Magnetic and structural properties of Co films deposited onto obliquely sputtered Pt underlayers

Co films deposited on obliquely sputtered Pt underlayers of 100 Angstrom or greater have produced coercivities in excess of 800 Oe, and anisotropy fields over 950 Oe. The coercivity and anisotropy field increase with Pt deposition angle and thickness. A Pt capping layer has a detrimental effect on properties but a Cu capping layer does not. Films with an obliquely deposited underlayer exhibit reduced density and increased interface roughness compared to normally deposited films. Normally deposited Pt underlayers display a (111) texture, while those deposited obliquely show an increasingly random texture with Pt thickness and deposition angle. The trilayers fabricated in this study are presented as candidates for use in giant magnetoresistance sensors. (C) 2002 American Institute of Physics.

Relative energetics and structural properties of zirconia using a self-consistent tight-binding model

We describe an empirical, self-consistent, orthogonal tight-binding model for zirconia, which allows for the polarizability of the anions at dipole and quadrupole levels and for crystal field splitting of the cation d orbitals, This is achieved by mixing the orbitals of different symmetry on a site with coupling coefficients driven by the Coulomb potentials up to octapole level. The additional forces on atoms due to the self-consistency and polarizabilities are exactly obtained by straightforward electrostatics, by analogy with the Hellmann-Feynman theorem as applied in first-principles calculations. The model correctly orders the zero temperature energies of all zirconia polymorphs. The Zr-O matrix elements of the Hamiltonian, which measure covalency, make a greater contribution than the polarizability to the energy differences between phases. Results for elastic constants of the cubic and tetragonal phases and phonon frequencies of the cubic phase are also presented and compared with some experimental data and first-principles calculations. We suggest that the model will be useful for studying finite temperature effects by means of molecular dynamics.

Metabolic and structural properties of human obestatin {1-23} and two fragment peptides

Obestatin is a peptide produced in the oxyntic mucosa of the stomach and co-localizes with ghrelin on the periphery of pancreatic islets. Several studies demonstrate that obestatin reduces food and water intake, decreases body weight gain, inhibits gastrointestinal motility, and modulates glucose-induced insulin secretion. In this study we evaluated the acute metabolic effects of human obestatin {1-23} and fragment peptides {1-10} or {11-23} in high-fat fed mice, and then investigated their solution structure by NMR spectroscopy and molecular modelling. Obestatins {1-23} and {11-23} significantly reduced food intake (86% and 90% respectively) and lowered glucose responses to feeding, whilst leaving insulin responses unchanged. No metabolic changes could be detected following the administration of obestatin (1-10). In aqueous solution none of the obestatin peptides possessed secondary structural features. However, in a 2,2,2-trifluoroethanol (TFE-d(3))-H2O solvent mixture, the structure of obestatin {1-23} was characterized by an a-helix followed by a single turn helix conformation between residues Pro(4) and Gln(15) and His(19) and Ala(22) respectively. Obestatin {1-10} showed no structural components whereas {11-23} contained an a-helix between residues Val(14) and Ser(20) in a mixed solvent. These studies are the first to elucidate the structure of human obestatin and provide clear evidence that the observed a-helical structures are critical for in vivo activity. Future structure/function studies may facilitate the design of novel therapeutic agents based on the obestatin peptide structure. (C) 2010 Elsevier Inc. All rights reserved.

Oxygen vacancy formation in CeO2 and Ce1-xZrxO2 solid solutions:electron localization, electrostatic potential and structural relaxation

Ceria (CeO2) and ceria-based composite materials, especially Ce1-xZrxO2 solid solutions, possess a wide range of applications in many important catalytic processes, such as three-way catalysts, owing to their excellent oxygen storage capacity (OSC) through the oxygen vacancy formation and refilling. Much of this activity has focused on the understanding of the electronic and structural properties of defective CeO2 with and without doping, and comprehending the determining factor for oxygen vacancy formation and the rule to tune the formation energy by doping has constituted a central issue in material chemistry related to ceria. However, the calculation on electronic structures and the corresponding relaxation patterns in defective CeO2-x oxides remains at present a challenge in the DFT framework. A pragmatic approach based on density functional theory with the inclusion of on-site Coulomb correction, i.e. the so-called DFT + U technique, has been extensively applied in the majority of recent theoretical investigations. Firstly, we review briefly the latest electronic structure calculations of defective CeO2(111), focusing on the phenomenon of multiple configurations of the localized 4f electrons, as well as the discussions of its formation mechanism and the catalytic role in activating the O-2 molecule. Secondly, aiming at shedding light on the doping effect on tuning the oxygen vacancy formation in ceria-based solid solutions, we summarize the recent theoretical results of Ce1-xZrxO2 solid solutions in terms of the effect of dopant concentrations and crystal phases. A general model on O vacancy formation is also discussed; it consists of electrostatic and structural relaxation terms, and the vital role of the later is emphasized. Particularly, we discuss the crucial role of the localized structural relaxation patterns in determining the superb oxygen storage capacity in kappa-phase Ce1-xZr1-xO2. Thirdly, we briefly discuss some interesting findings for the oxygen vacancy formation in pure ceria nanoparticles (NPs) uncovered by DFT calculations and compare those with the bulk or extended surfaces of ceria as well as different particle sizes, emphasizing the role of the electrostatic field in determining the O vacancy formation.

Tuning the Electronic and Chemical Properties of Monolayer MoS2Adsorbed on Transition Metal Substrates

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First-Principles Study of the Electronic and Magnetic Properties of Defects in Carbon Nanostructures

Understanding the magnetic properties of graphenic nanostructures is instrumental in future spintronics applications. These magnetic properties are known to depend crucially on the presence of defects. Here we review our recent theoretical studies using density functional calculations on two types of defects in carbon nanostructures: Substitutional doping with transition metals, and sp$^3$-type defects created by covalent functionalization with organic and inorganic molecules. We focus on such defects because they can be used to create and control magnetism in graphene-based materials. Our main results are summarized as follows: i)Substitutional metal impurities are fully understood using a model based on the hybridization between the $d$ states of the metal atom and the defect levels associated with an unreconstructed D$_{3h}$ carbon vacancy. We identify three different regimes, associated with the occupation of distinct hybridization levels, which determine the magnetic properties obtained with this type of doping; ii) A spin moment of 1.0 $\mu_B$ is always induced by chemical functionalization when a molecule chemisorbs on a graphene layer via a single C-C (or other weakly polar) covalent bond. The magnetic coupling between adsorbates shows a key dependence on the sublattice adsorption site. This effect is similar to that of H adsorption, however, with universal character; iii) The spin moment of substitutional metal impurities can be controlled using strain. In particular, we show that although Ni substitutionals are non-magnetic in flat and unstrained graphene, the magnetism of these defects can be activated by applying either uniaxial strain or curvature to the graphene layer. All these results provide key information about formation and control of defect-induced magnetism in graphene and related materials.

Electronic structures and bonding properties of chlorine-treated nitrogenated carbon nanotubes: X-ray absorption and scanning photoelectron microscopy studies

The electronic and bonding properties of nitrogenated carbon nanotubes (N-CNTs) exposed to chlorine plasma were investigated using C and N K-edge x-ray absorption near-edge structure (XANES) and scanning photoelectron microscopy (SPEM). The C and N K-edge XANES spectra of chlorine-treated N-CNTs consistently reveal the formation of pyridinelike N-CNTs by the observation of 1s ->pi(*)(e(2u)) antibonding and 1s ->pi(*)(b(2g)) bonding states. The valence-band photoemission spectra obtained from SPEM images indicate that chlorination of the nanotubes enhances the C-N bonding. First-principles calculations of the partial densities of states in conjunction with C K-edge XANES data identify the presence of C-Cl bonding in chlorine treated N-CNTs. (C) 2007 American Institute of Physics.

Understanding catalytic reactions over zeolites: A density functional theory study of selective catalytic reduction of NOX by NH3 over Cu-SAPO-34

Metal exchanged CHA-type (SAPO-34 and SSZ-13) zeolites are promising catalysts for selective catalytic reduction (SCR) of NOx by NH3. However, the understanding of the process at the molecular level is still limited, which hinders the identification of its mechanism and the design of more efficient zeolite catalysts. In this work, modelling the reaction over Cu-SAPO-34, a periodic density functional theory (DFT) study of NH3-SCR was performed using hybrid functional with the consideration of van der Waals (vdW) interactions. A mechanism with a low N–N coupling barrier is proposed to account for the activation of NO. The redox cycle of Cu2+ and Cu+, which is crucial for the SCR process, is identified with detailed analyses. Besides, the decomposition of NH2NO is shown to readily occur on the Brønsted acid site by a hydrogen push-pull mechanism, confirming the collective efforts of Brønsted acid and Lewis acid (Cu2+) sites. The special electronic and structural properties of Cu-SAPO-34 are demonstrated to play an essential role the reaction, which may have a general implication on the understanding of zeolite catalysis.

Electronic, structural, and reactive properties of ultrathin aluminum oxide films on Pt(111)

Low-energy electron diffraction, X-ray photoelectron spectroscopy, high-resolution electron energy-loss spectroscopy, scanning tunneling microscopy, and temperature-programmed reaction spectrometry results are reported for the structural and reactive behavior of alumina films grown on Pt(111) as a function of thickness and oxidation temperature. Submonolayer Al films undergo compete oxidation at 300 K, annealing at 1100 K resulting in formation of somewhat distorted crystalline gamma-alumina, Thicker deposits require 800 K oxidation to produce Al2O3, and these too undergo crystallization at 800 K, yielding islands of apparently undistorted gamma-alumina on the Pt(111) surface. Oxidation of a p(2 x 2) Pt3Al surface alloy occurs only at>800 K, resulting in Al extraction, These alumina films on Pt(lll) markedly increase the coverage of adsorbed SO4 resulting from SO2 chemisorption onto oxygen-precovered surfaces. This results in enhanced propane uptake and subsequent reactivity relative to SO4/Pt(111). A bifunctional mechanism is proposed to account for our observations, and the relevance of these to an understanding of the corresponding dispersed systems is discussed.

Structural and magnetic properties of sol-gel Co2xNi0.5-xZn0.5-xFe2O4 thin films

Nanocrystalline Co2xNi0.5-xZn0.5-xFe2O4 (x = 0-0.5) thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology as well as magnetic and microwave absorption properties of the films calcined at 1073 K were studied using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. All films were uniform with out microcracks . The Co content in the Co-Ni-Zn films resulted in a grain size ranging from 15 to 32 nm while it ranged from 33 to 49 nm in the corresponding powders. Saturation and remnant magnetization increased with increase in grain size, while coercivity demonstrated a drop due to multidomain behavior of crystallites for a given value of x. Saturation magnetization increased and remnant magnetization had a maximum as a function of grain size in dependent of x. In turn, coercivity increased with x independent of grain size. Complex permittivity of the Co-Ni-Zn ferrite films was measured in the frequency range 2-15 GHz. The highest hysteretic heating rate in the temperature range 315-355 K was observed in CoFe2O4. The maximum absorption band shifted from 13 to 11GHz as cobalt content increased from x = 0.1 to 0.2.

Epitaxial strain and electric boundary condition effects on the structural and ferroelectric properties of BiFeO3 films

The influence of both compressive and tensile epitaxial strain along with the electrical boundary conditions on the ferroelastic and ferroelectric domain patterns of bismuth ferrite films was studied. BiFeO3 films were grown on SrTiO3(001), DyScO3(110), GdScO3(110), and SmScO3(110) substrates to investigate the effect of room temperature in-plane strain ranging from -1.4% to +0.75%. Piezoresponse force microscopy, transmission electron microscopy, x-ray diffraction measurements, and ferroelectric polarization measurements were performed to study the properties of the films. We show that BiFeO3 films with and without SrRuO3 bottom electrode have different growth mechanisms and that in both cases reduction of the domain variants is possible. Without SrRuO3, stripe domains with reduced variants are formed on all rare earth scandate substrates because of their monoclinic symmetry. In addition, tensile strained films exhibit a rotation of the unit cell with increasing film thickness. On the other side, the presence of SrRuO3 promotes step flow growth of BiFeO3. In case of vicinal SrTiO3 and DyScO3 substrates with high quality SrRuO3 bottom electrode and a low miscut angle of approximate to 0.15 degrees we observed suppression of the formation of certain domain variants. The quite large in-plane misfit of SrRuO3 with GdScO3 and SmScO3 prevents the growth of high quality SrRuO3 films and subsequent domain variants reduction in BiFeO3 on these substrates, when SrRuO3 is used as a bottom electrode.

Effect of quantization of vibrations on the structural properties of crystals

We study the structural effects produced by the quantization of vibrational degrees of freedom in periodic crystals at zero temperature. To this end we introduce a methodology based on mapping a suitable subspace of the vibrational manifold and solving the Schrödinger equation in it. A number of increasingly accurate approximations ranging from the quasiharmonic approximation (QHA) to the vibrational self-consistent field (VSCF) method and the exact solution are described. A thorough analysis of the approximations is presented for model monatomic and hydrogen-bonded chains, and results are presented for a linear H-F chain where the potential-energy surface is obtained via first-principles electronic structure calculations. We focus on quantum nuclear effects on the lattice constant and show that the VSCF is an excellent approximation, meaning that correlation between modes is not extremely important. The QHA is excellent for covalently bonded mildly anharmonic systems, but it fails for hydrogen-bonded ones. In the latter, the zero-point energy exhibits a nonanalytic behavior at the lattice constant where the H atoms center, which leads to a spurious secondary minimum in the quantum-corrected energy curve. An inexpensive anharmonic approximation of noninteracting modes appears to produce rather good results for hydrogen-bonded chains for small system sizes. However, it converges to the incorrect QHA results for increasing size. Isotope effects are studied for the first-principles H-F chain. We show how the lattice constant and the H-F distance increase with decreasing mass and how the QHA proves to be insufficient to reproduce this behavior.

Thermodynamic properties and atomistic structure of the dry amorphous silica surface from a reactive force field model

A force field model of the Keating type supplemented by rules to break, form, and interchange bonds is applied to investigate thermodynamic and structural properties of the amorphous SiO2 surface. A simulated quench from the liquid phase has been carried out for a silica sample made of 3888 silicon and 7776 oxygen atoms arranged on a slab similar to 40 angstrom thick, periodically repeated along two directions. The quench results into an amorphous sample, exposing two parallel square surfaces of similar to 42 nm(2) area each. Thermal averages computed during the quench allow us to determine the surface thermodynamic properties as a function of temperature. The surface tension turns out to be gamma=310 +/- 20 erg/cm(2) at room temperature and gamma=270 +/- 30 at T=2000 K, in fair agreement with available experimental estimates. The entropy contribution Ts-s to the surface tension is relatively low at all temperatures, representing at most similar to 20% of the surface energy. Almost without exceptions, Si atoms are fourfold coordinated and oxygen atoms are twofold coordinated. Twofold and threefold rings appear only at low concentration and are preferentially found in proximity of the surface. Above the glass temperature T-g=1660 +/- 50 K, the mobility of surface atoms is, as expected, slightly higher than that of bulk atoms. The computation of the height-height correlation function shows that the silica surface is rough in the equilibrium and undercooled liquid phase, becoming smooth below the glass temperature T-g.

Structural investigations and magnetic properties of sol-gel Ni0.5Zn0.5Fe2O4 thin films for microwave heating

Nanocrystalline Ni0.5Zn0.5Fe2O4 thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology, magnetic, and microwave absorption properties of the films calcined in the 673-1073 K range were studied with x-ray diffraction, scanning electron microscopy, x-ray photoelectron spectroscopy, atomic force microscopy, vibrating sample magnetometry, and evanescent microwave microscopy. All films were uniform without microcracks. Increasing the calcination temperature from 873 to 1073 K and time from 1 to 3 h resulted in an increase of the grain size from 12 to 27 nm. The saturation and remnant magnetization increased with increasing the grain size, while the coercivity demonstrated a maximum near a critical grain size of 21 nm due to the transition from monodomain to multidomain behavior. The complex permittivity of the Ni-Zn ferrite films was measured in the frequency range of 2-15 GHz. The heating behavior was studied in a multimode microwave cavity at 2.4 GHz. The highest microwave heating rate in the temperature range of 315-355 K was observed in the film close to the critical grain size.

Fabrication of cerium oxide nanoparticles: Characterization and optical properties

Ceria (CeO2) is a technologically important rare earth material because of its unique properties and various engineering and biological applications. A facile and rapid method has been developed to prepare ceria nanoparticles using microwave with the average size 7 nm in the presence of a set of ionic liquids based on the bis (trifluoromethylsulfonyl) imide anion and different cations of 1-alkyl-3-methyl-imidazolium. The structural features and optical properties of the nanoparticles were determined in depth with X-ray powder diffraction, transmission electron microscope, N-2 adsorption-desorption technique, dynamic light scattering (DLS) analysis, FTIR spectroscopy, Raman spectroscopy, UV-vis absorption spectroscopy, and Diffuse reflectance spectroscopy. The energy band gap measurements of nanoparticles of ceria have been carried out by UV-visible absorption spectroscopy and diffuse reflectance spectroscopy. The surface charge properties of colloidal ceria dispersions in ethylene glycol have been also studied. To the best of our knowledge, this is the first report on using this type of ionic liquids in ceria nanoparticle synthesis. (C) 2011 Elsevier Inc. All rights reserved.