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.

We studied the low-pressure (0-10 GPa) phase diagram of crystalline benzene using quantum Monte Carlo and density functional theory (DFT) methods. We performed diffusion quantum Monte Carlo (DMC) calculations to obtain accurate static phase diagrams as benchmarks for modern van der Waals density functionals. Using density functional perturbation theory, we computed the phonon contributions to the free energies. Our DFT enthalpy-pressure phase diagrams indicate that the Pbca and P2(1)/c structures are the most stable phases within the studied pressure range. The DMC Gibbs free-energy calculations predict that the room temperature Pbca to P2(1)/c phase transition occurs at 2.1(1) GPa. This prediction is consistent with available experimental results at room temperature. Our DMC calculations give 50.6 +/- 0.5 kJ/mol for crystalline benzene lattice energy. Published by AIP Publishing.

The potassium (K) and water (H2O) cycles in subduction zones are predominately controlled by the stability of K-and H2O-bearing minerals, such as K-mica, lawsonite, and dense hydrous magnesium silicates (DHMS). K-micas (muscovite or phlogopite) are the principal H2O and K hosts in subduction zones and Earth's upper mantle and play a significant role in the deep H2O and K cycles. The Mg-10 angstrom phase, normally appearing in hydrated peridotite in high-pressure experiments, has been considered as an important water-carrier in subducted hydrated peridotite. In this study, we found a K-bearing Al-10 angstrom phase in the MORB+H2O system (hydrated basalt) at high pressures according to X-ray diffraction and stoichiometry. We experimentally constrained its stability field at high pressure. By considering newly and previously documented compositions of the 10 angstrom phase and micas, we confirmed a continuous solid solution or mixed layering between the 10 angstrom phase and K-mica at the interlayer site, suggesting that the K cycle and the H2O cycle in subduction zones are coupled. From the discussion of the effect of f(H2O) on stability of the Al-10 angstrom phase, we conclude that a cold subduction zone can host and carry more bulk H2O and K into Earth's deep mantle than a hot one. This work expands the stability regions of the 10 angstrom phase from the ultramafic system (Mg-10 angstrom phase) to the mafic system (Al-10 angstrom phase), and emphasizes the significance of the 10 angstrom phase for the deep H2O and K cycle in subduction zone.