The rotational and translational dynamics of molecular hydrogen trapped within beta-hydroquinone clathrate (H-2@beta-HQ)-a practical example of a quantum particle trapped within an anisotropic confining potential-were investigated using inelastic neutron scattering and Raman spectroscopy. High-resolution vibrational spectra, including those collected from the VISION spectrometer at Oak Ridge National Laboratory, indicate relatively strong attractive interaction between guest and host with a strikingly large splitting of rotational energy levels compared with similar guest-host systems. Unlike related molecular systems in which confined H-2 exhibits nearly free rotation, the behavior of H-2@beta-HQ is explained using a two-dimensional (2D) hindered rotor model with barrier height more than 2 times the rotational constant (-16.2 meV).

Using the dynamic compression technique, the sound velocities of Fe-11.8wt%S were measured up to 211.4 (4.5)GPa and 6,150K. Discontinuities both in shock velocity and sound velocity indicate that Fe-11.8wt%S completely melts at a pressure of 111.3 (2.3)GPa. By the energy conservation law, the calculated liquidus temperature is about 2,500 (300)K. Extrapolated to the inner-core boundary based on the Lindeman law, the liquidus temperature of Fe-11.8wt%S is 4,300 (300)K. We developed a thermodynamic model fit to the experimental data, which allows calculation of the densities and sound velocities of liquid Fe-S under core conditions. For liquid Fe-11.8wt%S and Fe-10wt%S, good agreement was achieved between the extrapolations using our model and experimental measurements at very low pressure. Under the conditions of the outer core, the densities and bulk sound velocities of Fe-10wt%S provide a good fit to observed seismic profiles of Earth's core. Our results imply that an upper limit of 10wt% S content in Earth's core satisfies the geophysical constraints. Simultaneously considering other geochemical constraints, the outer core may contain about 6wt% sulfur and 4wt% silicon.

We study Mn substitution for Ti in BaTiO3 with and without compensating oxygen vacancies using density functional theory (DFT) in combination with dynamical mean-field theory (DMFT). We find strong charge and spin fluctuations. Without compensating oxygen vacancies, the ground state is found to be a quantum superposition of two distinct atomic valences, 3d(4) and 3d(5). Introducing a compensating oxygen vacancy at a neighboring site reduces both charge and spin fluctuations due to the reduction of electron hopping from Mn to its ligands. As a consequence, valence fluctuations are reduced, and the valence is closely fixed to the high spin 3d(5) state. Here we show that inclusion of charge and spin fluctuations is necessary to obtain an accurate ground state of transition metal-doped ferroelectrics.

The chemical stability of solid cubane under highpressure was examined with in situ Raman spectroscopy and synchrotron powder X-ray diffraction (PXRD) in a diamond anvil cell (DAC) up to 60 GPa. The Raman modes associated with solid cubane were assigned by comparing experimental data with calculations based on density functional perturbation theory, and low-frequency lattice modes are reported for the first time. The equation of state of solid cubane derived from the PXRD measurements taken during compression gives a bulk modulus of 14.5(2) GPa. In contrast with previous work and chemical intuition, PXRD and Raman data indicate that solid cubane exhibits anomalously large stability under extreme pressure, despite its immensely strained 90 degrees C-C-C bond angles.

Despite the pioneering efforts to explore the nature of carbon in carbon-bearing silicate melts under compression, experimental data for the speciation and the solubility of carbon in silicate melts above 4 GPa have not been reported. Here, we explore the speciation of carbon and pressure-induced changes in network structures of carbon-bearing silicate (Na2O-3SiO(2), NS3) and sodium aluminosilicate (NaAlSi3O8, albite) glasses quenched from melts at high pressure up to 8 GPa using multinuclear solid-state NMR. The Al-27 triple quantum (3Q) MAS NMR spectra for carbon-bearing albite melts revealed the pressure-induced increase in the topological disorder around 4 coordinated Al (Al-[4]) without forming Al-[5,Al-6]. These structural changes are similar to those in volatile-free albite melts at high pressure, indicating that the addition of CO2 in silicate melts may not induce any additional increase in the topological disorder around Al at high pressure. C-13 MAS NMR spectra for carbon-bearing albite melts show multiple carbonate species, including Si-[4](CO3)Si-[4], Si-[4](CO3)Al-[4], Al-[4](CO3)Al-[4], and free CO32-. The fraction of Si-[4](CO3)Al-[4] increases with increasing pressure, while those of other bridging carbonate species decrease, indicating that the addition of CO2 may enhance mixing of Si and Al at high pressure. A noticeable change is not observed for Si-29 NMR spectra for the carbon-bearing albite glasses with varying pressure at 1.5-6 GPa. These NMR results confirm that the densification mechanisms established for fluid-free, polymerized aluminosilicate melts can be applied to the carbon-bearing albite melts at high pressure.

We report the catalyst-free synthesis of monolithic mesoporous nanopolycrystalline diamond from periodic mesoporous carbon at pressures between 15 and 21 GPa and a temperature of 1300 degrees C. We investigated the pressure-dependence of the porosity with 3-dimensional electron tomography. We have observed that surface areas increase from 56 to 90, 138 m(2) g(-1), and porosities increase from 10, 24, to 33% for materials produced at 15, 18, and 21 GPa, respectively. The increased porosity at higher pressure may be due to the earlier onset of the nucleation of diamond at higher pressure. (C) 2018 Published by Elsevier Ltd on behalf of Acta Materialia Inc.

We compute the thermal conductivity and electrical resistivity of solid hcp Fe to pressures and temperatures of Earth's core. We find significant contributions from electron-electron scattering, usually neglected at high temperatures in transition metals. Our calculations show a quasilinear relation between the electrical resistivity and temperature for hcp Fe at extreme high pressures. We obtain thermal and electrical conductivities that are consistent with experiments considering reasonable error. The predicted thermal conductivity is reduced from previous estimates that neglect electron-electron scattering. Our estimated thermal conductivity for the outer core is 77 +/- 10 Wm(-1) K-1 and is consistent with a geodynamo driven by thermal convection.