Hydrogen bond symmetrisation in D2O ice observed by neutron diffraction.

Hydrogen bond symmetrisation is the phenomenon where a hydrogen atom is located at the centre of a hydrogen bond. Theoretical studies predict that hydrogen bonds in ice VII eventually undergo symmetrisation upon increasing pressure, involving nuclear quantum effect with significant isotope effect and drastic changes in the elastic properties through several intermediate states with varying hydrogen distribution. Despite numerous experimental studies conducted, the location of hydrogen and hence the transition pressures reported up to date remain inconsistent. Here we report the atomic distribution of deuterium in D2O ice using neutron diffraction above 100 GPa and observe the transition from a bimodal to a unimodal distribution of deuterium at around 80 GPa. At the transition pressure, a significant narrowing of the peak widths of 110 is also observed, attributed to the structural relaxation by the change of elastic properties.

Temperature dependence of nitrogen solubility in bridgmanite and evolution of nitrogen storage capacity in the lower mantle.

Relative nitrogen abundance normalized by carbonaceous chondrites in the bulk silicate Earth appears to be depleted compared to other volatile elements. Especially, nitrogen behavior in the deep part of the Earth such as the lower mantle is not clearly understood. Here, we experimentally investigated the temperature dependence of nitrogen solubility in bridgmanite which occupies 75 wt.% of the lower mantle. The experimental temperature ranged from 1400 to 1700 °C at 28 GPa in the redox state corresponding to the shallow lower mantle. The maximum nitrogen solubility in bridgmanite (MgSiO3) increased from 1.8 ± 0.4 to 5.7 ± 0.8 ppm with increasing temperature from 1400 to 1700 °C. The nitrogen storage capacity of Mg-endmember bridgmanite under the current temperature conditions is 3.4 PAN (PAN: mass of present atmospheric nitrogen). Furthermore, the nitrogen solubility of bridgmanite increased with increasing temperature, in contrast to the nitrogen solubility of metallic iron. Thus, the nitrogen storage capacity of bridgmanite can be larger than that of metallic iron during the solidification of the magma ocean. Such a "hidden" nitrogen reservoir formed by bridgmanite in the lower mantle may have depleted the apparent nitrogen abundance ratio in the bulk silicate Earth.

EXAFS investigations on the pressure induced local structural changes of GeSe2glass under different hydrostatic conditions.

Pressure-induced transformations in glassy GeSe2have been studied using the x-ray absorption spectroscopy. Experiments have been carried out at the scanning-energy beamline BM23 (European Synchrotron Radiation Facility) providing a micrometric x-ray focal spot up to pressures of about 45 GPa in a diamond anvil cell. Both Se and Ge K-edge experiments were performed under different hydrostatic conditions identifying the metallization onsets by accurate determinations of the edge shifts. The semiconductor-metal transition was observed to be completed around 20 GPa when neon was used as a pressure transmitting medium (PTM), while this transition was slightly shifted to lower pressures when no PTM was used. Accurate double-edge extended x-ray absorption fine structure (EXAFS) refinements were carried out using advanced data-analysis methods. EXAFS data-analysis confirmed the trend shown by the edge shifts for this disordered material, showing that the transition from tetrahedral to octahedral coordination for Ge sites is not fully achieved at 45 GPa. Results of present high pressure EXAFS experiments have shown the absence of significant neon incorporation into the glass within the pressure range up to 45 GPa.

Atomic distribution and local structure in-situ VII from in situ neutron diffraction.

Ice polymorphs show extraordinary structural diversity depending on pressure and temperature. The behavior of hydrogen-bond disorder not only is a key ingredient for their structural diversity but also controls their physical properties. However, it has been a challenge to determine the details of the disordered structure in ice polymorphs under pressure, because of the limited observable reciprocal space and inaccuracies related to high-pressure techniques. Here, we present an elucidation of the disordered structure of ice VII, the dominant high-pressure form of water, at 2.2 GPa and 298 K, from both single-crystal and powder neutron-diffraction techniques. We reveal the three-dimensional atomic distributions from the maximum entropy method and unexpectedly find a ring-like distribution of hydrogen in contrast to the commonly accepted discrete sites. In addition, total scattering analysis at 274 K clarified the difference in the intermolecular structure from ice VIII, the ordered counterpart of ice VII, despite an identical molecular geometry. Our complementary structure analyses robustly demonstrate the unique disordered structure of ice VII. Furthermore, these findings are related to proton dynamics, which drastically vary with pressure, and will contribute to an understanding of the structural origin of anomalous physical properties of ice VII under pressures.

Plastic Deformation and Strengthening Mechanisms of Nanopolycrystalline Diamond.

Bulk nanopolycrystalline diamond (NPD) samples were deformed plastically within the diamond stability field up to 14 GPa and above 1473 K. Macroscopic differential stress Δσ was determined on the basis of the distortion of the 111 Debye ring using synchrotron X-ray diffraction. Up to ∼5(2)% strain, Debye ring distortion can be satisfactorily described by lattice strain theories as an ellipse. Beyond ∼5(2)% strain, lattice spacing d111 along the Δσ direction becomes saturated and remains constant with further deformation. Transmission electron microscopy on as-synthesized NPD shows well-bonded grain boundaries with no free dislocations within the grains. Deformed samples also contain very few free dislocations, while density of {111} twins increases with plastic strain. Individual grains display complex contrast, exhibiting increasing misorientation with deformation according electron diffraction. Thus, NPD does not deform by dislocation slip, which is the dominated mechanism in conventional polycrystalline diamond composites (PCDCs, grain size >1 µm). The nonelliptical Debye ring distortion is modeled by nucleating 12⟨110⟩ dislocations or their dissociated 16⟨112⟩ partials gliding in the {111} planes to produce deformation twinning. With increasing strain up to ∼5(2)%, strength increases rapidly to ∼20(1) GPa, where d111 reaches saturation. Strength beyond the saturation shows a weak dependence on strain, reaching ∼22(1) GPa at >10% strain. Overall, the strength is ∼2-3 times that of conventional PCDCs. Combined with molecular dynamics simulations and lattice rotation theory, we conclude that the rapid rise of strength with strain is due to defect-source strengthening, whereas further deformation is dominated by nanotwinning and lattice rotation.

Halogen molecular modifications at high pressure: the case of iodine.

Metallization and dissociation are key transformations in diatomic molecules at high densities particularly significant for modeling giant planets. Using X-ray absorption spectroscopy and atomistic modeling, we demonstrate that in halogens, the formation of a connected molecular structure takes place at pressures well below metallization. Here we show that the iodine diatomic molecule first elongates by ∼0.007 Å up to a critical pressure of Pc ∼ 7 GPa, developing bonds between molecules. Then its length continuously decreases with pressure up to 15-20 GPa. Universal trends in halogens are shown and allow us to predict for chlorine a pressure of 42 ± 8 GPa for molecular bond-length reversal. Our findings contribute to tackling the molecule invariability paradigm in diatomic molecular phases at high pressures and may be generalized to other abundant diatomic molecules in the universe, including hydrogen.

Interplay between local structure, vibrational and electronic properties on CuO under pressure.

The electronic and local structural properties of CuO under pressure have been investigated by means of X-ray absorption spectroscopy (XAS) at Cu K edge and ab initio calculations, up to 17 GPa. The crystal structure of CuO consists of Cu motifs within CuO4 square planar units and two elongated apical Cu-O bonds. The CuO4 square planar units are stable in the studied pressure range, with Cu-O distances that are approximately constant up to 5 GPa, and then decrease slightly up to 17 GPa. In contrast, the elongated Cu-O apical distances decrease continuously with pressure in the studied range. An anomalous increase of the mean square relative displacement (EXAFS Debye-Waller, σ2) of the elongated Cu-O path is observed from 5 GPa up to 13 GPa, when a drastic reduction takes place in σ2. This is interpreted in terms of local dynamic disorder along the apical Cu-O path. At higher pressures (P > 13 GPa), the local structure of Cu2+ changes from a 4-fold square planar to a 4+2 Jahn-Teller distorted octahedral ion. We interpret these results in terms of the tendency of the Cu2+ ion to form favorable interactions with the apical O atoms. Also, the decrease in Cu-O apical distance caused by compression softens the normal mode associated with the out-of-plane Cu movement. CuO is predicted to have an anomalous rise in permittivity with pressure as well as modest piezoelectricity in the 5-13 GPa pressure range. In addition, the near edge features in our XAS experiment show a discontinuity and a change of tendency at 5 GPa. For P < 5 GPa the evolution of the edge shoulder is ascribed to purely electronic effects which also affect the charge transfer integral. This is linked to a charge migration from the Cu to O, but also to an increase of the energy band gap, which show a change of tendency occurring also at 5 GPa.

High nitrogen solubility in stishovite (SiO2) under lower mantle conditions.

Nitrogen is a crucial volatile element in the early Earth's evolution and the origin of life. Despite its importance, nitrogen's behavior in the Earth's interior remains poorly understood. Compared to other volatile elements, nitrogen is depleted in the Earth's atmosphere (the so-called "missing nitrogen"), calling for a hidden deep reservoir. To investigate nitrogen's behavior in the deep Earth including how the reservoir formed, high-pressure and high-temperature experiments were conducted at 28 GPa and 1,400-1,700 °C. To reproduce the conditions in the lower mantle, the redox was controlled using a Fe-FeO buffer. We observed that depending on the temperature conditions, stishovite can incorporate up to 90-404 ppm nitrogen, experimentally demonstrating that stishovite has the highest nitrogen solubility among the deep mantle minerals. Stishovite is the main mineral component of subducted nitrogen-rich sedimentary rocks and eroded continental crust that are eventually transported down to the lower mantle. Our results suggest that nitrogen could have been continuously transported into the lower mantle via subduction, ever since plate tectonics began.

Mechanism of pressure induced amorphization of SnI4: A combined x-ray diffraction-x-ray absorption spectroscopy study.

We have studied the amorphization process of SnI4 up to 26.8 GPa with unprecedented experimental details by combining Sn and I K-edge x-ray absorption spectroscopy and powder x-ray diffraction. Standard and reverse Monte Carlo extended x-ray absorption fine structure (EXAFS) refinements confirm that the penta atomic SnI4 structural unit tetrahedron is a fundamental structural unit that appears preserved through the crystalline phase-I to crystalline phase-II transition that has been previously reported between 7 GPa and 10 GPa. Up to now, unexploited iodine EXAFS reveals to be extremely informative and confirms the progressive formation of iodine-iodine short bonds close to 2.85 Å. A coordination number increase of Sn in the crystalline phase-II region appears to be excluded, while the deformation of the tetrahedral units proceeds through a flattening that keeps the average I-Sn-I angle close to 109.5°. Moreover, we put in evidence the impact of pressure on the Sn near edge structure under competing geometrical and electronic effects.

High-pressure rotational deformation apparatus to 135 GPa.

A large-strain, torsional deformation apparatus has been developed based on diamond anvil cells at high pressures, up to 135 GPa with a help of hard nano-polycrystalline diamond anvils. These pressure conditions correspond to the base of the Earth's mantle. An X-ray laminography technique is introduced for high-pressure in situ 3D observations of the strain markers. The technique developed in this study introduces the possibility of the in situ rheological measurements of the deep Earth materials under ultrahigh-pressure conditions.

Iron partitioning and density changes of pyrolite in Earth's lower mantle.

Phase transitions and the chemical composition of minerals in Earth's interior influence geophysical interpretations of its deep structure and dynamics. A pressure-induced spin transition in olivine has been suggested to influence iron partitioning and depletion, resulting in a distinct layered structure in Earth's lower mantle. For a more realistic mantle composition (pyrolite), we observed a considerable change in the iron-magnesium partition coefficient at about 40 gigapascals that is explained by a spin transition at much lower pressures. However, only a small depletion of iron is observed in the major high-pressure phase (magnesium silicate perovskite), which may be explained by preferential retention of the iron ion Fe3+. Changes in mineral proportions or density are not associated with the change in partition coefficient. The observed density profile agrees well with seismological models, which suggests that pyrolite is a good model composition for the upper to middle parts of the lower mantle.