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At least 1,729 records · Page 96

Relationship between crystal structure and thermo-mechanical properties of kaolinite clay: Beyond standard density functional theory

In this study, the structural, mechanical and thermodynamic properties of 1 : 1 layered dioctahedral kaolinite clay, with ideal Al 2 Si 2 O 5 (OH) 4 stoichiometry, were investigated using density functional theory corrected for dispersion interactions (DFT-D2). The bulk moduli of 56.2 and 56.0 GPa predicted at 298 K using the Vinet and Birch–Murnaghan equations of state, respectively, are in good agreement with the recent experimental value of 59.7 GPa reported for well-crystallized samples. The isobaric heat capacity computed for uniaxial deformation of kaolinite along the stacking direction reproduces calorimetric data within 0.7–3.0% from room temperature up to its thermal stability limit.

36 MATERIALS SCIENCE↗

Electronic and protonic conduction in LaFeO 3

Perovskite-type LaFeO3 has promising applications as a negative-electrode material for Ni/metal-hydride batteries. To further improve electrode performance, a thorough understanding of its charge-transport mechanisms is required. We use hybrid density functional theory to investigate the structural and electronic properties of bulk LaFeO3, as well as the effect of point defects and polarons on charge transport. Electronic charge localizes in the form of small hole and electron polarons; this self-trapping occurs in the bulk and also in the vicinity of point defects and impurities. We find that oxygen vacancies act as deep donors, while Fe and La vacancies are acceptors with the induced holes trapped as small polarons. Hydrogen interstitials and Ge and Ti impurities, on the other hand, act as donors that can trap small electron polarons. Hydrogen binds strongly to the La and Fe vacancies and hence these defects are detrimental to protonic conduction. We also elucidate how doping with Sr enhances the electrode performance of LaFeO3:Sr impurities substituting on La sites act as acceptors and enable electronic conductivity through hole polarons, with a hopping barrier of 0.39 eV. In addition, Sr impurities suppress the formation of cation vacancies, thereby enhancing proton conductivity.

Zhu, Zhen↗

Role of disorder in limiting the true multi-electron redox in ε-LiVOPO 4

Recent advances in materials syntheses have enabled ε-LiVOPO 4 to deliver capacities approaching, and in some cases exceeding the theoretical value of 305 mA h g –1 for 2Li intercalation, despite its poor electronic and ionic conductivity. However, not all of the capacity corresponds to the true electrochemical intercalation/deintercalation reactions as evidenced upon systematic tracking of V valence through combined operando and rate-dependent ex situ X-ray absorption study presented herein. Structural disorder and defects introduced in the material by high-energy ball milling impede kinetics of the high-voltage V 5+ /V 4+ redox more severely than the low-voltage V 4+ /V 3+ redox, promoting significant side reaction contributions in the high-voltage region, irrespective of cycling conditions. In conclusion, the present work emphasizes the need for nanoengineering of active materials without compromising their bulk structural integrity in order to fully utilize high-energy density of multi-electron cathode materials.

25 ENERGY STORAGE↗

Molecular origins of bulk viscosity in liquid water

The shear viscous response of water is closely associated with changes in network connectivity on the sub ps timescale. The bulk viscous response is shown here to be associated with local density fluctuations and rotational motion around 1–3 ps.

Yahya, Ahmad↗

Understanding helicon plasmas

This paper presents a comprehensive overview of work on the helicon plasmas and also discusses various aspects of RF power deposition in such plasmas. Some of the work presented here is a review of earlier work on theoretical [A. Ganguli et al., Phys. Plasmas 14, 113503 (2007)] and experimental [A. Ganguli et al., Plasma Sources Sci. Technol. 20(1), 015021 (2011)] investigations on helicon plasmas in a conducting cylindrical waveguide for m = -1 mode. This work also presents an approach to investigate the mechanisms by which the helicon and associated Trivelpiece-Gould (TG) waves are responsible for RF power deposition in Helicon discharges. Experiment design adopts the recent theory of damping and absorption of Helicon modes in conducting waveguides [A. Ganguli et al., Phys. Plasmas 14, 113503 (2007)]. The effort has also been made to detect the warm electrons, which are necessary for ionization, because Helicon discharges are of high density, low T{sub e} discharges and the tail of the bulk electron population may not have sufficient high-energy electrons. Experimental set up also comprises of the mirror magnetic field. Measurements using RF compensated Langmuir probes [A. Ganguli et al., Plasma Sources Sci. Technol. 17, 015003 (2008)], B-dot probe and computations based on the theory shows that the warm electrons at low pressure (0.2-0.3 mTorr) Helicon discharges, are because of the Landau damping of TG waves. In collisional environment, at a pressure Almost-Equal-To 10 mTorr, these high-energy electrons are due to the acceleration of bulk electrons from the neighboring regions across steep potential gradients possibly by the formation of double layers.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Time-, frequency-, and wavevector-resolved x-ray diffraction from single molecules

Using a quantum electrodynamic framework, we calculate the off-resonant scattering of a broadband X-ray pulse from a sample initially prepared in an arbitrary superposition of electronic states. The signal consists of single-particle (incoherent) and two-particle (coherent) contributions that carry different particle form factors that involve different material transitions. Single-molecule experiments involving incoherent scattering are more influenced by inelastic processes compared to bulk measurements. The conditions under which the technique directly measures charge densities (and can be considered as diffraction) as opposed to correlation functions of the charge-density are specified. The results are illustrated with time- and wavevector-resolved signals from a single amino acid molecule (cysteine) following an impulsive excitation by a stimulated X-ray Raman process resonant with the sulfur K-edge. Our theory and simulations can guide future experimental studies on the structures of nano-particles and proteins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ab-initio study of oxygen defects in pure ThO{sub 2}

First principles calculations using projector augmented wave potentials and generalized gradient approximations predicts the structural relaxations due to neutral and positively charged oxygen defects (+1 and +2) in bulk thoria leads to symmetric distortion around the vacancy site. Electronic Density of states (DOS) analysis shows presence of defects states mainly contributed by Th d and f states near the conduction band minima for the double positively charged oxygen vacancy which is having lowest energy of formation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Curvature and bow of bulk GaN substrates

We investigate the bow of free standing (0001) oriented hydride vapor phase epitaxy grown GaN substrates and demonstrate that their curvature is consistent with a compressive to tensile stress gradient (bottom to top) present in the substrates. The origin of the stress gradient and the curvature is attributed to the correlated inclination of edge threading dislocation (TD) lines away from the [0001] direction. A model is proposed and a relation is derived for bulk GaN substrate curvature dependence on the inclination angle and the density of TDs. The model is used to analyze the curvature for commercially available GaN substrates as determined by high resolution x-ray diffraction. The results show a close correlation between the experimentally determined parameters and those predicted from theoretical model.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Ecosystem consequences of a nitrogen-fixing proto-organelle

Microscale symbioses can be critical to ecosystem functions, but the mechanisms of these interactions in nature are often cryptic. Here, we use a combination of stable isotope imaging and tracing to reveal carbon (C) and nitrogen (N) exchanges among three symbiotic primary producers that fuel a salmon-bearing river food web. Bulk isotope analysis, nanoSIMS (secondary ion mass spectrometry) isotope imaging, and density centrifugation for quantitative stable isotope probing enabled quantification of organism-specific C- and N-fixation rates from the subcellular scale to the ecosystem. After winters with riverbed-scouring floods, the macroalga Cladophora glomerata uses nutrients in spring runoff to grow streamers up to 10 m long. During summer flow recession, riverine N concentrations wane and Cladophora becomes densely epiphytized by three species of Epithemia, diatoms with N-fixing endosymbionts (proto-organelles) descended from a free-living Crocosphaera cyanobacterium. Over summertime epiphyte succession on Cladophora, N-fixation rates increased as Epithemia spp. became dominant, Cladophora C-fixation declined to near zero, and Epithemia C-fixation increased. Carbon transfer to caddisflies grazing on Cladophora with high densities of Epithemia was 10-fold higher than C transfer to caddisflies grazing Cladophora with low Epithemia loads. In response to demand for N, Epithemia allocates high levels of newly fixed C to its endosymbiont. Consequently, these endosymbionts have the highest rates of C and N accumulation of any taxon in this tripartite symbiosis during the biologically productive season and can produce one of the highest areal rates of N-fixation reported in any river ecosystem.

Marks, Jane C. [Northern Arizona Univ., Flagstaff,↗

Metal-insulator transition in quasi-one-dimensional HfTe 3 in the few-chain limit

The quasi-one-dimensional linear chain compound HfTe 3 is experimentally and theoretically explored in the few- to single-chain limit. Confining the material within the hollow core of carbon nanotubes allows isolation of the chains and prevents the rapid oxidation which plagues even bulk HfTe 3 . High-resolution transmission electron microscopy coupled with density functional theory calculations reveals that, once the triple-chain limit is reached, the normally parallel chains spiral about each other, and simultaneously a short-wavelength trigonal anti-prismatic rocking distortion occurs that opens a significant energy gap. This ends in a size-driven metal-insulator transition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Bulk Dirac Points in Distorted Spinels

Here, we report on a Dirac-like Fermi surface in three-dimensional bulk materials in a distorted spinel structure on the basis of density functional theory as well as tight-binding theory. The four examples we provide in this Letter are BiZnSiO 4 , BiCaSiO 4 , BiAlInO 4 , and BiMgSiO 4 . A necessary characteristic of these structures is that they contain a Bi lattice which forms a hierarchy of chainlike substructures, with consequences for both fundamental understanding and materials design.

36 MATERIALS SCIENCE↗

Low-energy surface states in the normal state of α - PdBi 2 superconductor

Topological superconductors as characterized by Majorana surface states have been actively searched for their significance in fundamental science and technological implication. The large spin-orbit coupling in Bi-Pd binaries has stimulated extensive investigations on the topological surface states in these superconducting compounds. Here we report a study of normal-state electronic structure in a centrosymmetric α-PdBi 2 within density functional theory calculations. By investigating the electronic structure from the bulk to slab geometries in this system, we predict for the first time that α-PdBi 2 can host orbital-dependent and asymmetric Rashba surface states near the Fermi energy. This study suggests that α-PdBi 2 will be a good candidate to explore the relationship between superconductivity and topology in condensed matter physics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Solid-state batteries: The critical role of mechanics

Solid-state batteries with lithium metal anodes have the potential for higher energy density, longer lifetime, wider operating temperature, and increased safety. Although the bulk of the research has focused on improving transport kinetics and electrochemical stability of the materials and interfaces, there are also critical challenges that require investigation of the mechanics of materials. In batteries with solid-solid interfaces, mechanical contacts, and the development of stresses during operation of the solid-state batteries, become as critical as the electrochemical stability to keep steady charge transfer at these interfaces. In conclusion, this review will focus on stress and strain that result from normal and extended battery cycling and the associated mechanisms for stress relief, some of which lead to failure of these batteries.

25 ENERGY STORAGE↗

Materials Data on Fe3(O2F)2 (SG:1) by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗

Materials Data on FeClO (SG:59) by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗

Materials Data on CrO3 (SG:40) by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗

Materials Data on Ba2MnReO6 (SG:225) by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗

Materials Data on Ba2ReNiO6 (SG:225) by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗