid during laser-heating at high-pressures. This was also found for (Mg<sub>0.9</sub>,Fe<sub>0.1</sub>)O ferropericlase starting material. The intensity of the diffraction peak of ferropericlase was dramatically decreased at high-pressure and high-temperature conditions, which indicates that (Mg<sub>0.9</sub>,Fe<sub>0.1</sub>)O is soluble in H<sub>2</sub>O-liquid. From chemical analysis, we found the dome-like structures, which showed that domes are Mg-rich and below the domes is Si-rich. Between Mg-rich and Si-rich regions, porous structures (almost empty) were positioned, meaning that MgO-rich fluid existed at high-pressure and high-temperature conditions. In summary, the textural and chemical analysis combined with XRD data indicates a selective leaching of MgO preferentially from silicate during laser heating, making MgO-dissolved in high-temperature fluid, which peaks between 20 and 40 GPa and above 1,500 K [4].</p> <p>For water-rich planets with 1–6 Earth masses, the chemical reaction at the deep H<sub>2</sub>O–rock interface would lead to high concentrations of MgO in the H<sub>2</sub>O layer. For Uranus and Neptune, our experiments indicate that the top ~3% of the H<sub>2</sub>O layer of them, the pressure and temperature conditions of which have been achieved in this study, would have a large storage capacity for MgO. If an early dynamic process enables the H<sub>2</sub>O–rock reaction, the topmost H<sub>2</sub>O layer may be rich in MgO, possibly affecting the thermal history of the planet.</p> <p> </p> <p>[1] Batalha, N. M. Proc. Natl Acad. Sci. USA 111, 12647–12654 (2014). [2] Guillot, T. Annu. Rev. Earth Planet. Sci. 33, 493–530 (2005). [3] Helled, R., Nettelmann, N. & Guillot, T. Space Sci. Rev. 216, 38 (2020). [4] Kim, T. et al. Nat. Astron. (2021).</p>


2015 ◽  
Vol 79 (1) ◽  
pp. 1-10 ◽  
Author(s):  
Xueyin Yuan ◽  
Haifei Zheng

AbstractRaman scattering experiments of natural FeS2 pyrite were performed at simultaneous high-pressure and high-temperature conditions up to 675 K and 2100 MPa using a hydrothermal diamond anvil cell combined with micro-Raman spectroscopy. Four out of five Raman active modes [Eg, Ag, Tg(1) and Tg(3)] were resolved at ambient conditions, the remaining Tg(2) [∼377 cm–1] mode was weak and unresolved occurring ∼2 cm–1 from the intense Ag [379 cm–1] mode. The frequency shifts of the Eg [343 cm–1] and Ag [379 cm–1] modes were determined to be quadratic functions of pressure and temperature: ν343 = 343.35 – 0.0178 × ΔT – 8.4E – 6 × (ΔT)2 + 0.00367 × Δp 3.7E–7 × (Δp)2 + 1.0E–6 × ΔT × Δp and ν379 = 379.35 – 0.0295 × ΔT – 9.0E–6 × (ΔT)2 + 0.00460 × Δp – 5.3E–7 × (Δp)2 + 7.0E–7 × ΔT × Δp. The positive pressure dependence of both modes indicates stress-induced contraction of S–S and Fe–S bonds, whereas the negative temperature dependence shows temperature-induced expansion of them. The Raman spectra of pyrite were used to derive its bulk modulus at high temperatures, thermal expansion coefficient at high pressures and anharmonic parameters at high-pressure and high-temperature conditions.


2007 ◽  
Vol 1040 ◽  
Author(s):  
Peter Kroll

AbstractWe apply our procedure of including nitrogen fugacity into thermochemical calculations to compute phase diagrams in the rhenium-nitrogen and ruthenium-nitrogen systems. The combination of first-principle and thermochemical calculations let us predict the sequential nitridation of Re at high-pressure/high-temperature conditions. At 3000 K, Re will react with nitrogen at about 32 GPa yielding ReN. Formation of ReN2 with CoSb2-type structure is predicted for pressures exceeding 50 GPa at this temperature. The recently proposed marcasite-type RuN2 will be attainable at 3000 K at pressures above 30 GPa from a mixture of Ru and RuN2.


1998 ◽  
Vol 278-281 ◽  
pp. 612-617 ◽  
Author(s):  
Bogdan F. Palosz ◽  
Svetlana Stelmakh ◽  
Stanislaw Gierlotka ◽  
M. Aloszyna ◽  
Roman Pielaszek ◽  
...  

2005 ◽  
Vol 71 (704) ◽  
pp. 1183-1189 ◽  
Author(s):  
Hiroyuki NISHIDA ◽  
Takuma OGAWA ◽  
Eiji WAKISAKA ◽  
Takeshi TACHIBANA

2004 ◽  
Vol 59 (2) ◽  
pp. 202-215 ◽  
Author(s):  
Holger Emme ◽  
Tanja Nikelski ◽  
Thomas Schleid ◽  
Rainer Pöttgen ◽  
Manfred Heinrich Möller ◽  
...  

The new orthorhombic meta-oxoborates RE(BO2)3 (≡REB3O6) (RE = Dy-Lu) have been synthesized under high-pressure and high-temperature conditions in a Walker-type multianvil apparatus at 7.5 GPa and 1100 °C. They are isotypic to the known ambient pressure phase Tb(BO2)3, space group Pnma. In contrast to Dy(BO2)3, which was also obtained in small amounts under high-temperature conditions, the preparation of the higher orthorhombic homologues RE(BO2)3 (RE = Ho-Lu) was only possible using high-pressure. The meta-oxoborates RE(BO2)3 (RE = Dy-Er) were synthesized as pure products, whereas the orthorhombic phases with RE = Tm-Lu were only obtained as byproducts. With the exception of Yb(BO2)3 it was possible to establish single crystal data for all compounds. The results of temperature-resolved in-situ powder-diffraction measurements, DTA, IR-spectroscopic investigations, and magnetic properties are also presented.


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