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The interplay between crystal–melt and grain boundary interfaces in partially melted polycrystalline aggregates controls many physical properties of mantle rocks. To understand this process at the fundamental level requires improved knowledge about the interfacial structures and energetics. Here, we report the results of first-principles molecular dynamics simulations of two grain boundaries of (0l1)/[100] type for tilt angles of 30.4° and 49.6° and the corresponding solid–liquid interfaces in Mg₂SiO₄forsterite at the conditions of the upper mantle. Our analysis of the simulated position time series shows that structural distortions at the solid–liquid interfacial region are stronger than intergranular interfacial distortions. The calculated formation enthalpy of the solid–solid interfaces increases nearly linearly from 1.0 to 1.4 J/m²for the 30.4° tilt and from 0.8 to 1.0 J/m²for the 49.6° tilt with pressure from 0 to 16 GPa at 1500 K, being consistent with the experimental data. The solid–liquid interfacial enthalpy takes comparable values in the range 0.9 to 1.5 J/m²over similar pressure interval. The dihedral angle of the forsterite–melt system estimated using these interfacial enthalpies takes values in the range of 67° to 146°, showing a decreasing trend with pressure. The predicted dihedral angle is found to be generally larger than the measured data for silicate systems, probably caused by compositional differences between the simulation and the measurements.

 

Abstract Grain boundaries in mantle minerals are of critical importance to geophysical and geochemical processes of the Earth’s interior. One of the fundamental issues is to understand how the water (H2O) component influences the properties of grain boundaries in silicate materials. Here, we report the results of the structure and stability of several tilt grain boundaries in Mg2SiO4 forsterite over the pressure range 0 to 15 GPa using density functional theory-based first-principles simulations. The results suggest greater energetic stability and hydration-driven volume collapse (negative excess volume) at zero pressure for the majority of hydrous grain boundaries relative to the anhydrous (dry) ones. All the hydrous grain boundaries become increasingly favorable at elevated pressures as the calculated hydration enthalpy systematically decreases with increasing pressure. The hydrous components at the interfacial regions are predominantly in the hydroxyl form and, to a lesser extent, in the molecular H2O form. Their calculated ratio ranges from 1.6 to 8.7 among the different grain boundary configurations. Our structural analysis also reveals that the hydroxyls are bound to either both Mg and Si or to Mg only. In comparison, the molecular species are bound only to Mg sites. Besides direct oxygen-hydrogen bonding, intermolecular hydrogen bonding becomes important with compression. On the basis of our results, we suggest that local atomic rearrangements caused by dissociative adsorption of water facilitate efficient compaction of the boundary interfaces, which, in turn, results in greater relative stability of hydrous grain boundaries. This means that water prefers to be incorporated within the grain boundaries over the bulk of silicate materials. 

Probe is the core component of an optical scanning probe microscope such as scattering-type scanning near-field optical microscopy (s-SNOM). Its ability of concentrating and localizing light determines the detection sensitivity of nanoscale spectroscopy. In this paper, a novel plasmonic probe made of a gradient permittivity material (GPM) is proposed and its nanofocusing performance is studied theoretically and numerically. Compared with conventional plasmonic probes, this probe has at least two outstanding advantages: First, it doesn't need extra structures for surface plasmon polaritons (SPPs) excitation or localized surface plasmon resonance (LSPR), simplifying the probe system; Second, the inherent nanofocusing effects of the conical probe structure can be further reinforced dramatically by designing the distribution of the probe permittivity. As a result, the strong near-field enhancement and localization at the tip apex improve both spectral sensitivity and spatial resolution of a s-SNOM. We also numerically demonstrate that a GPM probe as well as its enhanced nanofocusing effects can be realized by conventional semiconductor materials with designed doping distributions. The proposed novel plasmonic probe promises to facilitate subsequent nanoscale spectroscopy applications. 

The viscosity of iron alloy liquids is the key for the core dynamo and core‐mantle differentiation of terrestrial bodies. Here we measured the viscosity of Fe‐Ni‐C liquids up to 7 GPa using the floating sphere viscometry method and up to 330 GPa using first‐principles calculations. We found a viscosity increase at ∼3–5 GPa, coincident with a structural transition in the liquids. After the transition, the viscosity reaches ∼14–27 mPa·s, a factor of 2–4 higher than that of Fe and Fe‐S liquids. Our computational results from 5 to 330 GPa also indicate a high viscosity of the Fe‐Ni‐C liquids. For a carbon‐rich core in large terrestrial body, the level of turbulence in the outer core would be lessened approaching the inner core boundary. It is also anticipated that Fe‐Ni‐C liquids would percolate in Earth's deep silicate mantle at a much slower speed than Fe and Fe‐S liquids.

 

The presence of light elements in the metallic cores of the Earth, the Moon, and other rocky planetary bodies has been widely proposed. Carbon is among the top candidates in light of its high cosmic abundance, siderophile nature, and ubiquity in iron meteorites. It is, however, still controversial whether carbon‐rich core compositional models can account for the seismic velocity observations within the Earth and lunar cores. Here, we report the density and elasticity of Fe₉₀Ni₁₀‐3 wt.% C and Fe₉₀Ni₁₀‐5 wt.% C liquid alloys using synchrotron‐based X‐ray absorption experiments and first‐principles molecular dynamics simulations. Our results show that alloying of 3 wt.% and 5 wt.% C lowers the density of Fe₉₀Ni₁₀liquid by ∼2.9–3.1% at 2 GPa, and ∼3.4–3.6% at 9 GPa. More intriguingly, our experiments and simulations both demonstrate that the bulk moduli of the Fe‐Ni‐C liquids are similar to or slightly higher than those of Fe‐Ni liquids. Thus, the calculated compressional velocities (v_p) of Fe‐Ni‐C liquids are higher than that of pure Fe‐Ni alloy, promoting carbon as a possible candidate to explain the elevatedv_pin the Earth's outer core. However, the values and slopes of both density andv_pof the studied two Fe‐Ni‐C liquids do not match the outer core seismic models, suggesting that carbon may not be the sole principal light element in Earth's outer core. The highv_pof Fe‐Ni‐C liquids does not match the presumptivev_pof the lunar outer core well, indicating that carbon is less likely to be its dominant light element.