The density of silicate melts at high pressure determined the efficiency of gravitational differentiation in the solidifying magma ocean and thus the starting conditions for the Earth's evolution. The denisty also controls the migration of melts in the lithosphere and their stabilization in the transition zone and near the core mantle boundary. Yet, no density systematic exists for melts across the pressure range of the mantle. This is primarily because of severe experimental difficulties associated with measuring the density of silicate liquids at mantle pressures and temperatures (tiny sample size, melt chemical reactivity, lack of crystalline structure). The use of glasses as proxies of melts at high pressure lifts some but not all of these challenges, and may prove important in developing theoretical models of melts physical behavior at high pressures. Here we report on the density of MORB glass up to 32.3 GPa at room temperature measured by the recently developed all-optical method in a diamond anvil cell. The comparison of the MORB glass density to that for other basaltic glasses reported in the literature reveals contradictions, similarly to those existing between data available for MORB-like melts, which underscore the need for consistent, systematic melt and glass density measurements at high pressure across a broad compositional space. More broadly, the compression behavior of MORB and other basaltic glasses, SiO2, MgSiO3, and Mg2SiO4 glasses suggests that the incorporation of SiO2 and/or large network-modifiers (larger than Mg) softens the glass (smaller isothermal bulk modulus and its pressure derivative). Future all-optical measurements of glass density may provide fundamental, critical input to develop models of complex glasses and melts physical properties, and help assessing the solidification of the primordial magma ocean, the initiation and development of physical and chemical heterogeneity in the mantle, and the migration or stabilization of melts at different levels in the deep Earth.

Physical properties of mantle minerals are essential for comprehensive geodynamic modeling. High-pressure experiments allow measurements of physical properties but fundamental insights into their evolution with pressure are often experimentally inaccessible. Here we report the first in situ experimental determination of the optical refractive index, its wavelength-dispersion, and optical absorption coefficient of ferropericlase up to similar to 140 GPa at room temperature. All these properties change gradually in dominantly high-spin (below similar to 50 GPa) and low-spin (above similar to 80 GPa) ferropericlase. However, in the mixed-spin state (i.e., significant presence of both high- and low-spin iron), the index dispersion and the absorption coefficient decrease by a factor of three and similar to 30%, respectively. These anomalies suggest that charge transport by small polaron is reduced in mixed-spin ferropericlase, providing fundamental insights into the factor-of-three lower electrical conductivity of ferropericlase at similar to 50-70 GPa.

Quaternary kesterite-type (KS) compounds have attracted worldwide attention from the scientific community as promising materials for solar cells. On the route to optimizing their performance, the effect of stress and strain constitutes a critical factor when it comes to thin film applications. Following a recent theoretical study, we report here joint experimental and computational high-pressure investigations on the KS Ag2ZnSnS4 and wurtz–kesterite (WZ–KS)-type Ag2CdSnS4 compounds. Our results reveal that both materials undergo successive transformations, first into a GeSb-type and then toward a CrN-type modification at ambient temperature. Our theoretical calculations predict a metallic character for all Ag2ZnSnS4 and Ag2CdSnS4 high-pressure phases. In addition, structural disorder is observed in KS Ag2ZnSnS4 upon moderate compression, prior to its KS → GeSb-type transition. Decompression leads to the recovery of a disordered zinc blende-type structure in the latter, whereas Ag2CdSnS4 retains the disordered GeSb-type modification. The similarities and deviations from the archetypical KS Cu2ZnSnS4 are discussed.

The evolution of chemical bonding in ferropericlase, (Mg,Fe)O, with pressure may affect the physical and chemical properties of the Earth's lower mantle. Here, we report high-pressure optical absorption spectra of single-crystalline ferropericlase ((Mg0.87Fe0.13)O) up to 135 GPa. Combined with a re-evaluation of published partial fluorescence yield X-ray absorption spectroscopy data, we show that the covalency of the Fe-O bond increases with pressure, but the iron spin transition at 57-76.5 GPa reverses this trend. The qualitative crossover in chemical bonding suggests that the spin-pairing transition weakens the Fe-O bond in ferropericlase. We find, that the spin transition in ferropericlase is caused by both the increase of the ligand field-splitting energy and the decrease in the spin-pairing energy of high-spin Fe2+.

We report the first direct measurements of the refractive index of silica glass up to 145 GPa that allowed quantifying its density, bulk modulus, Lorenz-Lorentz polarizability, and band gap. These properties show two major anomalies at ∼10 and ∼40  GPa. The anomaly at ∼10  GPa signals the onset of the increase in Si coordination, and the anomaly at ∼40  GPa corresponds to a nearly complete vanishing of fourfold Si. More generally, we show that the compressibility and density of noncrystalline solids can be accurately measured in simple optical experiments up to at least 110 GPa.

Refractive index provides fundamental insights into the electronic structure of materials. At high pressure, however, the determination of refractive index and its wavelength dispersion is challenging, which limits our understanding of how physical properties of even simple materials, such as MgO, evolve with pressure. Here, we report on the measurement of room-temperature refractive index of MgO up to ∼140 GPa. The refractive index of MgO at 600 nm decreases by ∼2.4% from ∼1.737 at 1 atm to ∼1.696 (±0.017) at ∼140 GPa. Despite the index at 600 nm is essentially pressure independent, the absolute wavelength dispersion of the refractive index at 550–870 nm decreases by ∼28% from ∼0.015 at 1 atm to ∼0.011 (±8.04 × 10−4) at ∼103 GPa. Single-effective-oscillator analysis of our refractive index data suggests that the bandgap of MgO increases by ∼1.1 eV from 7.4 eV at 1 atm to ∼8.5 (±0.6) eV at ∼103 GPa.

Experiments in laser‐heated diamond anvil cells (LH DACs) are conducted to assess phase diagrams of planetary materials at high pressure‐temperature ( P‐T ) conditions; thus, reliable determination of temperature in LH DAC experiments is essential. Radiometric temperature determination in LH DACs relies on the assumption of sample's wavelength‐independent optical properties (graybody assumption), which is not justified for major lower mantle materials. The result is that experimental phase diagrams contain systematic unconstrained errors. Here we estimate the systematic error in radiometric temperature of nongray polycrystalline bridgmanite (Bgm; Mg 0.96 Fe 2+ 0.036 Fe 3+ 0.014 Si 0.99 O 3 ) in a LH DAC by modeling emission and absorption of thermal radiation in a sample with experimentally‐constrained optical properties. A comparison to experimental data validates the models and reveals that thermal spectra measured in LH DAC experiments record the interaction of radiation with the hot nongray sample. The graybody assumption in the experiments on translucent Bgm (light extinction coefficient, k < ∼ 250 cm ‐1 at 500–900 nm) yields temperatures ∼5% higher than the maximum temperature in the sample heated to ∼1900 K. In contrast, the graybody temperature of dark Bgm ( k > ∼1500 cm −1 ), such as that produced upon melt quenching in LH DACs, underestimates the maximum temperature by ∼10%. Our experimental results pose quantitative constraints on the effect of nongray optical properties on the uncertainty of radiometric temperature determination in Bgm in the LH DACs. Evaluating nongray temperature in the future would enable a revision of the Bgm to post‐perovskite phase transition and the high‐pressure melting curve of Bgm.

Optical studies of materials at high pressure-temperature (P-T) conditions provide insights into their physical properties that may be inaccessible to direct determination at extreme conditions. Incandescent light sources, however, are insufficiently bright to optically probe samples with radiative temperatures above ∼1000 K. Here we report on a system to perform optical absorption experiments in a laser-heated diamond anvil cell at T up to at least 4000 K. This setup is based on a pulsed supercontinuum (broadband) light probe and a gated CCD detector. Precise and tight synchronization of the detector gates (3 ns) to the bright probe pulses (1 ns) diminishes the recorded thermal background and preserves an excellent probe signal at high temperature. We demonstrate the efficiency of this spectroscopic setup by measuring the optical absorbance of solid and molten (Mg,Fe)SiO3, an important constituent of planetary mantles, at P ∼30 GPa and T ∼1200 K to 4150 K. Optical absorbance of the hot solid (Mg,Fe)SiO3 is moderately sensitive to temperature but increases abruptly upon melting and acquires a strong temperature dependence. Our results enable quantitative estimates of the opacity of planetary mantles with implications to their thermal and electrical conductivities, all of which have never been constrained at representative P-T conditions, and call for an optical detection of melting in silicate-bearing systems to resolve the extant ambiguity in their high-pressure melting curves.