Magnetic properties of Fe(3)O(4) nanoparticles coated with oleic and dodecanoic acids

Magnetic nanoparticles (NP) of magnetite (Fe(3)O(4)) coated with oleic acid (OA) and dodecanoic acid (DA) were synthesized and investigated through transmission electron microscopy (TEM), magnetization M, and ac magnetic susceptibility measurements. The OA coated samples were produced with different magnetic concentrations (78%, 76%, and 65%) and the DA sample with 63% of Fe(3)O(4). Images from TEM indicate that the NP have a nearly spherical geometry and mean diameter similar to 5.5 nm. Magnetization measurements, performed in zero-field cooled (ZFC) and field cooled processes under different external magnetic fields H, exhibited a maximum at a given temperature T(B) in the ZFC curves, which depends on the NP coating (OA or DA), magnetite concentration, and H. The temperature T(B) decreases monotonically with increasing H and, for a given H, the increase in the magnetite concentration results in an increase in T(B). The observed behavior is related to the dipolar interaction between NP, which seems to be an important mechanism in all samples studied. This is supported by the results of the ac magnetic susceptibility chi(ac) measurements, where the temperature in which chi' peaks for different frequencies follows the Vogel-Fulcher model, a feature commonly found in systems with dipolar interactions. Curves of H versus T(B)/T(B) (H=0) for samples with different coatings and magnetite concentrations collapse into a universal curve, indicating that the qualitative magnetic behavior of the samples may be described by the NP themselves, instead of the coating or the strength of the dipolar interaction. Below T(B), M versus H curves show a coercive field (H(C)) that increases monotonically with decreasing temperature. The saturation magnetization (M(S)) follows the Bloch's law and values of M(S) at room temperature as high as 78 emu/g were estimated, a result corresponding to similar to 80% of the bulk value. The overlap of M/M(S) versus H/T curves for a given sample and the low H(C) at high temperatures suggest superparamagnetic behavior in all samples studied. The overlap of M/M(S) versus H curves at constant temperature for different samples indicates that the NP magnetization behavior is preserved, independently of the coating and magnetite concentration. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3311611]

Transport properties of single vacancies in nanotubes

We present density of states and electronic transport calculations of single vacancies in carbon nanotubes. We confirm that the defect reconstructs into a pentagon and a nonagon, following the removal of a single carbon atom. This leads to the formation of a dangling bond. Finally, we demonstrate that care must be taken when calculating the density of states of impurities in one-dimensional systems in general. Traditional treatments of these systems using periodic boundary conditions leads to the formation of minigaps even in the limit of large unit cells.

Experimental studies of di-jet survival and surface emission bias in Au plus Au collisions via angular correlations with respect to back-to-back leading hadrons

We report first results from an analysis based on a new multi-hadron correlation technique, exploring jet-medium interactions and di-jet surface emission bias at the BNL Relativistic Heavy Ion Collider (RHIC). Pairs of back-to-back high-transverse-momentum hadrons are used for triggers to study associated hadron distributions. In contrast with two-and three-particle correlations with a single trigger with similar kinematic selections, the associated hadron distribution of both trigger sides reveals no modification in either relative pseudorapidity Delta eta or relative azimuthal angle Delta phi from d + Au to central Au + Au collisions. We determine associated hadron yields and spectra as well as production rates for such correlated back-to-back triggers to gain additional insights on medium properties.

Nonmonotonic thickness dependence of spin wave energy in ultrathin Fe films: Experiment and theory

High wave-vector spin waves in ultrathin Fe/W(110) films up to 20 monolayers (MLs) thick have been studied using spin-polarized electron energy-loss spectroscopy. An unusual nonmonotonous dependence of the spin wave energies on the film thickness is observed, featuring a pronounced maximum at 2 ML coverage. First-principles theoretical study reveals the origin of this behavior to be in the localization of the spin waves at the surface of the film, as well as in the properties of the interlayer exchange coupling influenced by the hybridization of the electron states of the film and substrate and by the strain.

Structural and optical properties of rare earth-doped (Ba(0.77)Ca(0.23))(1-x)(Sm, Nd, Pr, Yb)(x)TiO(3)

The structural, dielectric, and vibrational properties of pure and rare earth (RE)-doped Ba(0.77) Ca(0.23)TiO(3) (BCT23; RE = Nd, Sm, Pr, Yb) ceramics obtained via solid-state reaction were investigated. The pure and RE-doped BCT23 ceramics sintered at 1450 degrees C in air for 4 h showed a dense microstructure in all ceramics. The use of RE ions as dopants introduced lattice-parameter changes that manifested in the reduction of the volume of the unit cell. RE-doped BCT23 samples exhibit a more homogenous microstructure due to the absence of a Ti-rich phase in the grain boundaries as demonstrated by scanning electron microscopy imaging. The incorporation of REs led to perturbations of the local symmetry of TiO(6) octahedra and the creation of a new Raman mode. The results of Raman scattering measurements indicated that the Curie temperature of the ferroelectric phase transition depends on the RE ion and ion content, with the Curie temperature shifting toward lower values as the RE content increases, with the exception of Yb(3+) doping, which did not affect the ferroelectric phase transition temperature. The phase transition behavior is explained using the standard soft mode model. Electronic paramagnetic resonance measurements showed the existence of Ti vacancies in the structure of RE-doped BCT23. Defects are created via charge compensation mechanisms due to the incorporation of elements with a different valence state relative to the ions of the pure BCT23 host. It is concluded that the Ti vacancies are responsible for the activation of the Raman mode at 840 cm(-1), which is in agreement with lattice dynamics calculations. (c) 2011 American Institute of Physics. [doi:10.1063/1.3594710]

Semiconducting Sn(3)O(4) nanobelts: Growth and electronic structure

The study of structures based on nonstoichiometric SnO(2-x) compounds, besides experimentally observed, is a challenging task taking into account their instabilities. In this paper, we report on single crystal Sn(3)O(4) nanobelts, which were successfully grown by a carbothermal evaporation process of SnO(2) powder in association with the well known vapor-solid mechanism. By combining the structural data and transport properties, the samples were investigated. The results showed a triclinic semiconductor structure with a fundamental gap of 2.9 eV. The semiconductor behavior was confirmed by the electron transport data, which pointed to the variable range hopping process as the main conduction mechanism, thus giving consistent support to the mechanisms underlying the observed semiconducting character.

Structural and optical analysis of GaAsP/GaP core-shell nanowires

The structural and optical properties of GaAsP/GaP core-shell nanowires grown by gas source molecular beam epitaxy were investigated by transmission electron microscopy, Raman spectroscopy, photoluminescence (PL), and magneto-PL. The effects of surface depletion and compositional variations in the ternary alloy manifested as a redshift in GaAsP PL upon surface passivation, and a decrease in redshift in PL in the presence of a magnetic field due to spatial confinement of carriers.

Fluoride-modified electrical properties of lead borate glasses and electrochemically induced crystallization in the glassy state

Lead fluoroborate glasses were prepared by the melt-quenching technique and characterized in terms of (micro)structural and electrical properties. The study was conducted on as prepared as well as temperature- and/or electric field-treated glass samples. The results show that, in the as-prepared glassy-state materials, electrical conductivity improved with increasing the PbF(2) glass content. This result involves both an increase of the fluoride charge carrier density and, especially, a decrease of the activation energy from a glass structure expansion improving charge carrier mobility. Moreover, for the electric field-treated glass samples, surface crystallization was observed even below the glass transition temperature. As previously proposed in literature, and shown here, the occurrence of this phenomenon arose from an electrochemically induced redox reaction at the electrodes, followed by crystallite nucleation. Once nucleated, growth of beta-PbF(2) crystallites, with the indication of incorporating reduced lead ions (Pb(+)), was both (micro)structurally and electrically detectable and analyzed. The overall crystallization-associated features observed here adapt well with the floppy-rigid model that has been proposed to further complete the original continuous-random-network model by Zachariasen for closely addressing not only glasses' structure but also crystallization mechanism. Finally, the crystallization-modified kinetic picture of the glasses' electrical properties, through application of polarization/depolarization measurements originally combined with impedance spectroscopy, was extensively explored. (c) 2008 American Institute of Physics.

Surface characterization of absorbing polymer films deposited on transparent glasses

PANI films were deposited on glass substrates by in-situ polymerization and characterized by UV-VIS spectroscopy and atomic force microscopy. A method is developed to accurately analyze ellipsometric data obtained for transparent glass substrates before and after modification with absorbing polymer films. Surface modification was made with an overlayer such as polyaniline ( PANI), which exhibits different optical properties by varying its oxidation state. First, the issue of using transparent substrates for ellipsometry studies was examined and then, spectroscopic ellipsometry was used to characterize absorbing overlayers on transparent glasses. The same methodologies of data analysis can be also applied to other absorbing films on transparent substrates, and deposited by different techniques.

Universal zero-bias conductance for the single-electron transistor

The thermal dependence of the zero-bias conductance for the single electron transistor is the target of two independent renormalization-group approaches, both based on the spin-degenerate Anderson impurity model. The first approach, an analytical derivation, maps the Kondo-regime conductance onto the universal conductance function for the particle-hole symmetric model. Linear, the mapping is parametrized by the Kondo temperature and the charge in the Kondo cloud. The second approach, a numerical renormalization-group computation of the conductance as a function the temperature and applied gate voltages offers a comprehensive view of zero-bias charge transport through the device. The first approach is exact in the Kondo regime; the second, essentially exact throughout the parametric space of the model. For illustrative purposes, conductance curves resulting from the two approaches are compared.

The role of electron localization in the atomic structure of transition-metal 13-atom clusters: the example of Co(13), Rh(13), and Hf(13)

The crystalline structure of transition-metals (TM) has been widely known for several decades, however, our knowledge on the atomic structure of TM clusters is still far from satisfactory, which compromises an atomistic understanding of the reactivity of TM clusters. For example, almost all density functional theory (DFT) calculations for TM clusters have been based on local (local density approximation-LDA) and semilocal (generalized gradient approximation-GGA) exchange-correlation functionals, however, it is well known that plain DFT fails to correct the self-interaction error, which affects the properties of several systems. To improve our basic understanding of the atomic and electronic properties of TM clusters, we report a DFT study within two nonlocal functionals, namely, the hybrid HSE (Heyd, Scuseria, and Ernzerhof) and GGA + U functionals, of the structural and electronic properties of the Co(13), Rh(13), and Hf(13) clusters. For Co(13) and Rh(13), we found that improved exchange-correlation functionals decrease the stability of open structures such as the hexagonal bilayer (HBL) and double simple-cubic (DSC) compared with the compact icosahedron (ICO) structure, however, DFT-GGA, DFT-GGA + U, and DFT-HSE yield very similar results for Hf(13). Thus, our results suggest that the DSC structure obtained by several plain DFT calculations for Rh(13) can be improved by the use of improved functionals. Using the sd hybridization analysis, we found that a strong hybridization favors compact structures, and hence, a correct description of the sd hybridization is crucial for the relative energy stability. For example, the sd hybridization decreases for HBL and DSC and increases for ICO in the case of Co(13) and Rh(13), while for Hf(13), the sd hybridization decreases for all configurations, and hence, it does not affect the relative stability among open and compact configurations.

Strong reduction of V(4+) amount in vanadium oxide/hexadecylamine nanotubes by doping with Co(2+) and Ni(2+) ions: Electron paramagnetic resonance and magnetic studies

In this work we present a complete characterization and magnetic study of vanadium oxide/hexadecylamine nanotubes (VO(x)/Hexa NT's) doped with Co(2)+ and Ni(2+) ions. The morphology of the NT's has been characterized by transmission electron microscopy, while the metallic elements have been quantified by the instrumental neutron activation analysis technique. The static and dynamic magnetic properties were studied by collecting data of magnetization as a function of magnetic field and temperature and by electron paramagnetic resonance. At difference of the majority reports in the literature, we do not observe magnetic dimers in vanadium oxide nanotubes. Also, we observed that the incorporation of metallic ions (Co(2+), S = 3/2 and Ni(2+), S = 1) decreases notably the amount of V(4+) ions in the system, from 14-16% (nondoped case) to 2%-4%, with respect to the total vanadium atoms (fact corroborated by XPS experiments) anyway preserving the tubular nanostructure. The method to decrease the amount of V(4+) in the nanotubes improves considerably their potential technological applications as Li-ion batteries cathodes. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3580252]

Structure, stability, depolarized light scattering, and vibrational spectra of fullerenols from all-electron density-functional-theory calculations

We have investigated the stability, electronic properties, Rayleigh (elastic), and Raman (inelastic) depolarization ratios, infrared and Raman absorption vibrational spectra of fullerenols [C(60)(OH)(n)] with different degrees of hydroxylation by using all-electron density-functional-theory (DFT) methods. Stable arrangements of these molecules were found by means of full geometry optimizations using Becke's three-parameter exchange functional with the Lee, Yang, and Parr correlation functional. This DFT level has been combined with the 6-31G(d,p) Gaussian-type basis set, as a compromise between accuracy and capability to treat highly hydroxylated fullerenes, e.g., C(60)(OH)(36). Thus, the molecular properties of fullerenols were systematically analyzed for structures with n=1, 2, 3, 4, 8, 10, 16, 18, 24, 32, and 36. From the electronic structure analysis of these molecules, we have evidenced an important effect related to the weak chemical reactivity of a possible C(60)(OH)(24) isomer. To investigate Raman scattering and the vibrational spectra of the different fullerenols, frequency calculations are carried out within the harmonic approximation. In this case a systematic study is only performed for n=1-4, 8, 10, 16, 18, and 24. Our results give good agreements with the expected changes in the spectral absorptions due to the hydroxylation of fullerenes.

Reconstruction of core and surface nanoparticles: The example of Pt(55) and Au(55)

Cuboctahedron (CUB) and icosahedron (ICO) model structures are widely used in the study of transition-metal (TM) nanoparticles (NPs), however, it might not provide a reliable description for small TM NPs such as the Pt(55) and Au(55) systems in gas phase. In this work, we combined density-functional theory calculations with atomic configurations generated by the basin hopping Monte Carlo algorithm within the empirical Sutton-Chen embedded atom potential. We identified alternative lower energy configurations compared with the ICO and CUB model structures, e. g., our lowest energy structures are 5.22 eV (Pt(55)) and 2.01 eV (Au(55)) lower than ICO. The energy gain is obtained by the Pt and Au diffusion from the ICO core region to the NP surface, which is driven by surface compression (only 12 atoms) on the ICO core region. Therefore, in the lowest energy configurations, the core size reduces from 13 atoms (ICO, CUB) to about 9 atoms while the NP surface increases from 42 atoms (ICO, CUB) to about 46 atoms. The present mechanism can provide an improved atom-level understanding of small TM NPs reconstructions.

Mechanistic studies of the 'blue' Cu enzyme, bilirubin oxidase, as a highly efficient electrocatalyst for the oxygen reduction reaction

The 'blue copper' enzyme bilirubin oxidase from Myrothecium verrucaria shows significantly enhanced adsorption on a pyrolytic graphite 'edge' (PGE) electrode that has been covalently modified with naphthyl-2-carboxylate functionalities by diazonium coupling. Modified electrodes coated with bilirubin oxidase show electrocatalytic voltammograms for the direct, four-electron reduction of O(2) by bilirubin oxidase with up to four times the current density of an unmodified PGE electrode. Electrocatalytic voltammograms measured with a rapidly rotating electrode (to remove effects of O(2) diffusion limitation) have a complex shape (an almost linear dependence of current on potential below pH 6) that is similar regardless of how PGE is chemically modified. Importantly, the same waveform is observed if bilirubin oxidase is adsorbed on Au(111) or Pt(111) single-crystal electrodes (at which activity is short-lived). The electrocatalytic behavior of bilirubin oxidase, including its enhanced response on chemically-modified PGE, therefore reflects inherent properties that do not depend on the electrode material. The variation of voltammetric waveshapes and potential-dependent (O(2)) Michaelis constants with pH and analysis in terms of the dispersion model are consistent with a change in rate-determining step over the pH range 5-8: at pH 5, the high activity is limited by the rate of interfacial redox cycling of the Type 1 copper whereas at pH 8 activity is much lower and a sigmoidal shape is approached, showing that interfacial electron transfer is no longer a limiting factor. The electrocatalytic activity of bilirubin oxidase on Pt(111) appears as a prominent pre-wave to electrocatalysis by Pt surface atoms, thus substantiating in a single, direct experiment that the minimum overpotential required for O(2) reduction by the enzyme is substantially smaller than required at Pt. At pH 8, the onset of O(2) reduction lies within 0.14 V of the four-electron O(2)/2H(2)O potential.