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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 importantmore »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.« less

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.