Comment on: Evidence and Stability Field of fcc Superionic Water Ice Using Static Compression

Weck et al. (1) report on the existence and stability fields of two superionic (SI) phases of H2O ice at high P-T (P-T) conditions, which has been a topic of static and dynamic experiments and theoretical calculations (see Ref. (2) and references therein). They confirm Ref. (2) in that there are two SI phases with bcc and fcc oxygen sublattices with the stability at low- and high-P. However, they report on an extended stability field of fcc-SI ice toward lower T but no sign of it below 57 GPa. Here we argue that the reported phase boundaries of fcc-SI phase are not well experimentally justified due to difficulties to perform adequate X-ray diffraction (XRD) and radiometric measurements.Comment: 2 pages, 2 figures, 2 reference

High-Pressure Synthesis of a Pentazolate Salt

The pentazolates, the last all-nitrogen members of the azole series, have been notoriously elusive for the last hundred years despite enormous efforts to make these compounds in either gas or condensed phases. Here we report a successful synthesis of a solid state compound consisting of isolated pentazolate anions N5-, which is achieved by compressing and laser heating cesium azide (CsN3) mixed with N2 cryogenic liquid in a diamond anvil cell. The experiment was guided by theory, which predicted the transformation of the mixture at high pressures to a new compound, cesium pentazolate salt (CsN5). Electron transfer from Cs atoms to N5 rings enables both aromaticity in the pentazolates as well as ionic bonding in the CsN5 crystal. This work provides a critical insight into the role of extreme conditions in exploring unusual bonding routes that ultimately lead to the formation of novel high nitrogen content species

The thermal equation of state of (Mg, Fe)SiO3 bridgmanite (perovskite) and implications for lower mantle structures

The high‐pressure/high‐temperature equation of state (EOS) of synthetic 13% Fe‐bearing bridgmanite (Mg silicate perovskite) is measured using powder X‐ray diffraction in a laser‐heated diamond anvil cell with a quasi‐hydrostatic neon pressure medium. We compare these results, which are consistent with previous 300 K sound speed and compression studies, with a reanalysis of Fe‐free Mg end‐member data from Tange et al. (2012) to determine the effect of iron on bridgmanite’s thermoelastic properties. EOS parameters are incorporated into an ideal lattice mixing model to probe the behavior of bridgmanite at deep mantle conditions. With this model, a nearly pure bridgmanite mantle composition is shown to be inconsistent with density and compressibility profiles of the lower mantle. We also explore the buoyant stability of bridgmanite over a range of temperatures and compositions expected for Large Low‐Shear Velocity Provinces, concluding that bridgmanite‐dominated thermochemical piles are more likely to be passive dense layers externally supported by convection, rather than internally supported metastable domes. The metastable dome scenario is estimated to have a relative likelihood of only 4–7%, given the narrow range of compositions and temperatures consistent with seismic constraints. If buoyantly supported, such structures could not have remained stable with greater thermal contrast early in Earth’s history, ruling out formation scenarios involving a large concentration of heat producing elements.Key PointsHigh P‐T equation of state of 13% and 0% Fe bridgmanite (perovksite) is obtainedPure bridgmanite mantle is inconsistent with PREM at any Fe contentBuoyant stability of LLSVPs favors passive chemical piles over metastable domesPeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/141021/1/jgrb51327.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/141021/2/jgrb51327_am.pd

Thermal equation of state and stability of (Mg_(0.06)Fe_(0.94))O

We present the pressure-volume-temperature (P-V-T) equation of state of polycrystalline (Mg_(0.06)Fe_(0.94))O (Mw94) determined from laser-heated x-ray diffraction experiments up to 122 GPa and 2100 K, conditions approaching those of the deep mantle. We conducted two sets of experiments, one with an in situ Fe metal oxygen fugacity buffer and one without such a buffer. The internal pressure markers used in these experiments were B2-NaCl and hcp-Fe in the buffered experiment and B2-NaCl in the unbuffered experiment. In the sampled P-T range of the high temperature part of this study, only the B1 structure of Mw94 was observed, indicating that the addition of Mg to FeO stabilizes the B1 phase with respect to the B8 phase at these conditions. Both datasets were fit to a Birch-Murnaghan and Mie-Grüneisen-Debye thermal equation of state using a new open-source fitting routine, also presented here. Analysis of these data sets using the same internal pressure marker shows that the P–V–T data of Mw94 obtained in the unbuffered experiment are well explained by the equation of state parameters determined from the buffered data set. We have also compared the thermal equation of state of Mw94 with that of wüstite and conclude that Mw94 has measurably distinct thermoelastic properties compared with those of wüstite. We use the results obtained in the buffered experiment to determine the density and bulk sound velocity of Mw94 at the base of the mantle and compare these values to geophysical observations of ultralow-velocity zones