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Ferropericlase [(Mg,Fe)O] is one of the most abundant minerals of the earth’s lower mantle. The high-spin (HS) to low-spin (LS) transition in the Fe 2+ ions may dramatically alter the physical and chemical properties of (Mg,Fe)O in the deep mantle. To understand the effects of compression on the ground electronic state of iron, electronic and magnetic states of Fe 2+ in (Mg 0.75 Fe 0.25 )O have been investigated using transmission and synchrotron Mössbauer spectroscopy at high pressures and low temperatures (down to 5 K). Our results show that the ground electronic state of Fe 2+ at the critical pressure P c of the spin transition close to T = 0 is governed by a quantum critical point ( T = 0, P = P c ) at which the energy required for the fluctuation between HS and LS states is zero. Analysis of the data gives P c = 55 GPa. Thermal excitation within the HS or LS states ( T > 0 K) is expected to strongly influence the magnetic as well as physical properties of ferropericlase. Multielectron theoretical calculations show that the existence of the quantum critical point at temperatures approaching zero affects not only physical properties of ferropericlase at low temperatures but also its properties at P-T of the earth’s lower mantle.

[1] We have critically reviewed and discussed currently available information regarding the spin and valence states of iron in lower mantle minerals and the associated effects of the spin transitions on physical, chemical, and transport properties of the deep Earth. A high-spin to low-spin crossover of Fe2+ in ferropericlase has been observed to occur at pressure-temperature conditions corresponding to the middle part of the lower mantle. In contrast, recent studies consistently show that Fe2+ predominantly exhibits extremely high quadrupole splitting values in the pseudo-dodecahedral site (A site) of perovskite and post-perovskite, indicative of a strong lattice distortion. Fe3+ in the A site of these structures likely remains in the high-spin state, while a high-spin to low-spin transition of Fe3+ in the octahedral site of perovskite occurs at pressures of 15–50 GPa. In post-perovskite, the octahedral-site Fe3+ remains in the low-spin state at the pressure conditions of the lowermost mantle. These changes in the spin and valence states of iron as a function of pressure and temperature have been reported to affect physical, chemical, rheological, and transport properties of the lower mantle minerals. The spin crossover of Fe2+ in ferropericlase has been documented to affect these properties and is discussed in depth here, whereas the effects of the spin transition of iron in perovskite and post-perovskite are much more complex and remain debated. The consequences of the transitions are evaluated in terms of their implications to deep Earth geophysics, geochemistry, and geodynamics including elasticity, element partitioning, fractionation and diffusion, and rheological and transport properties.

Elastic properties of the major constituent minerals in the Earth's upper mantle at relevant high pressure–temperature ( P–T ) conditions are crucial for understanding the composition and seismic velocity structures of this region. In this study, for the first time, we have measured the single-crystal elasticity of natural Fe-bearing pyrope, Mg 2.04 Fe 0.74 Ca 0.16 Mn 0.05 Al 2 Si 3 O 12 , using in situ Brillouin spectroscopy and X-ray diffraction at simultaneous high P–T conditions up to 20 GPa and 750 K in an externally-heated diamond anvil cell. The derived aggregate adiabatic bulk and shear moduli ( K S 0 , G 0 ) at ambient conditions are 168.2 (±1.8) GPa (the value in parentheses represents propagated uncertainties ±1 σ ) and 92.1 (±1.1) GPa, respectively, consistent with literature results. Using the third-order Eulerian finite-strain equation to model the high P–T data, the derived pressure derivatives of the bulk and shear moduli at constant temperature are ( ∂K S / ∂P ) T =4.4 (±0.1) and ( ∂G / ∂P ) T =1.2 (±0.1), respectively, whereas the temperature derivatives of these moduli at constant pressure are ( ∂K S / ∂T ) P =−16.8 (±1.3) MPa/K and ( ∂G / ∂T ) P =−5.1 (±1.1) MPa/K, respectively. Compared to literature values, our results show that addition of 25 mol% Fe in pyrope increases the pressure derivative of the bulk modulus by 7%, but has a negligible effect on other elastic parameters. Extrapolation of our results shows that Fe-bearing pyrope remains almost elastically isotropic at relevant P–T conditions of the upper mantle, indicating that it may not have a significant contribution to seismic V P and V S anisotropy in the upper mantle. Together with the elasticity of olivine and pyroxene minerals in the upper mantle, we have constructed new velocity profiles for two representative compositional models, pyrolite and piclogite, along a representative geotherm of the Earth's upper mantle. These velocity models show V S profiles consistent with seismic observations, although V P profiles are slightly lower than global seismic observations. Our analyses also show that approximately 30% garnet in a mineralogical model is needed to best match both seismic V P and V S profiles of the region, although such high garnet content needs to be reconciled with our current geochemical understanding. Our results here provide new insights into seismic profiles and mineralogical models of the upper mantle region.

The pressure dependences of the electronic and crystal structures of ${\mathrm{LaCo}}_{5}$ have been studied with high-resolution x-ray absorption spectroscopy (XAS) and x-ray diffraction comprehensively. The lattice constant ratio of $a/c$ shows an anomaly around 12--18 GPa without change in the lattice symmetry. In the XAS spectra with partial fluorescence mode as well as in the integrated absolute difference values of the Co $K\ensuremath{\beta}$ emission spectra, a change in the electronic structure was found at around a similar pressure range as the lattice constant anomaly. Density functional theory calculations confirm the presence of a magnetic anomaly around the same pressure region. No temperature dependence of the electronic structure for ${\mathrm{LaCo}}_{5}$ and ${\mathrm{YCo}}_{5}$ was observed.

All single-valent oxide spinels are insulators. The relatively small activation energy in the temperature dependence of resistivity in vanadate spinels led to the speculation that the spinels are near the crossover from localized to itinerant electronic behavior, and the crossover could be achieved under pressure. We have performed a number of experiments and calculations aimed at obtaining information regarding structural changes under high pressure for the whole series of vanadate spinels, as well as transport and magnetic properties under pressure for $\mathrm{Mg}{\mathrm{V}}_{2}{\mathrm{O}}_{4}$. We have also studied the crystal structure under pressure of wide-gap insulators $A\mathrm{C}{\mathrm{r}}_{2}{\mathrm{O}}_{4}$ ($A=\phantom{\rule{0.16em}{0ex}}\mathrm{Mg}$, Mn, Fe, Zn) for comparison. Moreover, the relationship between the bulk modulus and the cell volume of $A{\mathrm{V}}_{2}{\mathrm{O}}_{4}$ ($A=\phantom{\rule{0.16em}{0ex}}\mathrm{Mg}$, Mn, Fe, Co, Zn) has been simulated by a density functional theory calculation. The proximity of $A{\mathrm{V}}_{2}{\mathrm{O}}_{4}$ spinels to the electronic state crossover under high pressure has been tested by three criteria: (1) a predicted critical V-V bond length, (2) the observation of a sign change in the pressure dependence of N\'eel temperature, and (3) measurement of a reduced bulk modulus. The obtained results indicate that, although the crossover from localized to itinerant \ensuremath{\pi} bonding $\text{V-}3d$ electrons in the $A{\mathrm{V}}_{2}{\mathrm{O}}_{4}$ spinels is approached by reducing under pressure the V-V separation $R$, the critical separation ${R}_{\mathrm{c}}$ is not reached by 20 GPa in $\mathrm{Co}{\mathrm{V}}_{2}{\mathrm{O}}_{4}$, which has the smallest V-V separation in the $A{\mathrm{V}}_{2}{\mathrm{O}}_{4}$ ($A=\phantom{\rule{0.16em}{0ex}}\mathrm{Mg}$, Mn, Fe, Co, Zn) spinels.

Iron spin transition directly affects properties of lower mantle minerals and can thus alter geophysical and geochemical characteristics of the deep Earth. While the spin transition in ferropericlase has been vigorously established at P ~ 60 GPa and 300 K, experimental evidence for spin transitions in other rock-forming minerals, such as bridgmanite and post-perovskite, remains controversial. Multiple valence, spin, and coordination states of iron in bridgmanite and post-perovskite are difficult to resolve with conventional spin-probing techniques. Optical spectroscopy, on the other hand, is sensitive to high/low spin ferrous/ferric iron at different sites; thus, it can be a powerful probe for spin transitions. Here we establish the optical signature of low spin Fe3+O6, a plausible low spin unit in bridgmanite and post-perovskite, by optical absorption experiments in diamond anvil cells. We show that the optical absorption of Fe3+O6 in NAL (new aluminous phase) is very sensitive to the iron spin state and represents a model behavior of bridgmanite and post-perovskite in the deep lower mantle across a spin transition. Specifically, an absorption band centered at ~ 19000 cm-1 is characteristic of the 2T2g to 2T1g (2A2g) transition in low spin Fe3+ in NAL at 40 GPa. This new spectroscopic information constrains the crystal field splitting energy of low spin Fe3+ to ~ 22200 cm-1 which we also independently confirm by our first-principles calculations. Together with available information on the electronic structure of Fe3+O6-compounds, we constrain the spin-pairing energy of Fe3+ in an octahedral field to ~ 20000-23000 cm-1. This implies that octahedrally-coordinated Fe3+ in bridgmanite is low spin at P > ~ 40 GPa., 15 pages, 7 figures

To help our understanding of the structural and superconducting transitions in ferropnictides, partial phonon density of states (PDOS) of iron in a single-crystal $\mathrm{SrF}{\mathrm{e}}_{2}\mathrm{A}{\mathrm{s}}_{2}$ pnictide have been investigated from both out-of-plane and in-plane polarizations with respect to the basal plane of the crystal structure using nuclear resonant inelastic x-ray scattering in a high-pressure diamond anvil cell at ambient temperature. The partial PDOS of iron in the pnictide crystal changes dramatically at approximately 8 GPa, which can be associated with the tetragonal (T) to collapsed tetragonal (CT) isostructural transition as evidenced in high-pressure x-ray diffraction measurements and theoretical calculations. Across the T-CT phase transition, analysis of the PDOS spectra shows a rapid stiffening of the optical phonon modes and a dramatic increase of the Lamb-M\"ossbauer factor (${f}_{\mathrm{LM}}$) and mean force constant which can be associated with the rapid decrease of the $c$ axis and the anomalous expansion of the $a$ axis. Theoretically calculated Fe partial PDOS and lattice parameters of $\mathrm{SrF}{\mathrm{e}}_{2}\mathrm{A}{\mathrm{s}}_{2}$ further reveal the strong correlation between the lattice parameters and phonons. Our results show that the T-CT transition can induce significant changes in the vibrational, elastic, and thermodynamic properties of $\mathrm{SrF}{\mathrm{e}}_{2}\mathrm{A}{\mathrm{s}}_{2}$ single crystal at high pressure.

Determination of the full elastic constants (cij) of methane hydrates (MHs) at extreme pressure-temperature environments is essential to our understanding of the elastic, thermodynamic, and mechanical properties of methane in MH reservoirs on Earth and icy satellites in the solar system. Here, we have investigated the elastic properties of singe-crystal cubic MH-sI, hexagonal MH-II, and orthorhombic MH-III phases at high pressures in a diamond anvil cell. Brillouin light scattering measurements, together with complimentary equation of state (pressure-density) results from X-ray diffraction and methane site occupancies in MH from Raman spectroscopy, were used to derive elastic constants of MH-sI, MH-II, and MH-III phases at high pressures. Analysis of the elastic constants for MH-sI and MH-II showed intriguing similarities and differences between the phases′ compressional wave velocity anisotropy and shear wave velocity anisotropy. Our results show that these high-pressure MH phases can exhibit distinct elastic, thermodynamic, and mechanical properties at relevant environments of their respective natural reservoirs. These results provide new insight into the determination of how much methane exists in MH reservoirs on Earth and on icy satellites elsewhere in the solar system and put constraints on the pressure and temperature conditions of their environment.

Pressure dependence of the electronic and crystal structures of KxFe2−ySe2, which has pressure-induced two superconducting domes of SC I and SC II, was investigated by x-ray emission spectroscopy and diffraction. X-ray diffraction data show that compressibility along the c-axis changes around 12 GPa, where a new superconducting phase of SC II appears. This suggests a possible tetragonal to collapsed tetragonal phase transition. X-ray emission spectroscopy data also shows the change in the electronic structure around 12 GPa. These results can be explained by the scenario that the two SC domes under pressure originate from the change of Fermi surface topology. Our results here show the pronounced increase of the density of states near the Fermi surface under pressure with a structural phase transition, which can help address our fundamental understanding for the appearance of the SC II phase.

A unique way of achieving controllable, pressure-induced charge transfer doping in the graphene/MoS2 heterostructure is proposed. The charge transfer causes an upward shift in the Dirac point with respect to Fermi level at a rate of 15.7 meV GPa(-1) as a function of applied hydrostatic pressure, leading to heavy p-type doping in graphene. The doping was confirmed by I2D /IG measurements.

article i nfo 0.026)Si1.00H0.179O4 with 1.1 wt.% H2O using Brillouin scattering combined with X-ray diffraction in an externally-heated diamond anvil cell up to 16 GPa and 673 K. Up to 12 GPa at 300 K, the presence of 1.1 wt.% H2O lowers the elastic moduli of ringwoodite by 5-9%, but does not affect the pressure derivatives of the elastic moduli compared to anhydrous ringwoodite. The reduction caused by hydration is significantly enhanced when temperatures are elevated at high pressures. At 12 GPa, increasing temperature by ΔT=100 K leads to a 1.3-2.4% reduction in the elastic moduli (C11, C12, and C14). Comparing our results with seismic observations, we have evaluated the potential H2O content in the lower part of the transition zone. Our results indicate that the observed seismic velocity anomalies and related depth depression of the 660-km discontinuity could be attributed to thermal variations together with the presence of ~0.1 wt.% H2O. © 2012 Elsevier B.V. All rights reserved.

The electronic spin and valence states of iron in lower-mantle silicate perovskite have been previously investigated at high pressures using various experimental and theoretical techniques. However, experimental results and their interpretation remain highly debated. Here we have studied a well-characterized silicate perovskite starting sample [(Mg 0.9 ,Fe 0.1 )SiO 3 ] in a chemically inert Ne pressure medium at pressures up to 120 GPa using synchrotron Mossbauer spectra. Analyses of the Mossbauer spectra explicitly show a high-spin to low-spin transition of the octahedral-site Fe 3+ occurring at ~13–24 GPa, as evidenced from a significant increase in the hyperfine quadrupole splitting. Two quadrupole doublets of the A-site Fe 2+ , with extremely high-QS values of 4.1 and 3.1 mm/s, occur simultaneously with the spin transition of the octahedral-site Fe 3+ and continue to develop to 120 GPa. It is conceivable that the spin-pairing transition of the octahedral-site Fe 3+ causes a volume reduction and a change in the local atomic-site configurations that result in a significant increase of the quadrupole splitting in the dodecahedral-site Fe 2+ at 13–24 GPa. Our results here provide a coherent explanation for recent experimental and theoretical results on the spin and valence states of iron in perovskite, and assist in comprehending the effects of the spin and valence states of iron on the properties of the lower-mantle minerals.

Ferromagnesite [(Mg,Fe)CO3] has been proposed as a candidate host mineral for carbon in the Earth’s mantle. Studying its physical and chemical properties at relevant pressures and temperatures helps our understanding of deep-carbon storage in the planet’s interior and on its surface. Here we have studied high-pressure vibrational and elastic properties of magnesian siderite [(Mg0.35Fe0.65)CO3] across the electronic spin transition by Raman and X-ray diffraction spectroscopies in a diamond-anvil cell. Our results show an increase in Raman shift of the observed lattice modes of magnesian siderite across the spin transition at 45 GPa as a result of an ∼8% unit-cell volume collapse and a 10% stiffer lattice (higher bulk modulus). C-O bond lengthening in the strong, rigid (CO3) 2– unit across the spin transition contributes to a competitive decrease in Raman shift, most evident in the Raman shift decrease of the symmetric stretching mode. Combined vibrational and elastic results are used to derive the mode Gruneisen parameter of each mode, which drops significantly across the transition. These results suggest that the low-spin state has distinctive vibrational and elastic properties compared to the high-spin state. Analyses of all recent experimental results on the (Mg,Fe)CO3 system show no appreciable compositional effect on the transition pressure, indicating weak iron-iron exchange interactions. Our results provide new insight into understanding the effects of the spin transition on the vibrational, elastic, and thermodynamic properties of (Mg,Fe)CO3 as a candidate carbon-host in the deep mantle.

Pressure- and temperature-induced changes in the Ce valence and $c\ensuremath{-}f$ hybridization of the Ce115 superconductors have been studied systematically. Resonant x-ray-emission spectroscopy indicated that the increase of the Ce valence with pressure was significant for ${\mathrm{CeCoIn}}_{5}$, and moderate for $\mathrm{CeIr}{({\mathrm{In}}_{0.925}{\mathrm{Cd}}_{0.075})}_{5}$. We found no abrupt change of the Ce valence in the Kondo regime for $\mathrm{CeIr}{({\mathrm{In}}_{0.925}{\mathrm{Cd}}_{0.075})}_{5}$, which suggests that valence fluctuations are unlikely to mediate the superconductivity in this material. X-ray-diffraction results were consistent with the pressure-induced change in the Ce valence. High-resolution photoelectron spectroscopy revealed a temperature-dependent reduction of the spectral intensity at the Fermi level, indicating enhanced $c\ensuremath{-}f$ hybridization on cooling.

Knowing the elasticity of ferropericlase across the spin transition can help explain seismic and mineralogical models of the lower-mantle including the origin of seismic heterogeneities in the middle to lowermost parts of the lower mantle1,2,3,4. However, the effects of spin transition on full elastic constants of ferropericlase remain experimentally controversial due to technical challenges in directly measuring sound velocities under lower-mantle conditions1,2,3,4,5. Here we have reliably measured both VP and VS of a single-crystal ferropericlase ((Mg0.92,Fe0.08)O) using complementary Brillouin Light Scattering and Impulsive Stimulated Light Scattering coupled with a diamond anvil cell up to 96 GPa. The derived elastic constants show drastically softened C11 and C12 within the spin transition at 40–60 GPa while C44 is not affected. The spin transition is associated with a significant reduction of the aggregate VP/VS via the aggregate VP softening because VS softening does not visibly occur within the transition. Based on thermoelastic modelling along an expected geotherm, the spin crossover in ferropericlase can contribute to 2% reduction in VP/VS in a pyrolite mineralogical model in mid lower-mantle. Our results imply that the middle to lowermost parts of the lower-mantle would exhibit enhanced seismic heterogeneities due to the occurrence of the mixed-spin and low-spin ferropericlase.

Silicate perovskite and ferropericlase are thought to be the primary constituents of the lower mantle, whereas silicate post-perovskite is more likely found in the lowermost mantle. Because these minerals contain certain amounts of iron, their properties and, consequently, those of the deep mantle, are strongly influenced by iron’s spin and valence states. A high-spin to low-spin crossover in ferropericlase has been observed to occur in the middle part of the lower-mantle conditions. Recent Mossbauer results consistently show that Fe2 + predominantly exhibits extremely high quadrupole splittings in perovskite and post-perovskite, whereas a high-spin to low-spin transition of Fe3 + in the octahedral site occurs at high pressures. These results provide a new venue for discussion of the effects of the spin and valence states of iron on the physical and chemical properties of the lower mantle.

The equations of state of perovskite with (Mg{sub 0.75},Fe{sub 0.25})SiO{sub 3} and MgSiO{sub 3} compositions have been investigated by synchrotron X-ray diffraction up to 130 GPa at 300 K in diamond anvil cells. Here we show that the addition of 25% Fe in MgSiO{sub 3} perovskite increases its density and bulk sound velocity (V{phi}) by 4-6% and 6-7%, respectively, at lower-mantle pressures. Based on concurrent synchrotron X-ray emission and Moessbauer spectroscopic studies of the samples, the increase in V{phi} and density can be explained by the occurrence of the low-spin Fe3+ and the extremely high-quadrupole component of Fe{sup 2+}. Combining these experimental results with thermodynamic modeling, our results indicate that iron-rich perovskite can produce an increase in density and a value of V{phi} that is compatible with seismic observations of reduced shear-wave velocity in regions interpreted as dense, stiff piles in the lower mantle. Therefore, the existence of the Fe-rich perovskite in the lower mantle may help elucidate the cause of the lower-mantle large low-shear-velocity provinces (LLSVPs) where enhanced density and V{phi} are seismically observed to anti-correlate with the reduced shear wave velocity.

Many seismological studies have confirmed that Vp travels 3–4% faster along the rotation axis of the Earth than along the equatorial plane in the inner core, indicating that the inner core is elastically anisotropic. However, seismic and mineral physics observations of the polarized Vs are still emerging. Thus far, the Vs anisotropy of the constitute iron crystals at relevant pressures of the Earth's core has remained mostly theoretical mainly because of the technical difficulties involved in measuring reliable Vs velocities of iron crystals. Here we have measured azimuthal Vs anisotropy of highly textured hcp-Fe at high pressures using nuclear resonant inelastic X-ray scattering, a technique sensitive to Vs, in a diamond anvil cell. Our results show that the azimuthal Vs is 2–4% faster along the crystallographic c axis than along the a axis at 158 GPa and 172 GPa. If one describes the Vp anisotropy of the inner core as a result of the textured hcp-Fe crystals, it is conceivable that azimuthal and polarized Vs anisotropies with a magnitude of a few percent also exist in the region. Since Vp and Vs of candidate iron phases behave quite differently in theoretical predictions, our results here indicate that future seismic observations of the Vs and Vp anisotropies of the inner core thus hold the key to deciphering the causes for the seismic and dynamic signatures as well as constitute iron phase(s) of the region.

ab ST rac T Electronic states of iron in Earth’s mantle minerals including ferropericlase, silicate perovskite, and post-perovskite have been previously investigated at high pressures and/or temperatures using various experimental techniques, including X-ray emission and Mossbauer spectroscopies. Although such methods have been used to infer changes in the electronic spin and valence states of iron in lower mantle minerals, they do not directly probe the 3d electronic states quantitatively. Here we use 1s2p resonant X-ray emission spectroscopy (RXES) at the Fe K pre-edge to directly probe and assess the 3d electronic states and the crystal-field splittings of Fe 2+ in the lower-mantle ferropericlase [(Mg0.75,Fe0.25) O] at pressures up to 90 GPa. The pre-edge features from X-ray absorption spectroscopy in the partial fluorescence yield (PFY-XAS) and RXES results explicitly show three excited states for high-spin Fe 2+ (a lower-energy 4 T1g state, a 4 T2g state, and a higher-energy 4 T1g state) and a single 2 Eg state for low-spin Fe 2+ , attributed to the (t2g) 0 (eg) 3 excited configuration. This latter feature begins to appear at 48 GPa and grows with pressure, while the peaks related to high-spin Fe 2+ vanish above 80 GPa. The observed pre-edge features are consistent with purely quadrupolar transitions resulting from the centrosymmetric character of the Fe 2+ site. The K pre-edge RXES spectra at the incident energy of

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.

The spin states of Fe2+ ions in (Mg0.75,Fe0.25)O magnesiowustite crystals at hydrostatic pressures up to 90 GPa created in a diamond-anvil cell with helium as a pressure-transmitting medium have been investi-gated by transmission and synchrotron Mossbauer spectroscopy at room temperature. An electron transition from the high-spin (HS) state to the low-spin (LS) state (HS-LS crossover) has been observed in the pressure range of 55–70 GPa. The true HS-LS transition occurs in a narrow pressure range and the extension of the electron transition to ∼15 GPa is attributed to the effect of the nearest environment and to thermal fluctuations between the high-spin and low-spin states at finite temperatures. It has been found that the lowest pressure at which the electron HS-LS transition can occur in the Mg1 − x Fe x system is 50–55 GPa.

A new miniature panoramic diamond anvil cell (mini-pDAC) as well as a unique gas membrane-driven mechanism is developed and implemented to measure electronic, magnetic, vibrational, and thermodynamic properties of materials using the nuclear resonant inelastic X-ray scattering (NRIXS) and the synchrotron Mossbauer spectroscopy (SMS) simultaneously at high pressure (over Mbar) and low temperature (T < 10 K). The gas membrane system allows in situ pressure tuning of the mini-pDAC at low temperature. The mini-pDAC fits into a specially designed compact liquid helium flow cryostat system to achieve low temperatures, where liquid helium flows through the holder of the mini-pDAC to cool the sample more efficiently. The system has achieved sample temperatures as low as 9 K. Using the membrane, sample pressures of up to 1.4 Mbar have been generated from this mini-pDAC. The instrument has been routinely used at 3-ID, Advanced Photon Source, for NRIXS and SMS studies. The same instrument can easily be used for other X-ray techniques, such as X-ray radial diffraction, X-ray Raman scattering, X-ray emission spectroscopy, and X-ray inelastic scattering under high pressure and low temperature. In this paper, technical details of the mini-pDAC, membrane engaging mechanism, and the cryostat system are described, and some experimental results are discussed.

The electronic spin state of Fe^(2+) in ferropericlase, (Mg_(0.75)Fe_(0.25))O, transitions from a high-spin (spin unpaired) to low-spin (spin paired) state within the Earth’s mid-lower mantle region. To better understand the local electronic environment of high-spin Fe^(2+) ions in ferropericlase near the transition, we obtained synchrotron Mössbauer spectra (SMS) of (Mg_(0.75),Fe_(0.25))O in externally heated and laser-heated diamond anvil cells at relevant high pressures and temperatures. Results show that the quadrupole splitting (QS) of the dominant high-spin Fe^(2+) site decreases with increasing temperature at static high pressure. The QS values at constant pressure are fitted to a temperature-dependent Boltzmann distribution model, which permits estimation of the crystal-field splitting energy (Δ_3) between the d_(xy_ and d_(xz) or d_(zy) orbitals of the t_(2g) states in a distorted octahedral Fe^(2+) site. The derived Δ_3 increases from approximately 36 meV at 1 GPa to 95 meV at 40 GPa, revealing that both high pressure and high temperature have significant effects on the 3d electronic shells of Fe^(2+) in ferropericlase. The SMS spectra collected from the laser-heated diamond cells within the time window of 146 ns also indicate that QS significantly decreases at very high temperatures. A larger splitting of the energy levels at high temperatures and pressures should broaden the spin crossover in ferropericlase because the degeneracy of energy levels is partially lifted. Our results provide information on the hyperfine parameters and crystal-field splitting energy of high-spin Fe^(2+) in ferropericlase at high pressures and temperatures, relevant to the electronic structure of iron in oxides in the deep lower mantle.

Electronic spin-pairing transitions of iron and associated effects on the physical properties of host phases have been reported in lower-mantle minerals including ferropericlase, silicate perovskite, and possibly in post-perovskite at lower-mantle pressures. Here we evaluate current understanding of the spin and valence states of iron in the lower-mantle phases, emphasizing the effects of the spin transitions on the density, sound velocities, chemical behavior, and transport properties of the lower-mantle phases. The spin transition of iron in ferropericlase occurs at approximately 50 GPa and room temperature but turns into a wide spin crossover under lower-mantle temperatures. Current experimental results indicate a continuous nature of the spin crossover in silicate perovskite at high pressures, but which valence state of iron undergoes the spin crossover and what is its associated crystallographic site remain uncertain. The spin transition of iron results in enhanced density, incompressibility, and sound velocities, and reduced radiative thermal conductivity and electrical conductivity in the low-spin ferropericlase, which should be considered in future geophysical and geodynamic modeling of the Earth's lower mantle. In addition, a reduction in sound velocities within the spin transition is recently reported. Our evaluation of the experimental and theoretical pressure–volume results shows that the spin crossover of iron results in a density increase of 2–4% in ferropericlase containing 17–20% FeO. Here we have modeled the density and bulk modulus profiles of ferropericlase across the spin crossover under lower-mantle pressure–temperature conditions and shown how the ratio of the spin states of iron affects our understanding of the state of the Earth's lower mantle.

The pressure-volume equation of state (EoS) of single-crystal MgO has been studied in diamondanvil cells loaded with helium to 118 GPa and in a non-hydrostatic KCl pressure medium to 87 GPa using monochromatic synchrotron X-ray diffraction. A third-order Birch-Murnaghan fit to the nonhydrostatic P-V data (KCl medium) yields typical results for the initial volume, V0 = 74.698(7) A 3

The Earth’s lowermost mantle displays an important mineralogical transition from perovskite to post-perovskite but the spin state of iron in these phases remains poorly known. Experimental results suggest that iron occurs in the intermediate spin state in both of these phases, which implies that changes in physical properties of the lower mantle must be governed by factors other than spin transitions in iron.

Knowledge of the physical and chemical properties of candidate deep-carbon carriers such as ferromagnesite [(Mg,Fe)CO3] at high pressure and temperature of the deep mantle is necessary for our understanding of deep-carbon storage as well as the global carbon cycle of the planet. Previous studies have reported very different scenarios for the (Mg,Fe)CO3 system at deep-mantle conditions including the chemical dissociation to (Mg,Fe)O+CO2, the occurrence of the tetrahedrally-coordinated carbonates based on CO4 structural units and various high-pressure phase transitions. Here we have studied the phase stability and compressional behavior of (Mg,Fe)CO3 carbonates up to relevant lower-mantle conditions of approximately 120 GPa and 2400 K. Our experimental results show that the rhombohedral siderite (Phase I) transforms to an orthorhombic phase (Phase II with Pmm2 space group) at approximately 50 GPa and 1400 K. The structural transition is likely driven by the spin transition of iron accompanied by a volume collapse in the Fe-rich (Mg,Fe)CO3 phases; the spin transition stabilizes the high-pressure phase II at much lower pressure conditions than its Mg-rich counterpart. It is conceivable that the low-spin ferromagnesite phase II becomes a major deep-carbon carrier at the deeper parts of the lower mantle below 1900 km in depth.

system in the electronic transition of the Fe 2+ ion from the high-spin to low-spin state (spin crossover) near 62 GPa is analyzed as a function of the sample thickness, degree of nonhydrostaticity, and focusing and collimation conditions of a synchrotron beam. It is found that the inclusion of dynamical beats associated with the sample thickness is very important in the approximation of the experimental NFS spectra. It is shown that the electronic transition occurs in a much narrower pressure range ( ± 6 GPa) rather than in a broad range as erroneously follows from experiments with thick samples under strongly nonhydrostatic conditions.

We investigated the valence state and spin state of iron in an Al-bearing ferromagnesian silicate perovskite sample with the composition (Mg0.88Fe0.09) (Si0.94Al0.10)O3 between 1 bar and 100 GPa and at 300 K, using diamond cells and synchrotron Moss- bauer spectroscopy techniques. At pressures below 12 GPa, our Mossbauer spectra can be sufficiently fitted by a ''two-doublet'' model, which assumes one ferrous Fe 2+ -like site and one ferric Fe 3+ -like site with distinct hyperfine parameters. The simplest interpre- tation that is consistent with both the Mossbauer data and previous X-ray emission data on the same sample is that the Fe 2+ -like site is high-spin Fe 2+ , and the Fe 3+ -like site is high-spin Fe 3+ . At 12 GPa and higher pressures, a ''three-doublet'' model is necessary and sufficient to fit the Mossbauer spectra. This model assumes two Fe 2+ -like sites and one Fe 3+ -like site distinguished by their hyperfine parameters. Between

The pressure-induced phase transformations in pure LiAlH4 have been studied using in situ Raman spectroscopy up to 7 GPa. The analyses of Raman spectra reveal a phase transition at approximately 3 GPa from the ambient pressure monoclinic alpha-LiAlH4 phase (P2(1)/c) to a high pressure phase (beta-LiAlH4, reported recently to be monoclinic with space group I4(1)/b) having a distorted [AlH4]- tetrahedron. The Al-H stretching mode softens and shifts dramatically to lower frequencies beyond the phase transformation pressure. The high pressure beta-LiAlH4 phase was pressure quenchable and can be recovered at lower pressures ( approximately 1.2 GPa). The Al-H stretching mode in the quenched state further shifts to lower frequencies, suggesting a weakening of the Al-H bond.

The development of a novel experimental capability of nuclear resonant inelastic X-ray scattering at high pressure and low temperature is presented. The new capability is demonstrated by studying the Fe-specific phonon density of states and magnetism in Eu57Fe2As2., A new synchrotron radiation experimental capability of coupling nuclear resonant inelastic X-ray scattering with the cryogenically cooled high-pressure diamond anvil cell technique is presented. The new technique permits measurements of phonon density of states at low temperature and high pressure simultaneously, and can be applied to studies of phonon contribution to pressure- and temperature-induced magnetic, superconducting and metal–insulator transitions in resonant isotope-bearing materials. In this report, a pnictide sample, EuFe2As2, is used as an example to demonstrate this new capability at beamline 3-ID of the Advanced Photon Source, Argonne National Laboratory. A detailed description of the technical development is given. The Fe-specific phonon density of states and magnetism from the Fe sublattice in Eu57Fe2As2 at high pressure and low temperature were derived by using this new capability.

This study demonstrates the use of monochromatic synchrotron X-ray radiation of 40 keV for high-precision equation-of-state studies on sets of single crystals analysed individually in the same diamond-anvil pressure cell. Angle-dispersive zone-axis diffraction patterns were obtained from crystals of wustite-Fe0.93O and magnesiowüstite-(Mg0.73Fe0.27)O to 51 GPa in a hydrostatic helium pressure medium. The rhombohedral phase of Fe0.93O was observed above 23 GPa, and its isothermal bulk modulus (K0) was determined to be 134 (+/-4) GPa, assuming K'=4. The rhombohedral phase of Fe(0.93)O is more compressible than B1-structured Fe0.93O, with K0=146 (+/-2) GPa. Magnesiowüstite-(Mg0.73Fe0.27)O remains cubic over the experimental pressure range, and has a bulk modulus of 154 (+/-3) GPa with K'=4.0 (+/-0.1).

Synchrotron-based X-ray emission spectroscopy (XES) is well suited to probing the local electronic structure of 3d transition metals such as Fe and Mn in their host phases. The laser-heated diamond anvil cell technique is uniquely capable of generating ultra-high static pressures and temperatures in excess of 100 GPa and 3000 K. Here X-ray emission spectroscopy and X-ray diffraction have been interfaced with the laser-heated diamond cell for studying the electronic spin states of iron in magnesiowüstite-(Mg0.75,Fe0.25)O and its crystal structure under lower-mantle conditions. X-ray emission spectra of the ferrous iron in a single crystal of magnesiowüstite-(Mg0.75,Fe0.25)O indicate that a high-spin to low-spin transition of ferrous iron occurs at 54 to 67 GPa and 300 K and the ferrous iron remains in the high-spin state up to 47 GPa and 1300 K. This pilot study points to the unique capability of the synchrotron-based XES and X-ray diffraction techniques for addressing the issue of electronic spin transition or crossover in 3d transition metals and compounds under extreme high-P-T conditions.

We introduce the combination of nuclear resonant inelastic X-ray scattering and synchrotron Mossbauer spectroscopy with the laser-heated diamond anvil cell technique for studying magnetic, elastic, thermodynamic, and vibrational properties of materials under high pressures and high temperatures. An Nd:YLF laser, operating in continuous donut mode (TEM01), has been used to heat samples inside a diamond anvil cell from both sides. Temperatures of the laser-heated sample are measured by means of spectral radiometry and by the detailed balance principle of the energy spectra. The temperature measured by the detailed balance principle is in very good agreement with values determined from the thermal radiation spectra fitted to the Planck radiation function up to 1700 K. Nuclear resonant scattering on 57 Fe-containing materials (i.e., Fe, FeO, Fe2O3) has been studied up to 2500 K and 100 GPa. A detailed description of the laser-heating optics, temperature determination, the X-ray monochromatization, and the X-ray focusing optics is given in this article.

We describe an in situ high pressure-temperature Raman technique for studying materials in laser-heated diamond anvil cells using a Nd:YLF laser (1053 nm) as the heating source and an ion laser as the Raman exciting source. Here we introduce the method of laser heating transparent samples using a metallic foil (Pt,Re, or W) as the laser absorber (internal heating furnace) in a diamond cell. The YLF laser is used to effectively laser-heat one side of a metal foil 5–15 μm thick with a small hole of 10–20 μm in diameter at the center. The foil, in turn, heats a transparent sample while the Raman signals excited by an Ar+ or Kr+ laser are measured. Temperature of the laser-heated foil is measured by means of spectroradiometry whereas the average temperature of the heated sample is independently determined from the intensity ratios of the anti-Stokes/Stokes excitation pairs. The intrinsic temperature-dependent asymmetry of the Raman spectra arises from the principle of the detailed balance and is independent of sample properties other than the temperatures. The average determined by the signal-to-noise ratio of anti-Stokes/Stokes excitation pairs gives the sample temperature with the statistical accuracy of the Raman spectra. Transparent samples such as CO2 have been heated up to 1600 K and 65 GPa and Raman spectra have been measured with temperature uncertainty of 50–100 K. In situ Raman spectroscopy by laser heating represents a powerful technique to characterize high pressure-temperature properties of materials including molecular systems present in planetary interiors.

Magnetic, elastic, thermodynamic, and vibrational properties of the most iron-rich sulfide, Fe3S, known to date have been studied with synchrotron Mossbauer spectroscopy (SMS) and nuclear resonant inelastic X-ray scattering (NRIXS) up to 57 GPa at room temperature. The magnetic hyperfine fields derived from the time spectra of the synchrotron Mossbauer spectroscopy show that the low-pressure magnetic phase displays two magnetic hyperfine field sites and that a magnetic collapse occurs at 21 GPa. The magnetic to non-magnetic transition significantly affects the elastic, thermodynamic, and vibrational properties of Fe3S. The magnetic collapse of Fe3S may also affect the phase relations in the iron–sulfur system, changing the solubility of sulfur in iron under higher pressures. Determination of the physical properties of the non-magnetic Fe3S phase is important for the interpretation of the amount and properties of sulfur present in the planetary cores. Sound velocities of Fe3S obtained from the measured partial phonon density of states (PDOS) for 57Fe incorporated in the alloy show that Fe3S has higher compressional and shear wave velocity than those of hcp-Fe and hcp-Fe0.92Ni0.08 alloy under high pressures, making sulfur a potential light element in the Earth's core based on geophysical arguments. The VP and VS of the non-magnetic Fe3S follow a Birch's law trend whereas the slopes decrease in the magnetic phase, indicating that the decrease of the magnetic moment significantly affects the sound velocities. If the Martian core is in the solid state containing 14.2 wt.% sulfur, it is likely that the non-magnetic Fe3S phase is a dominant component and that our measured sound velocities of Fe3S can be used to construct the corresponding velocity profile of the Martian core. It is also conceivable that Fe3P and Fe3C undergo similar magnetic phase transitions under high pressures.

Alumina (alpha-Al(2)O(3)) has been widely used as a pressure calibrant in static high-pressure experiments and as a window material in dynamic shock-wave experiments; it is also a model material in ceramic science. So understanding its high-pressure stability and physical properties is crucial for interpreting such experimental data, and for testing theoretical calculations. Here we report an in situ X-ray diffraction study of alumina (doped with Cr(3+)) up to 136 GPa and 2,350 K. We observe a phase transformation that occurs above 96 GPa and at high temperatures. Rietveld full-profile refinements show that the high-pressure phase has the Rh(2)O(3) (II) (Pbcn) structure, consistent with theoretical predictions. This phase is structurally related to corundum, but the AlO(6) polyhedra are highly distorted, with the interatomic bond lengths ranging from 1.690 to 1.847 A at 113 GPa. Ruby luminescence spectra from Cr(3+) impurities within the quenched samples under ambient conditions show significant red shifts and broadening, consistent with the different local environments of chromium atoms in the high-pressure structure inferred from diffraction. Our results suggest that the ruby pressure scale needs to be re-examined in the high-pressure phase, and that shock-wave experiments using sapphire windows need to be re-evaluated.

Recent advances in high-pressure diamond anvil cell experiments include high-energy synchrotron x-ray techniques as well as new cell designs and gasketing procedures. The success of high-pressure experiments usually depends on a well-prepared sample, in which the gasket plays an important role. Various gasket materials such as diamond, beryllium, rhenium, and stainless steel have been used. Here we introduce amorphous boron as another gasket material in high-pressure diamond anvil cell experiments. We have applied the boron gasket for laser-heating x-ray diffraction, radial x-ray diffraction, nuclear resonant inelastic x-ray scattering, and inelastic x-ray scattering. The high shear strength of the amorphous boron maximizes the thickness of the sample chamber and increases the pressure homogeneity, improving the quality of high-pressure data. Use of amorphous boron avoids unwanted x-ray diffraction peaks and reduces the absorption of incident and x rays exiting the gasket material. The high quality of the diffraction patterns makes it possible to refine the cell parameters with powder x-ray diffraction data under high pressure and high temperature. The reactivity of boron prevents its use at high temperatures, however. When heated, boron may also react with the specimen to produce unwanted phases. The relatively porous boron starting material at ambient conditions also poses some challenges for sample preparation.

Semiconducting transition metal dichalcogenides (TMDs) demonstrate a wide range of optoelectronic properties due to their diverse elemental compositions, and are promising candidates for next-generation optoelectronics and energy harvesting devices. However, effective band offset engineering is required to implement practical structures with desirable functionalities. Here, we explore the pressure-induced band structure evolution of monolayer WS2 and Mo0.5W0.5S2 using hydrostatic compressive strain applied in a diamond anvil cell (DAC) apparatus and theoretical calculations, in order to study the modulation of band structure and explore the possibility of band alignment engineering through different compositions. Higher W composition in Mo(1-x)W(x)S2 contributes to a greater pressure-sensitivity of direct band gap opening, with a maximum value of 54 meV GPa(-1) in WS2. Interestingly, while the conduction band minima (CBMs) remains largely unchanged after the rapid gap increase, valence band maxima (VBMs) significantly rise above the initial values. It is suggested that the pressure- and composition-engineering could introduce a wide variety of band alignments including type I, type II, and type III heterojunctions, and allow to construct precise structures with desirable functionalities. No structural transition is observed during the pressure experiments, implying the pressure could provide selective modulation of band offset.

Magnetite exhibits unique electronic, magnetic and structural properties in extreme conditions that are of great research interest. Previous studies have suggested a number of transitional models, although the nature of magnetite at high pressure remains elusive. We have studied a highly stoichiometric magnetite using inelastic X-ray scattering, X-ray diffraction and emission and Raman spectroscopies in diamond anvil cells up to ~20 GPa, while complementary electrical conductivity measurements were conducted in a cubic anvil cell up to 8.5 GPa. We have observed an elastic softening in the diagonal elastic constants (C11 and C44) and a hardening in the off-diagonal constant (C12) at ~8 GPa where significant elastic anisotropies in longitudinal and transverse acoustic waves occur, especially along the [110] direction. An additional vibrational Raman band between the A1g and T2g modes was also detected at the transition pressure. These abnormal elastic and vibrational behaviors of magnetite are attributed to the occurrence of the octahedrally-coordinated Fe2+-Fe3+-Fe2+ ions charge-ordering along the [110] direction in the inverse spinel structure. We propose a new phase diagram of magnetite in which the temperature for the metal-insulator and distorted structural transitions decreases with increasing pressure while the charge-ordering transition occurs at ~8 GPa and room temperature.

The correlation between the $4f$-conduction electron ($c$-$f$) hybridization and the transition temperature ${T}_{0}$ into the unconventional antiferromagnetically (AFM) ordered state in $\text{Ce}({\text{Ru}}_{1\ensuremath{-}x}$${\text{Fe}}_{x}{)}_{2}{\text{Al}}_{10}$ has been investigated. The impact of pressure on the crystal structure and the electronic structure has been measured using x-ray diffraction and resonant x-ray emission spectroscopy at the Ce ${L}_{3}$ absorption edge in a diamond anvil cell. Our results show that the lattice spacings imply some correlation with the disappearance of ${T}_{0}$. Analyses of the measured valence states, however, show only a weak correlation with the corresponding critical disappearance of the AFM order within experimental errors. Our results may be explained by a scenario based on the Kondo-Heisenberg model beyond the conventional Doniach phase diagram.

Pressure dependence of the Ce valence in ${\mathrm{CeCu}}_{2}{\mathrm{Ge}}_{2}$ has been measured up to 24 GPa at 300 K and to 17 GPa at 18--20 K using x-ray absorption spectroscopy in the partial fluorescence yield. A smooth increase of the Ce valence with pressure is observed across the two superconducting (SC) regions without any noticeable irregularity. The chemical pressure dependence of the Ce valence was also measured in ${\mathrm{Ce}({\mathrm{Cu}}_{1\ensuremath{-}x}{\mathrm{Ni}}_{x})}_{2}{\mathrm{Si}}_{2}$ at 20 K. A very weak, monotonic increase of the valence with $x$ was observed, without any significant change in the two SC regions. Within experimental uncertainties, our results show no evidence for the valence transition with an abrupt change in the valence state near the SC II region, challenging the valence-fluctuation mediated superconductivity model in these compounds at high pressure and low temperature.

Pressure dependence of the Yb valence in YbNiGe${}_{3}$ has been investigated up to 15.6 GPa at 300 K and up to 7.7 GPa at 17 K by means of x-ray absorption spectroscopy in $L{\ensuremath{\alpha}}_{1}$ partial fluorescence yield mode and resonant x-ray emission spectroscopy around the Yb ${L}_{3}$ absorption edge. The Yb valence in YbNiGe${}_{3}$ at ambient pressure strongly fluctuates with the mean valence of $v=2.52\ifmmode\pm\else\textpm\fi{}0.01$ at 300 K. The Yb valence rapidly changes toward a trivalent state with pressure up to $\ensuremath{\sim}$5 GPa, slowly increases up to $\ensuremath{\sim}$10 GPa, and then reaches a saturated value of $v\ensuremath{\sim}2.87$ at 15.6 GPa. The Yb valence at 17 K slightly decreases compared to that at 300 K; $v\ensuremath{\sim}2.45$ at ambient pressure and $\ensuremath{\sim}$$2.72$ at 7.7 GPa. We found that the pressure-induced change in the intensity of a quadrupole component in the x-ray absorption spectra shows the same trend as the Yb valence in YbNiGe${}_{3}$. In contrast to YbNiGe${}_{3}$, the Yb valence in YbNiSi${}_{3}$ is nearly 3 at ambient pressure with almost no temperature dependence.

Molybdenum disulphide is a layered transition metal dichalcogenide that has recently raised considerable interest due to its unique semiconducting and opto-electronic properties. Although several theoretical studies have suggested an electronic phase transition in molybdenum disulphide, there has been a lack of experimental evidence. Here we report comprehensive studies on the pressure-dependent electronic, vibrational, optical and structural properties of multilayered molybdenum disulphide up to 35 GPa. Our experimental results reveal a structural lattice distortion followed by an electronic transition from a semiconducting to metallic state at ~19 GPa, which is confirmed by ab initio calculations. The metallization arises from the overlap of the valance and conduction bands owing to sulphur-sulphur interactions as the interlayer spacing reduces. The electronic transition affords modulation of the opto-electronic gain in molybdenum disulphide. This pressure-tuned behaviour can enable the development of novel devices with multiple phenomena involving the strong coupling of the mechanical, electrical and optical properties of layered nanomaterials.