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At least 487 records · Page 27

Preserving Lagrangian Structure in Nonlinear Model Reduction with Application to Structural Dynamics

Our work proposes a model-reduction methodology that preserves Lagrangian structure and achieves computational efficiency in the presence of high-order nonlinearities and arbitrary parameter dependence. As such, the resulting reduced-order model retains key properties such as energy conservation and symplectic time-evolution maps. We focus on parameterized simple mechanical systems subjected to Rayleigh damping and external forces, and consider an application to nonlinear structural dynamics. To preserve structure, the method first approximates the system's “Lagrangian ingredients''---the Riemannian metric, the potential-energy function, the dissipation function, and the external force---and subsequently derives reduced-order equations of motion by applying the (forced) Euler--Lagrange equation with these quantities. Moreover, from the algebraic perspective, key contributions include two efficient techniques for approximating parameterized reduced matrices while preserving symmetry and positive definiteness: matrix gappy proper orthogonal decomposition and reduced-basis sparsification. Our results for a parameterized truss-structure problem demonstrate the practical importance of preserving Lagrangian structure and illustrate the proposed method's merits: it reduces computation time while maintaining high accuracy and stability, in contrast to existing nonlinear model-reduction techniques that do not preserve structure.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Insight into the structural ambiguity of actinide(IV) oxalate sheet structures: a case for alternate coordination geometries

Plutonium(IV) oxalate hexahydrate (Pu(C 2 O 4 ) 2 ∙ 6H 2 O; PuOx) is an important intermediate in the recovery of plutonium from used nuclear fuel. Its formation via precipitation is well studied, yet its crystal structure remains unknown. Instead, the crystal structure of PuOx is assumed to be isostructural with neptunium(IV) oxalate hexahydrate (Np(C 2 O 4 )­ 2 ∙ 6H 2 O; NpOx) and uranium(IV) oxalate hexahydrate (U(C 2 O 4 )­ 2 ∙ 6H 2 O; UOx) despite the high degree of unresolved disorder that exists when determining water positions in the crystal structures of the latter two compounds. Such assumptions regarding the isostructural behavior of the actinide elements have been used to predict the structure of PuOx for use in a wide range of studies. Herein, we report the first crystal structures for PuOx and Th(C 2 O 4 ) 2 · 6H 2 O (ThOx). This data, along with new characterization of UOx and NpOx, has resulted in the full determination of the structures and resolution of the disorder around the water molecules. Specifically, we identify the coordination of two water molecules with each metal center, which necessitates a change in oxalate coordination mode from axial to equatorial that has not been reported in the literature. Here this work exemplifies the need to revisit previous assumptions regarding fundamental actinide chemistry, which are heavily relied upon within the current nuclear field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural complexity of γ-Al 2 O 3 : The nature of vacancy ordering and the structure of complex antiphase boundaries

The structure of γ-Al2O3 remains largely undetermined despite decades of research. This is due to the high degree of disorder, which poses significant challenges for structural analysis using conventional crystallographic approaches. Herein, we study the structure of γ-Al2O3 with Scanning Transmission Electron Microscopy (STEM) and ab-initio calculations to provide a complete structural description. We show that the microstructure can be understood in terms of two key structural features of nanoscale spinel domains and finite thickness segments termed as complex antiphase boundaries (cAPB) that provide the domain interconnectivity. The spinel domains have a distinctive preference for vacancy ordering, which can be rationalized in terms of a structure with a stacking disorder. Tetragonal P4 1 2 1 2 or monoclinic P2 1 models, all based on the identical motif, can be considered as representative ordered forms. Individual spinel domains are interconnected via cAPBs, which adopt a distinct non-spinel bonding environment of δ-Al 2 O 3 . The most common cAPB consists of a single delta motif with thickness of just 0.6 nm on (001), with the resulting displacement a/4 [101]. Remarkably, the cAPBs are shown to energetically stabilize the spinel domains of γ-Al 2 O 3 explaining their high abundance. We demonstrate how the tetragonal distortions naturally arise in this intricate microstructure and place the proposed model in the context of phase transformations to high temperature transition aluminas.

36 MATERIALS SCIENCE↗

Crystal structures of the high temperature forms of V{sub 8}O{sub 15} and V{sub 9}O{sub 17} and structural trends in the V{sub n}O{sub 2n-1} Magneli series

We report the structure of the metallic high-temperature (ht) form of V{sub 9}O{sub 17}, determined from single crystal X-ray diffraction: space group=P-1 a=5.4219(7) A, b=7.0142(9) A, c=14.5252(19) A, {alpha}=97.0310(10) Degree-Sign , {beta}=90.9900(10) Degree-Sign , {gamma}=108.9630(10) Degree-Sign , V=517.53(12) A{sup 3}, and Z=2. We also report refinement of the structure of metallic ht-V{sub 8}O{sub 15}, space group=P-1, a=5.4315(17) A, b=7.015(2) A, c=13.147(5) A, {alpha}=100.144(4) Degree-Sign , {beta}=95.776(4) Degree-Sign , {gamma}=108.965(3) Degree-Sign , V=459.6(3) A{sup 3}, and Z=2. The structure of metallic V{sub 9}O{sub 17} is interpreted and discussed in the context of the V{sub n}O{sub 2n-1} Magneli phases, yielding trends about how the underlying forces contribute to the metal to insulator transition (MIT). The manner in which structural features of the metallic phases change as a function of n supports previous arguments that there is a turnover in the forces leading to the MIT between n=6 and n=8. - Graphical abstract: Left: The crystal structures of V{sub 8}O{sub 15} and V{sub 9}O{sub 17} shown in context of the crystallographic shear family V{sub n}O{sub 2n-1}. Right: The lattice parameters of V{sub n}O{sub 2n-1} as a function of n. The anamolous trend in b exhibits similar behavior as the metal to insulator (MIT) transition temperature (red). Highlights: Black-Right-Pointing-Pointer Crystal structures of the metallic forms of V{sub 8}O{sub 15} and V{sub 9}O{sub 17}. Black-Right-Pointing-Pointer General trends across the V{sub n}O{sub 2n-1} allow designation of two chain types in all phases. Black-Right-Pointing-Pointer Triclinic b lattice parameter varies anomalously with n, in V{sub n}O{sub 2n-1}. Black-Right-Pointing-Pointer Trend in b matches the metal to insulator transition temperature trend.

36 MATERIALS SCIENCE↗

Structure of β-AgGaO{sub 2}; ternary I–III–VI{sub 2} oxide semiconductor with a wurtzite-derived structure

The structure of the wurtzite-derived β-AgGaO{sub 2} was refined by Rietveld analysis of high-resolution powder diffraction data obtained using synchrotron X-ray radiation. The space group of the crystal is Pna2{sub 1} with lattice parameters of a{sub 0}=5.56175 Å, b{sub 0}=7.14749 Å, and c{sub 0}=5.46875 Å. The deviation of O–Ag–O and M–O–M bond angles from the regular tetrahedral angle of 109.5° was very large at ∼8° and ∼11°, respectively. The electronic structure of β-AgGaO{sub 2} is discussed based on its structure, and the indirect band gap of β-AgGaO{sub 2} was related to significant tetrahedral distortion. Although β-AgGaO{sub 2} decomposes into metallic silver and Ga{sub 2}O{sub 3} at a high temperature in any atmosphere, β-AgGaO{sub 2} is stable up to 690 °C under an O{sub 2} atmosphere. No direct transformation from the wurtzite-derived phase to a delafossite phase occurs in β-AgGaO{sub 2}. - Graphical abstract: Crystal structure of β-AgGaO{sub 2} was refined by Rietveld analysis. AgO{sub 4} and O(Ag,Ga){sub 4} tetrahedra are significantly distorted from ideal tetrahedron. - Highlights: • Orthorhombic β-AgGaO{sub 2} with a wurtzite-derived β-NaFeO{sub 2} structure was synthesized. • Its structure was refined by Rietveld analysis of high-resolution XRD data. • Silver and oxygen tetrahedra are significantly distorted from an ideal tetrahedron. • The extent of this tetrahedral distortion is related to the band gap nature. • β-AgGaO{sub 2} is a metastable phase but is stable up to 690 °C in an O{sub 2} atmosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Syntheses, structures, and ionic conductivities of perovskite-structured lithium–strontium–aluminum/gallium–tantalum-oxides

The ionic conductivities of new perovskite-structured lithium–strontium–aluminum/gallium–tantalum oxides were investigated. Solid solutions of the new perovskite oxides, (Li{sub x}Sr{sub 1−x})(Al{sub (1−x)/2}Ta{sub (1+x)/2})O{sub 3} and (Li{sub x}Sr{sub 1−x})(Ga{sub (1−x)/2}Ta{sub (1+x)/2})O{sub 3}, were synthesized using a ball-milled-assisted solid-state method. The partial substitution of the smaller Ga{sup +3} for Ta{sup +5} resulted in new compositions, the structures of which were determined by neutron diffraction measurements using a cubic perovskite structural model with the Pm−3m space group. Vacancies were introduced into the Sr(Li) sites by the formation of solid solutions with compositions (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3}, where the composition range of 0≤y≤0.20 was examined for x=0.2 and 0.25. The highest conductivity, 1.85×10{sup −3} S cm{sup −1} at 250 °C, was obtained for (Li{sub 0.25}Sr{sub 0.625}☐{sub 0.125})(Ga{sub 0.25}Ta{sub 0.75})O{sub 3} (x=0.25, y=0.125). Enhanced ionic conductivities were achieved by the introduction of vacancies at the A-sites. - Graphical abstract: Novel lithium-conducting oxides with the cubic perovskite structure (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3} provide a specific solid-solution region with various x and y values, exhibiting the highest ionic conductivity (1.85 S cm{sup −1} at 250 °C) for (Li{sub 0.25}Sr{sub 0.625}☐{sub 0.125})(Ga{sub 0.25}Ta{sub 0.75})O{sub 3} (x=0.25, y=0.125 in (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3}). The vacancies (☐) introduced into the A-sites contribute to the enhancement of lithium diffusion in the perovskite structure because of the enlargement of the bottleneck size and suppression of the interaction between lithium and oxygen. - Highlights: • The perovskite-structured novel Li–Sr–Al/Ga–Ta oxides were investigated. • The Ga cation offers a larger bottleneck by increasing the B−O bond length. • The greater conductivity was observed upon Ga-containing perovskite. • The ionic conductivity was improved by the introduction of vacancies into A-site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single crystal magnetic structure and susceptibility of CoSe{sub 2}O{sub 5}

The structure of CoSe{sub 2}O{sub 5} consists of one-dimensional ribbons of edge-sharing CoO{sub 6} octahedra bound together by polyanionic subunits of Se{sub 2}O{sub 5}. Previous work on polycrystalline samples reported a canted antiferromagnetic arrangement of the magnetic moments below the ordering temperature of 8.5 K. Here, we report a single crystal investigation using variable temperature and field magnetic susceptibility and low-temperature neutron diffraction to more precisely characterize the nature of the magnetic ground state of CoSe{sub 2}O{sub 5}. Contrary to previous reports, we find that the single crystal magnetic structure shows no canting of the antiferromagnetic ground state, and in the process have identified several field-induced changes to the magnetization. We discuss these results in the context of the revised magnetic structure and highlight the importance of crystal growth for the accurate characterization of these properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal Structure of Colloidally Prepared Metastable Ag 2 Se Nanocrystals

Structural polymorphism is known for many bulk materials; however, on the nanoscale metastable polymorphs tend to form more readily than in the bulk, and with more structural variety. One such metastable polymorph observed for colloidal Ag 2 Se nanocrystals has traditionally been referred to as the “tetragonal” phase. While there are reports on the chemistry and properties of this metastable polymorph, its crystal structure, and therefore electronic structure, has yet to be determined. We report that an anti-PbCl 2 -like structure type (space group P2 1 /n) more accurately describes the powder X-ray diffraction and X-ray total scattering patterns of colloidal Ag 2 Se nanocrystals prepared by several different methods. Density functional theory (DFT) calculations indicate that this anti-PbCl 2 -like Ag 2 Se polymorph is a dynamically stable, narrow-band-gap semiconductor. Here, the anti-PbCl 2 -like structure of Ag 2 Se is a low-lying metastable polymorph at 5–25 meV/atom above the ground state, depending on the exchange-correlation functional used.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Controlling Amphiphilic Polymer Folding beyond the Primary Structure with Protein-Mimetic Di(Phenylalanine)

While methods for polymer synthesis have proliferated, their functionality pales in comparison to natural biopolymers–strategies are limited for building the intricate network of noncovalent interactions necessary to elicit complex, protein-like functions. Using a bioinspired di(phenylalanine) acrylamide (FF) monomer, we explored the impact of various noncovalent interactions in generating ordered assembled structures. Amphiphilic copolymers were synthesized that exhibit β-sheet-like local structure upon collapsing into single-chain assemblies in aqueous environments. Here, the systematic analysis of a series of amphiphilic copolymers illustrated that the global collapse is primarily driven by hydrophobic forces. Hydrogen-bonding and aromatic interactions stabilize local structure, as β-sheet-like interactions were identified via circular dichroism and thioflavin T fluorescence. Similar analysis of phenylalanine (F) and alanine-phenylalanine acrylamide (AF) copolymers found that distancing the aromatic residue from the polymer backbone is sufficient to induce β-sheet-like local structure akin to the FF copolymers; however, the interactions between AF subunits are less stable than those formed by FF. Further, hydrogen-bond donating hydrophilic monomers disrupt internal structure formed by FF within collapsed assemblies. Collectively, these results illuminate design principles for the facile incorporation of multiple facets of protein-mimetic, higher-order structure within folded synthetic polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure of the Photo-catalytically Active Surface of SrTiO 3

A major goal of energy research is to use visible light to cleave water directly, without an applied voltage, into hydrogen and oxygen. Although SrTiO 3 requires ultraviolet light, after four decades, it is still the "gold standard" for the photo-catalytic splitting of water. It is chemically robust and can carry out both hydrogen and oxygen evolution reactions without an applied bias. While ultrahigh vacuum surface science techniques have provided useful insights, we still know relatively little about the structure of these electrodes in contact with electrolytes under operating conditions. Here, we report the surface structure evolution of a n-SrTiO 3 electrode during water splitting, before and after "training" with an applied positive bias. Operando high-energy X-ray reflectivity measurements demonstrate that training the electrode irreversibly reorders the surface. Scanning electrochemical microscopy at open circuit correlates this training with a 3-fold increase of the activity toward the photo-induced water splitting. A novel first-principles joint density functional theory simulation, constrained to the X-ray data via a generalized penalty function, identifies an anatase-like structure as the more active, trained surface.

36 MATERIALS SCIENCE↗

Physical properties and electronic structure of a new barium titanate suboxide Ba{sub 1+δ}Ti{sub 13−δ}O{sub 12} (δ = 0.11)

The structure, transport, thermodynamic properties, x-ray absorption spectra (XAS), and electronic structure of a new barium titanate suboxide, Ba{sub 1+δ}Ti{sub 13−δ}O{sub 12} (δ = 0.11), are reported. It is a paramagnetic poor metal with hole carriers dominating the transport. Fermi liquid behavior appears at low temperature. The oxidization state of Ti obtained by the XAS is consistent with the metallic Ti{sup 2+} state. Local density approximation band structure calculations reveal the material is near the Van Hove singularity. The pseudogap behavior in the Ti-d band and the strong hybridization between the Ti-d and O-p orbitals reflect the characteristics of the building blocks of the Ti{sub 13} semi-cluster and the TiO{sub 4} quasi-squares, respectively.

36 MATERIALS SCIENCE↗

A first principles study of structural stability, electronic structure and mechanical properties of beryllium alanate BeAlH{sub 5}

Ab initio calculations are performed to investigate the structural stability, electronic structure and mechanical properties of BeAlH{sub 5} for monoclinic crystal structures with two different types of space group namely P2{sub 1} and C{sub 2}/c. Among the considered structures monoclinic (P2{sub 1}) phase is found to be the most stable at ambient condition. The structural phase transition from monoclinic (P2{sub 1}) to monoclinic (C{sub 2}/c) phase is observed in BeAlH{sub 5}. The electronic structure reveals that this compound is insulator. The calculated elastic constants indicate that this material is mechanically stable at ambient condition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structures and magnetic properties of Co-Zr-B magnets studied by first-principles calculations

The structures and magnetic properties of Co-Zr-B alloys near the composition of Co{sub 5}Zr with B at. % ≤6% were studied using adaptive genetic algorithm and first-principles calculations. The energy and magnetic moment contour maps as a function of chemical composition were constructed for the Co-Zr-B magnet alloys through extensive structure searches and calculations. We found that Co-Zr-B system exhibits the same structure motif as the “Co{sub 11}Zr{sub 2}” polymorphs, and such motif plays a key role in achieving strong magnetic anisotropy. Boron atoms were found to be able to substitute cobalt atoms or occupy the “interruption” sites. First-principles calculations showed that the magnetocrystalline anisotropy energies of the boron-doped alloys are close to that of the high-temperature rhombohedral Co{sub 5}Zr phase and larger than that of the low-temperature Co{sub 5.25}Zr phase. Our calculations provide useful guidelines for further experimental optimization of the magnetic performances of these alloys.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Characterization of electronic structure of periodically strained graphene

We induced periodic biaxial tensile strain in polycrystalline graphene by wrapping it over a substrate with repeating pillar-like structures with a periodicity of 600 nm. Using Raman spectroscopy, we determined to have introduced biaxial strains in graphene in the range of 0.4% to 0.7%. Its band structure was characterized using photoemission from valance bands, shifts in the secondary electron emission, and x-ray absorption from the carbon 1s levels to the unoccupied graphene conduction bands. It was observed that relative to unstrained graphene, strained graphene had a higher work function and higher density of states in the valence and conduction bands. Furthermore, we measured the conductivity of the strained and unstrained graphene in response to a gate voltage and correlated the changes in their behavior to the changes in the electronic structure. From these sets of data, we propose a simple band diagram representing graphene with periodic biaxial strain.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗