The thermal conductivity of the Earth's core can be estimated from its electrical resistivity via the Wiedemann-Franz law. However, previously reported resistivity values are rather scattered, mainly due to the lack of knowledge with regard to resistivity saturation (violations of the Bloch-Gruneisen law and the Matthiessen's rule). Here we conducted high-pressure experiments and first-principles calculations in order to clarify the relationship between the resistivity saturation and the impurity resistivity of substitutional silicon in hexagonal-close-packed (hcp) iron. We measured the electrical resistivity of Fe-Si alloys (iron with 1, 2, 4, 6.5, and 9 wt.% silicon) using four-terminal method in a diamond anvil cell up to 90 GPa at 300 K. We also computed the electronic band structure of substitutionally disordered hcp Fe-Si and Fe-Nialloy systems by means of Korringa-Kohn-Rostoker method with coherent potential approximation (KKR-CPA). The electrical resistivity was then calculated from the Kubo-Greenwood formula. These experimental and theoretical results show excellent agreement with each other, and the first principles results show the saturation behavior at high silicon concentration. We further calculated the resistivity of Fe-Ni-Si ternary alloys and found the violation of the Matthiessen's rule as a consequence of the resistivity saturation. Such resistivity saturation has important implications for core dynamics. The saturation effect places the upper limit of the resistivity, resulting in that the total resistivity value has almost no temperature dependence. As a consequence, the core thermal conductivity has a lower bound and exhibits a linear temperature dependence. We predict the electrical resistivity at the top of the Earth's core to be 1.12 x 10(-6) Omega m, which corresponds to the thermal conductivity of 87.1 Wpm/K. Such high thermal conductivity suggests high isentropic heat flow, leading to young inner core age (<0.85 Gyr old) and high initial core temperature. It also strongly suppresses thermal convection in the core, which results in no convective motion in inner core and possibly thermally stratified layer in the outer core. (C) 2016 Elsevier B.V. All rights reserved.

Phase-pure samples of a metastable allotrope of silicon, Si-III or BC8, were synthesized by direct elemental transformation at 14 GPa and similar to 900 K and also at significantly reduced pressure in the Na-Si system at 9.5 GPa by quenching from high temperatures similar to 1000 K. Pure sintered polycrystalline ingots with dimensions ranging from 0.5 to 2 mm can be easily recovered at ambient conditions. The chemical route also allowed us to decrease the synthetic pressures to as low as 7 GPa, while pressures required for direct phase transition in elemental silicon are significantly higher. In situ control of the synthetic protocol, using synchrotron radiation, allowed us to observe the underlying mechanism of chemical interactions and phase transformations in the Na-Si system. Detailed characterization of Si-III using X-ray diffraction, Raman spectroscopy, Si-29 NMR spectroscopy, and transmission electron microscopy are discussed. These large-volume syntheses at significantly reduced pressures extend the range of possible future bulk characterization methods and applications.

Mn is used as a dopant to improve the electromechanical properties of perovskite oxides. We investigate the effects of Mn defects and associated vacancies on the electronic and atomic properties of BaTiO3. Using density functional theory (DFT) and DFT + U we investigate the equilibrium geometry and electronic properties of the Mn ion on A or B sites and with compensating oxygen vacancies. We study the change in the oxidation state of Mn in response to local environment changes, such as the presence of oxygen vacancies.

Minerals recovered from the deep mantle provide a rare glimpse into deep Earth processes. We report the first discovery of ferric iron-rich majoritic garnet found as inclusions in a host garnet within an eclogite xenolith originating in the deep mantle. The composition of the host garnet indicates an ultrahigh-pressure metamorphic origin, probably at a depth of similar to 200 km. More importantly, the ferric iron-rich majoritic garnet inclusions show a much deeper origin, at least at a depth of 380 km. The majoritic nature of the inclusions is confirmed by mineral chemistry, x-ray diffraction, and Raman spectroscopy, and their depth of origin is constrained by a new experimental calibration. The unique relationship between the majoritic inclusions and their host garnet has important implications for mantle dynamics within the deep asthenosphere. The high ferric iron content of the inclusions provides insights into the oxidation state of the deep upper mantle.

We report an accurate study of interactions between benzene molecules using variational quantum Monte Carlo (VMC) and diffusion quantum Monte Carlo (DMC) methods. We compare these results with density functional theory using different van derWaals functionals. In our quantum Monte Carlo (QMC) calculations, we use accurate correlated trial wave functions including three-body Jastrow factors and backflow transformations. We consider two benzene molecules in the parallel displaced geometry, and find that by highly optimizing the wave function and introducing more dynamical correlation into the wave function, we compute the weak chemical binding energy between aromatic rings accurately. We find optimal VMC and DMC binding energies of -2.3(4) and -2.7(3) kcal/mol, respectively. The best estimate of the coupled-cluster theory through perturbative triplets/complete basis set limit is -2.65(2) kcal/mol [Miliordos et al., J. Phys. Chem. A 118, 7568 (2014)]. Our results indicate that QMC methods give chemical accuracy for weakly bound van derWaals molecular interactions, comparable to results from the best quantum chemistry methods. (C) 2015 AIP Publishing LLC.

Silicon is essential for today's electronics because of its ability to show various electronic behaviors that are relevant to numerous fields of cutting-edge applications. It is not a pollutant and, therefore, an ideal candidate to replace the actual materials in photovoltaics, such as compounds based on the arsenic and heavy metals. However, conventional diamond-like Si is an indirect gap semiconductor and cannot absorb solar photons directly. This justifies intensive theoretical and experimental research for the direct-bandgap forms of silicon. Our recent high-pressure studies of the chemical interaction and phase transformations in the Na-Si system, revealed a number of interesting routes to new and known silicon compounds and allotropes. The pressure-temperature range of their formation is suitable for large-volume synthesis and future industrial scaling. The variety of properties observed (e.g. quasi-direct bandgap of open-framework allotrope Si-24) allows us to suggest future applications. (C) 2016 The Authors. Published by Elsevier Ltd.

Recent satellite inferences of hydrous sulfates as recurrent minerals on the surface of icy planetary bodies link with the potential mineral composition of their interior. Blodite, a mixed Mg-Na sulfate, is here taken as representative mineral of icy satellites surface to investigate its crystal structure and stability at conditions of the interior of icy bodies. To this aim we performed in situ synchrotron angle-dispersive X-ray powder diffraction experiments on natural blodite at pressures up to similar to 10.4 GPa and temperatures from similar to 118.8 K to similar to 490.0 K using diamond anvil cell technique to investigate the compression behavior and establish a low-to-high temperature equation of state that can be used as reference when modeling the interior of sulfate-rich icy satellites such as Ganymede.

The lithium-carbon binary system possesses a broad range of chemical compounds, which exhibit fascinating chemical bonding characteristics, which give rise to diverse and technologically important properties. While lithium carbides with various compositions have been studied or suggested previously, the crystal structures of these compounds are far from well understood. In this work, we present the first comprehensive survey of all ground state (GS) structures of lithium carbides over a broad range of thermodynamic conditions, using ab initio density functional theory (DFT) crystal structure searching methods. Thorough searches were performed for 29 stoichiometries ranging from Li12C to LiC12 at 0 and 40 GPa. Based on formation enthalpies from optimized van der Waals density functional calculations, three thermodynamically stable phases (Li4C3, Li2C2, and LiC12) were identified at 0 GPa, and seven thermodynamically stable phases (Li8C, Li6C, Li4C, Li8C3, Li2C, Li3C4, and Li2C3) were predicted at 40 GPa. A rich diversity of carbon bonding, including monomers, dimers, trimers, nanoribbons, sheets, and frameworks, was found within these structures, and the dimensionality of carbon connectivity existing within each phase increases with increasing carbon concentration. We find that the well-known composition LiC6 is actually a metastable one. We also find a unique coexistence of carbon monomers and dimers within the predicted thermodynamically stable phase Li8C3, and different widths of carbon nanoribbons coexist in a metastable phase of Li2C2 (Imm2). Interesting mixed sp(2)-sp(3) carbon frameworks are predicted in metastable phases with composition LiC6.

Periodic mesoporous hexagonal boron nitride was investigated as a precursor for nanoscale forms of cubic boron nitride. Cubic boron nitride (c-BN) nanocrystals were obtained at a pressure of 14 GPa and a temperature of 1300 degrees C. The synthesized nanocrystals have diameters of similar to 50 nm and are solutionprocessible. Mesoporous c-BN formed at a pressure of 10 GPa and 1000 degrees C. The mesoporous c-BN has a pore size distribution centered around 3 nm and a surface area of 122 m(2)/g as determined by electron tomography. At pressures of 8 and 6 GPa near monodisperse h-BN nanodiscs with diameters of 0.5-1 mm and 0.2-0.5 mm were formed, respectively. The discs formed colloidal solutions in acetone. The hydrodynamic radius of the discs matched the radii determined by dynamic light scattering indicating absence of nanodisc aggregation in solution.

The Group 14 element silicon possesses a complex free-energy landscape with many (local) minima, allowing for the formation of a variety of unusual structures, some of which may be stabilized at ambient conditions. Such exotic silicon allotropes represent a significant opportunity to address the ever-increasing demand for novel materials with tailored functionality since these exotic forms are expected to exhibit superlative properties including optimized band gaps for solar power conversion. The application of pressure is a well-recognized and uniquely powerful method to access exotic states of silicon since it promotes large changes to atomic bonding. Conventional high-pressure syntheses, however, lack the capability to access many of these local minima and only four forms of exotic silicon allotropes have been recovered over the last 50 years. However, more recently, significant advances in high pressure methodologies and the use of novel precursor materials have yielded at least three more recoverable exotic Si structures. This review aims to give an overview of these innovative methods of high-pressure application and precursor selection and the recent discoveries of new Si allotropes. The background context of the conventional pressure methods and multitude of predicted new phases are also provided. This review also offers a perspective for possible access to many further exotic functional allotropes not only of silicon but also of other materials, in a technologically feasible manner. Published by AIP Publishing.