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Although nitrogen in the Earth’s interior has attracted significant attention recently, it remains the most enigmatic of the light elements in the Earth’s core. In this work, synchrotron X-ray diffraction (XRD) and electrical conductivity experiments were conducted on iron nitrides (Fe2N and Fe4N) in diamond anvil cells (DACs) up to about 70 ​GPa ​at ambient temperature. These results show that iron nitrides are stable up to at least 70 ​GPa. From the equation of state (EOS) parameters, iron nitrides are more compressible than iron carbides. Moreover, using the van der Pauw method and Wiedemann-Franz law, the electrical and thermal conductivity of samples were determined to be much lower than that of iron carbides. The conductivities of Fe2N and Fe4N were similar at 20–70 ​GPa, suggesting no evident effects by varying the N stoichiometries in iron nitrides. Iron nitrides are less dense and conductive but more compressible than carbides at 0–70 ​GPa. This study indicates that less nitrogen than carbon can explain geophysical phenomena in the deep Earth, such as the density deficit.

Significance Earth’s liquid outer core is mainly composed of iron alloyed with ∼8 to 10% of light elements (e.g., silicon). Convection of the liquid core generates Earth’s magnetic field, which is controlled by the thermal conductivity of the core. In this study, we investigated the resistivity and thermal conductivity of iron-silicon alloys as a candidate composition in Earth’s core via high-pressure and -temperature experiments and numerical calculations. We found a near temperature independence of the resistivity in iron-silicon alloys at Earth core’s pressure and thus a high thermal conductivity. This work indicates that if silicon is the sole major light element in Earth’s core it could depress thermal convection and promote a thermally stratified layer at the topmost outer core., Light elements in Earth’s core play a key role in driving convection and influencing geodynamics, both of which are crucial to the geodynamo. However, the thermal transport properties of iron alloys at high-pressure and -temperature conditions remain uncertain. Here we investigate the transport properties of solid hexagonal close-packed and liquid Fe-Si alloys with 4.3 and 9.0 wt % Si at high pressure and temperature using laser-heated diamond anvil cell experiments and first-principles molecular dynamics and dynamical mean field theory calculations. In contrast to the case of Fe, Si impurity scattering gradually dominates the total scattering in Fe-Si alloys with increasing Si concentration, leading to temperature independence of the resistivity and less electron–electron contribution to the conductivity in Fe-9Si. Our results show a thermal conductivity of ∼100 to 110 W⋅m−1⋅K−1 for liquid Fe-9Si near the topmost outer core. If Earth’s core consists of a large amount of silicon (e.g., > 4.3 wt %) with such a high thermal conductivity, a subadiabatic heat flow across the core–mantle boundary is likely, leaving a 400- to 500-km-deep thermally stratified layer below the core–mantle boundary, and challenges proposed thermal convection in Fe-Si liquid outer core.

The melting curve of vanadium at high pressure and temperature (P-T) is of great interest to our understanding of $d$-orbital transition metals with simple crystal structures at extreme P-T conditions. Here we have investigated the melting curve and crystal structures of polycrystalline vanadium at high P-T using synchrotron x-ray diffraction (XRD) in laser-heated diamond anvil cells (LH DACs) up to \ensuremath{\sim}100 GPa and \ensuremath{\sim}4400 K, a two-stage light-gas gun with in situ shock temperature measurements up to \ensuremath{\sim}256 GPa and \ensuremath{\sim}6200 K, and ab initio molecular dynamics (AIMD) with density functional theory computations up to \ensuremath{\sim}200 GPa. The occurrence of the diffuse scattering signals in high P-T XRD patterns is used as the primary criterion to determine the melting curve of body-centered cubic (bcc) vanadium up to \ensuremath{\sim}100 GPa in LH DACs. Analysis of thermal radiation spectra of shocked vanadium using a quasispectral pyrometer constrains the melting curve up to \ensuremath{\sim}246 GPa and \ensuremath{\sim}5830 K, which is consistent with our static results using the Simon equation. The present static and dynamic experiments on the melting curve of vanadium are consistent with our AIMD simulations with the two-phase melting modeling, and are overall consistent with other theoretical simulations using the Z method. The results reconcile the recently reported theoretical discrepancy, and refute a higher melting curve report given by self-consistent ab initio lattice dynamics calculations. The consistencies among our studies indicate that one does not have to invoke superheating as a hypothesis to describe the solid-liquid equilibrium boundary of vanadium as an explanation for static vs dynamic experimental results. Our static and dynamic results with in situ diagnostics of melting and two-phase AIMD simulation have implications for studying melting curves of other $d$-orbital transition metals and their alloys at extreme P-T conditions.

${\mathrm{WN}}_{6}$ phase discovered at 126--165 GPa after heating of W in nitrogen. XRD refinements reveal a unit cell in space group $R\overline{3}m$ which is consistent with the ${\mathrm{WN}}_{6}$ structure with armchairlike hexazine (${\mathrm{N}}_{6}$) rings, while strong ${A}_{1g}$ Raman mode confirms its $\mathrm{N}─\mathrm{N}$ single bonds. Density functional theory (DFT) calculations reveal balanced contributions of attractive interactions between W and covalent ${\mathrm{N}}_{6}$ rings, and repulsions between ${\mathrm{N}}_{6}$ rings that make ${\mathrm{WN}}_{6}$ ultrastiff and tough. The ${\mathrm{WN}}_{6}$ phase displays long bond lengths in the nearest N-N and pressure-enhanced electronic band gap, which pave the way for finding novel nitrides.

Crystal structure prediction (CSP) methods recently proposed a series of new rare-earth (RE) hydrides at high pressures with novel crystal structures, unusual stoichiometries, and intriguing features such as high

Negative thermal expansion material TaVO5 is recently reported to have pressure induced structural phase transition and irreversible amorphization at 0.2 and above 8 GPa, respectively. Here, we hav...

Hydrogen-rich superhydrides are believed to be very promising high-Tc superconductors. Recent experiments discovered superhydrides at very high pressures, e.g. FeH5 at 130 GPa and LaH10 at 170 GPa. With the motivation of discovering new hydrogen-rich high-Tc superconductors at lowest possible pressure, here we report the prediction and experimental synthesis of cerium superhydride CeH9 at 80–100 GPa in the laser-heated diamond anvil cell coupled with synchrotron X-ray diffraction. Ab initio calculations were carried out to evaluate the detailed chemistry of the Ce-H system and to understand the structure, stability and superconductivity of CeH9. CeH9 crystallizes in a P63/mmc clathrate structure with a very dense 3-dimensional atomic hydrogen sublattice at 100 GPa. These findings shed a significant light on the search for superhydrides in close similarity with atomic hydrogen within a feasible pressure range. Discovery of superhydride CeH9 provides a practical platform to further investigate and understand conventional superconductivity in hydrogen rich superhydrides., Hydrogen-rich superhydrides are promising high-temperature superconductors which have been observed only at pressures above 170 GPa. Here the authors show that CeH9 can be synthesized at 80-100 GPa with laser heating, and is characterized by a clathrate structure with a dense 3-dimensional atomic hydrogen sublattice.

The Kohn anomaly and topological change of the Fermi surface in $d$-block metals can occur under high pressure with affiliated significant changes in elastic, mechanical, and transport properties. However, our understanding of their origin and associated physical phenomena remains limited both experimentally and theoretically. Here we study the pressure effect on the Kohn anomaly, electronic topological transition (ETT), and the associated anomalies in physical properties of body-centered cubic (bcc) single-crystal tantalum (Ta). The phonon dispersions of Ta crystal were directly measured up to $\ensuremath{\sim}47$ GPa using high-energy resolution inelastic x-ray scattering in a diamond anvil cell with hydrostatic helium medium. A Kohn anomaly in Ta was observed and became significantly stronger at 47.0 GPa at the reduced wave vector of $\ensuremath{\sim}0.7$ in the longitudinal acoustic mode along the [\ensuremath{\xi},0,0] direction. Our theoretical and experimental results indicate that the electron-phonon coupling and Fermi surface nesting mainly contribute to the Kohn anomaly, and the latter plays a dominant role at high pressures of 17--47 GPa. First-principles calculations further reveal an ETT with a topology change of the Fermi surface to occur at $\ensuremath{\sim}100$ GPa in Ta, which causes a softening in the elastic constants (${C}_{11}$ and ${C}_{44}$) and mechanical properties (shear, Young's, and bulk moduli). Our study shows that the $d$-orbital electrons in Ta play a key role in the stability of its electronic topological structure, where electron doping in Ta could significantly depress its ETT and elastic anomaly at high pressures. It is conceivable that our observed Kohn anomaly and ETT in a representative bcc Ta are much more prevalent in $d$-block transition metals under compression than previously thought.

Thermal and compositional convection in Earth's core are thought to be the main power sources driving geodynamo. The viability and strength of thermally and compositionally-driven convection over Earth's history depend on the adiabatic heat flow across the core-mantle boundary (CMB) which is governed by the thermal conductivity of a constituent Fe-Ni-light element alloy at the pressure-temperature (P-T) conditions relevant to the core. Silicon is often proposed to be an abundant light element alloyed with Fe along with ∼5 wt% Ni, but the thermal transport properties of Fe-Ni-Si alloys at high P-T remain largely uncertain. Here we measured the electrical resistivities of Fe-10wt%Ni and Fe-1.8wt%Si alloys up to ∼142 GPa and ∼3400 K using four-probe van der Pauw method in laser-heated diamond anvil cell experiments. Our results show that the resistivities of hcp-Fe-1.8Si and Fe-10Ni display quasi-linear temperature dependence from ∼1500 to 3400 K at each given high pressure. Addition of ∼2 wt% Si in hcp-Fe significantly increases its resistivity by ∼25% at ∼138 GPa and 4000 K, but Fe-10wt%Ni has similar resistivity to pure hcp-Fe at near CMB P-T conditions. Using our measured values of electrical resistivities, we model thermal conductivities via the Wiedemann-Franz law, giving a nominal thermal conductivity of ∼50 W m−1 K−1 for liquid Fe-5Ni-8Si alloy at the topmost outer core, implying an adiabatic (conductive) core heat flow of ∼8.0 TW. The outer core has a much lower thermal conductivity than the inner core due to light-element differentiation across the solidifying inner-core boundary. Our studies imply that the adiabatic core heat flow is low enough to enable thermal convection to drive the geodynamo over most and possibly all of Earth's history, while the strength of compositional convection increases with the inner-core growth and accounts for ∼83% of the buoyancy flux to the present-day geodynamo.

Herein we report results of pressure- and temperature-dependent Raman scattering studies on Pr2Ti2O7. Pressure-dependent studies performed up to 23 GPa suggest a reversible phase transition above 15 GPa with subtle changes. Temperature-dependent investigations performed in the range of 77–1073 K showed anomalous temperature dependence of some of the Raman modes. Temperature-dependent X-ray diffraction data indicated no structural transition but nonlinear expansion of unit-cell parameters with increasing temperature. With increasing temperature, the structure dilates anisotropically, and volume of coordination polyhedra around all the atoms expands. Also with increasing temperature the distortions in coordination polyhedra around all the atoms decrease, and appreciable decrease is observed in Pr(1)O10 and Pr(3)O9 units. The pressure evolution of Raman-mode frequencies was analyzed for both ambient as well as high-pressure phases, and mode Gruneisen parameters for ambient pressure phase were obtained. The t...

Phase evolution from CaZrTi 2 O 7 (zirconolite) to Y 2 Ti 2 O 7 (pyrochlore) have been delineated by systematic characterization of a series of sample with composition as Ca 1−x Zr 1−x Y 2x Ti 2 O 7 (0.00 ≤ x ≤ 1.00) by powder XRD, Raman spectroscopy, SEM and EDS analyses. Comparative analyses of XRD and Raman spectra revealed sequential evolution of phases with increasing concentration of Y 3+ in the compositions. From the XRD studies, three distinct phase fields, namely two layer (2M) and four layer (4M) zirconolite-types and cubic pyrochlore-type are observed in between zirconolite (CaZrTi 2 O 7 ) and Y 2 Ti 2 O 7. 4M-zirconolite phase is observed in a narrow range of composition, viz. 0.35 ≤ x ≤ 0.40 while cubic pyrochlore type phase is observed in the compositions with x ≥ 1.20. The unit cell volume of different phases shows a non-linear increasing trend with Y 3+ ion concentration which has been attributed to the distribution of cations in different structure and change in their coordination number.

Negative thermal expansion material TaVO

In this communication we report the details of the structural and thermal properties of monoclinic layered perovskite type Pr2Ti2O7 (PTO) using ambient to higher temperature XRD and Raman spectroscopic studies. The monoclinic (P21) structure is found to be the stable structure of PTO compared to the orthorhombic Pna21, Cmc21 or Cmcm and monoclinic P21/m structures. The crystal structure is further supported by the ab initio total energy calculations using density functional theory (DFT) formalism. The total energy calculation and structural relationship favour the ferroelectric (P21) to paraelectric (P21/m) displacive transition. The calculated electric polarization as observed from the displacement of ions is ∼8.3 μC cm−2. The calculated electron density of states indicated a band gap of about 2.7 eV, which closely agrees with that measured by UV-Vis diffuse reflectance spectroscopy. Variable temperature XRD and differential thermal analysis studies revealed no structural transition to Cmc21 in the temperature range from ambient to 1473 K as reported for analogous rare-earth titanates, like La2Ti2O7 and Nd2Ti2O7. A partial decomposition of PTO to cubic perovskite type structure is observed at around 1673 K. The measurement of field dependent electric polarization indicates the ferroelectric nature of PTO. The electrical properties of PTO have also been investigated by ac impedance spectroscopic studies from 173 to 1073 K. The low temperature dielectric data indicate two different types of relaxations, one at a lower frequency region and strongly temperature dependent while the other at a higher frequency region (>1 kHz) and nearly temperature independent. The low and high frequency relaxations have been attributed to the thermally activated polarization process arising from the grain boundaries and dipolar orientations, respectively. The activation energy for a thermally activated low frequency relaxation process is 0.38 eV, which is similar to the interfacial polarizations due to ionic movements. An appreciable contribution of ionic conductivity in PTO is observed at still higher temperature (∼700 K). The activation energy for ionic conductivity is about 0.60 eV.

Raman spectroscopic investigations were carried out on proposed nuclear fuel thorium dioxide–uranium dioxide (ThO2–UO2) solid solutions and simulated fuels based on ThO2–UO2. Raman spectra of ThO2–UO2 solid solutions exhibited two-mode behavior in the entire composition range. Variations in mode frequencies and relative intensities of Raman modes enabled estimation of composition, defects, and oxygen stoichiometry in these compounds that are essential for their application. The present study shows that Raman spectroscopy is a simple, promising analytical tool for nondestructive characterization of this important class of nuclear fuel materials.

Inelastic neutron scattering, Raman and X-ray diffraction measurements coupled with lattice dynamical calculations (employing a semi empirical transferable potential model) have been carried out to gain a detailed understanding of the peculiar vibrational spectrum exhibited by the mixed crystal ZnS1-xSex. Raman scattering measurements performed over a varying range of temperature (100-800 K) and pressure (up to 13 GPa) have confirmed that the additional mode observed in the spectra are visible over the entire range of temperature and pressure. Correlation of the individual motions of atoms (obtained from computed total and partial phonon density of states) with the inelastic neutron scattering measurements (carried out over the entire Brillouin zone) have then indicated that the existence of the additional mode in ZnS1-xSex is due to the vibrations of the Se atom being in resonance with that of the Saturn. Further, it has been shown that the presence of this additional mode can be tuned by varying the mass of the atom at the Se site. In addition, an analysis of bond length distribution with increasing Se concentration have elucidated that bond length spread is not responsible for the presence of the additional mode. An analysis of the peak shifts of the Raman modes with temperature and pressure indicate that the anharmonicity of the vibrational modes increases with increasing compositional disorder. This is attributed to the fact that increasing Se concentration gives rise to a distribution of bondlengths in ZnS1-xSex which is responsible for this compositional disorder induced anharmonicity. Our computations have thus revealed that mass of the anion is responsible for the presence of additional mode while bond-length distribution gives rise to the existence of compositional disorder induced anharmonicity in ZnS1-xSex. Further, it is observed that the contribution of explicit anharmonicity to the total anharmonicity becomes dominant at higher temperatures. This compound also exhibits negative thermal expansion at low temperatures as obtained from our X-ray diffraction measurements as a function of temperature (10-800 K). (C) 2013 Elsevier B.V. All rights reserved.

Herein we report results of pressure- and temperature-dependent Raman scattering studies on Pr

Raman spectroscopic studies on lead-free piezo-electric compound Bi12TiO20 is reported as a function of pressure upto 25 GPa at room temperature. Results indicate that the compound remains in stable crystalline phase upto 25 GPa. Temperature dependent Raman spectroscopic investigations on Bi12TiO20 indicate that the compound is also stable at high temperatures upto 850 K. From measurements of temperature and pressure dependence of Raman mode frequencies, intrinsic anharmonic parameters are calculated for each of the Raman active modes which are useful in modeling of thermodynamic entities. The results are compared with that of analogous compound Bi12SiO20.

Vibrational properties of ternary chalcopyrite semiconductor CuGaTe2 have been studied using Raman spectroscopy at high pressures upto 24 GPa. Pressure dependent softening is observed for two of the observed modes, which has been correlated with instability in the system leading to structural transition around 9 GPa to a disordered simple cubic phase. Beyond 11.5 GPa, no Raman spectra could be observed. This is possibly due to the transition could be also accompanied by reduction in band gap. On release of pressure, structurally disordered chalcopyrite phase is recovered.

To investigate the anharmonicity of different phonons in the negative thermal expansion material H3[Co(CN)6], temperature dependent Raman spectroscopic studies have been carried out in the temperature range 80–300 K. No discontinuous or slope changes of mode frequencies are observed with temperature implying that H3[Co(CN)6] is stable in the entire temperature range. The temperature dependence of mode frequencies and their linewidths (FWHMs) are analyzed using the anharmonicity models, which indicate that the three-phonon decay process is dominant over the four-phonon process.

Topological insulators have been the subject of intense research interest due to their unique surface states that are topologically protected against scattering or defects. However, the relationship between the crystal structure and topological insulator state remains to be clarified. Here, we show the effects of hydrostatic pressure on the structural, vibrational, and topological properties of the topological insulator Bi1.5Sb0.5Te1.8Se1.2 up to 45 GPa using X-ray diffraction and Raman spectroscopy in a diamond anvil cell, together with first-principles theoretical calculations. Two pressure-induced structural phase transitions were observed: from ambient rhombohedral R 3¯m phase to a monoclinic C2/m phase at ∼13 GPa, and to a disordered I4/mmm phase at ∼22 GPa. In addition, the alloy undergoes several electronic transitions within the R 3¯m phase: indirect to direct bulk band gap transition at ∼5.8 GPa, bulk gap closing with an appearance of Dirac semimetal (DSM) state at ∼8.2 GPa, and to a trivial semimetal state at ∼12.1 GPa. Anomalies in c/a ratio and Raman full width at half maximum that coincide with the DSM phase suggest the contribution of electron-phonon coupling to the transition. Compared to binary end members Bi2Te3, Bi2Se3, and Sb2Te3, the structural phase transition and anomaly were observed at higher pressures in Bi1.5Sb0.5Te1.8Se1.2. These results suggest that the topological transitions are precursors to the structural phase transitions.

Vibrational properties of Pr2Ti2O7 have been studied at high pressures upto 18 GPa using Raman spectroscopy. While all the Raman modes of Pr2Ti2O7 harden gradually with pressure without any anomaly, interesting intensity exchange, frequency variation and mode coupling is observed in Ti-O stretching modes under pressure. The present study indicates good structural stability of Pr2Ti2O7 over the investigated pressures.

Raman spectroscopic investigations of negative thermal expansion material TaVO5 is carried out at low temperatures. Changes in the Raman spectra observed across the orthorhombic to monoclinic phase transition are reported. The magnitude of temperature dependence of most of the Raman modes decreases across the transition indicating decrease in anharmonicity in the low temperature phase.

TaVO5 is a framework structured compound that exhibits negative thermal expansion (NTE) above room temperature, upto 1073 K. We report Raman spectroscopic investigation of TaVO5 as a function of temperature in the range 77-873 K, which confirms the reported reversible low temperature transition to monoclinic phase at 259 K. Structural stability of TaVO5 at high pressures investigated using in-situ Raman spectroscopy shows a reversible structural transition at around 0.2 GPa to a phase, which is probably the same monoclinic phase as the low temperature phase, indicating that this structural phase transition may be volume driven. From the pressure and temperature dependence of the Raman modes, some of the zone centre phonon modes, particularly, the librational modes, responsible for the NTE are identified and anharmonicity of the Raman modes is also estimated. We have found that explicit anharmonicity dominates over implicit anharmonicity and the low frequency modes have significant quartic anharmonicity. T...

Structural stability of a transparent conducting oxide CuLaO2 at high pressures is investigated using in-situ Raman spectroscopy, electrical resistance, and x-ray diffraction techniques. The present Raman investigations indicate a sequence of structural phase transitions at 1.8 GPa and 7 GPa. The compound remains in the first high pressure phase when pressure is released. Electrical resistance measurements carried out at high pressures confirm the second phase transition. These observations are further supported by powder x-ray diffraction at high pressures which also showed that a-axis is more compressible than c-axis in this compound. Fitting the pressure dependence of unit cell volume to 3rd order Birch-Murnaghan equation of state, zero pressure bulk modulus of CuLaO2 is determined to be 154(25) GPa. The vibrational properties in the ambient delafossite phase of CuLaO2 are investigated using ab-initio calculations of phonon frequencies to complement the Raman spectroscopic measurements. Temperature dependence of the Raman modes of CuLaO2 is investigated to estimate the anharmonicity of Raman modes.

Vibrational properties of delafossite CuLaO2 are investigated using Raman spectroscopy at ambient conditions and at high pressures. Changes are observed in the Raman spectrum at around 1.8 GPa which could be related to a phase transition. The changes observed are reversible from 7 GPa.