Optical properties of transition metal atom adsorbed graphene: A density functional theoretical calculation

Electronic and optical properties of 3d-transition metal adsorbed graphene system, theoretically studied in the framework of density functional theory, reveals significant modification compared to the pristine system. Due to adsorption of transition metal, the emergence of closely separated electronic bands leads to substantial amount of low energy optical absorption below 2.0 eV photon energy. Very significant enhancement of static dielectric constant and large value of reflectivity in the low optical energy regime has been identified for different adsorbed systems. In the different 3d-transition metal adsorbed systems, particularly up to the half filled d-shell transition metal atom, pronounced emergence of optical absorption line in the deep ultraviolet regime beyond 30.0 eV photon energy is observed.     

High-efficiency spin filtering in salophen-based molecular junctions modulated with different transition metal atoms

Based on the density functional theory and nonequilibrium Green's function methods, we investigate the spin transport properties of the molecular junctions constructed by a homologous series of 3d transition metal(II) salophens (TM-salophens, TM = Co, Fe, Ni and Mn) sandwiched between two gold electrodes. It is found that among the four molecular junctions only Co-salophen junction can act as an efficient spin filter distinctively. The conductance through Co-salophen molecular junction is dominated by spin-down electrons. The mechanism is proposed for these phenomena.     

Ab initio investigation of local magnetic structures around substitutional 3d transition metal impurities at cation sites in III-V and II-VI semiconductors

The local magnetic structures around substitutional 3d transition metal impurities at cation sites in zinc blende structures of III-V (GaN, GaAs) and II-VI (ZnTe) semiconductors are investigated by using a spin-polarized density functional theory. We find that Cr-, Co-, Cu-doped GaN, Cr-, Mn-doped GaAs and Cr-, Fe-, Ni-doped ZnTe are half metallic with 100% spin polarization. The magnetic moments due to these 3d transition metal (TM) ions are delocalized quite significantly on the surrounding ions of host semiconductors. These doped TM ions have long range interactions mediated through the induced magnetic moments in anions and cations of host semiconductors. For low impurity concentrations Mn in GaAs also has zero magnetic moment state due to Jahn-Teller structural distortions. Based upon half metallic character and delocalization of magnetic moments in the anions and cations of host semiconductors these above mentioned 3d TM-doped GaN, GaAs and ZnTe seem to be good candidates for spintronic applications.     

Optical manipulation of coupled spins in magnetic semiconductor systems: A path toward spin optoelectronics

Experimental results based on the optical excitations in the III–V-based ferromagnetic semiconductors are reviewed. On the bases of results obtained by both cw- and femto-second-pulse optical excitation, we point out the feasibility of magnetization rotation in the hole-mediated ferromagnetic semiconductor (Ga,Mn)As via the angular momentum and photon energy of light. Here, p–d exchange interaction is the effective channel that transmits a small change in spin axis of the valence band to the ferromagnetically coupled Mn spin sub-system. Within the limit of this picture, we also discuss a hole–Mn spin complex for which hole and Mn spins rotate and relax together upon optical excitation. Partial magnetization reversal observed in the experiments of the electrical current injection in (Ga,Mn)As-based magnetic-tunnel-junction devices is also reviewed in view of the effects caused by the spin-polarized holes. Here, we point out that a spin current of 10⁵ A/cm² may be reduced further if spin injection efficiency can be improved by the optimal designs of the device structure.     

Quantum phase transition in spin glasses with multi-spin interactions

We examine the phase diagram of the p-interaction spin glass model in a transverse field. We consider a spherical version of the model and compare with results obtained in the Ising case. The analysis of the spherical model, with and without quantization, reveals a phase diagram very similar to that obtained in the Ising case. In particular, using the static approximation, reentrance is observed at low temperatures in both the quantum spherical and Ising models. This is an artifact of the approximation and disappears when the imaginary time dependence of the order parameter is taken into account. The resulting phase diagram is checked by accurate numerical investigation of the phase boundaries.     

Intrinsic spin Hall effect in silicene: transition from spin Hall to normal insulator

An intrinsic contribution to the spin Hall effect in two‐dimensional silicene is considered theoretically within the linear response theory and Green's function formalism. When an external voltage normal to the silicene plane is applied, the spin Hall conductivity is shown to reveal a transition from the spin Hall insulator phase at low bias to the conventional insulator phase at higher voltages. This transition resembles the recently reported phase transition in bilayer graphene. The spin–orbit interaction responsible for this transition in silicene is much stronger than in graphene, which should make the transition observable experimentally. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

From sum rules to RPA: 3. Optical dipole response in metal clusters

The properties of plasmon resonances in metal clusters are computed within the random phase approximation (RPA), starting from the Kohn-Sham ground state within the jellium model. The paper aims at a systematic survey of the general trends with varying parameters such as electron number, angular momentum, Wigner-Seitz radius etc. To this end we exploit the flexibility of a particular RPA scheme which allows to switch easily between different levels of approximation.     

Theory of oxidation/reduction-induced valence transformations of metal ion dopants in oxide crystals mediated by oxide-vacancy diffusion: I. Thermodynamic analysis

We consider theoretically valence transformations of doping metal ions in oxide crystals induced by oxidation and reduction obtained by changes in the ambient oxygen partial pressure. Three types of oxygen vacancies are assumed to mediate transformations: neutral, singly ionized, and doubly ionized. We provide thermodynamic equilibrium analyses, yielding concentration relations among the oxygen vacancy, metal ions, holes and electrons as functions of the ambient oxygen pressure. The results suggest that experimental study of different species concentrations at thermodynamic equilibrium as functions of pressure and temperature should allow assessment of various reversible reaction constants controlling the process. In the Part II companion paper, the kinetic (diffusion) characteristics are considered in detail.     

Theory of oxidation/reduction-induced valence transformations of metal ion dopants in oxide crystals mediated by oxide-vacancy diffusion: II. Kinetic analysis

We consider theoretically valence transformations of doping metal ions in oxide crystals induced by oxidation and reduction obtained by changes in the ambient oxygen partial pressure. Three types of oxygen vacancies are assumed to mediate transformations: neutral, singly ionized, and doubly ionized. In the companion part I paper we provide thermodynamic analyses yielding concentration relations among the oxygen vacancy, metal ions, holes and electrons, as functions of the ambient oxygen pressure. In the present companion part II paper we provide time dependent concentration profiles of the various species and reaction rate profiles. The diffusion exhibits a complex behavior; under some conditions, it may be described by a constant diffusivity, and is symmetric with respect to oxidation and reduction. However, under a wide range of conditions, the ionic state changes are highly asymmetric with respect to oxidation and reduction. For example, in the case of a neutral vacancy, a very narrow reaction front may establish during reduction. In the inverse (oxidation) process, however, the different species' profiles are quite smooth.     

Localized canting of spins structure in the spinel oxide system: ZnzTizFe2−x−zCrx−zCoO4

The spinel oxide system Zn_zTi_zFe_2−x−zCr_x−zCoO₄; z=x²; x=0.60, 0.65, 0.70 and 0.80, was studied using neutron diffraction technique, low field DC magnetization measurements (ZFC–FC measurements), magnetic hysterisis, Mössbauer spectroscopy and low field AC susceptibility measurements. All the compositions show significantly less B-site magnetic moments at 10 K temperature derived from neutron diffraction data than the free ions site moments deduced assuming collinear arrangement of spins. This combined with some other features seen in the low temperature neutron diffraction patterns suggest localized canting of spins (LCS) type of magnetic ordering in the present system where a long range order of longitudinal component of moments co-exists along with totally disordered transverse component of moments. The conclusion is also supported by the features seen in the other measurements. The magnetic moments derived from 10 K neutron diffraction data are explained using the LCS approach for different exchange integrals ratios.     

UV-laser-light-controlled photoluminescence of metal oxide nanoparticles in different gas atmospheres: BaTiO3, SrTiO3 and HfO2

The photoluminescence (PL) enhancement has been studied at room temperature using various specimen atmospheres (O₂ gas, CO₂ gas, CO₂–H₂ mixture gas, Ar–H₂ mixture gas and vacuum) under 325 nm laser light irradiation on various metal oxides. Of them, the results obtained for BaTiO₃ nanocrystals, SrTiO₃ ones and HfO₂ powder crystal are given in the present paper. Their PL were considerably increased in intensity by irradiation of 325 nm laser light in CO₂ gas and CO₂–H₂ mixture gas. The cause of the PL intensity enhancements is discussed in the light of the exciton theory, the defect chemistry and the photocatalytic theory. The results may be applied for the utilization of greenhouse gas (CO₂) and the optical sensor for CO₂ gas.     

Effect of metal atoms on the electronic properties of metal oxide nanoclusters for use in drug delivery applications: a density functional theory study

To improve drug selectivity toward target cells, one interesting technique for drug delivery is to use nanostructured materials. Recent studies revealed that the fullerene-like nanoclusters can pass through cell walls and transport and release drugs in the target site. In this study, the reactivity, and electronic sensitivity of the Be12O12, Mg12O12, and Zn12O12 nanoclusters were investigated toward hydroxyurea (HU) anticancer drug using density functional theory calculations at gas phase and aqueous solution. Our results show that the electronic properties of Mg12O12 and Zn12O12 nanoclusters are significantly sensitive to the presence of HU and the nanoclusters may be a promising candidate for adsorption of this drug. The results show that all complexes are energetically favourable, especially in the aqueous phase. Also, our ultraviolet–visible results show that the electronic spectra of HU/(MO)12 complexes exhibit a blue shift toward lower wavelengths (higher energies). To go further and gain insight into the binding features of considered (MO)12 nanoclusters with HU drug, the Atoms in Molecules analysis was performed. Our results determine the electrostatic features of the HU/Mg12O12 and HU/Zn12O12 bonding. Consequently, the results demonstrated that the Mg12O12 and Zn12O12 nanoclusters could be used as potential carriers for the delivery of HU drug.     

To breathe or not to breathe—That is the question: An investigation of speech breathing kinematics in world class Shakespearean actors

Anteroposterior diameter changes of the rib cage and abdomen were recorded during respiratory and speaking activities in four adult subjects, three men and one woman, all of whom had extensive dramatic training and experience and were earning their livelihood as professional actors. Data were charted to solve for lung volume, and volume displacements of the rib cage and abdomen. The more vigorous and louder monologue performances by the professional actor subjects differed from other speaking and reading activities in the following parameters of lung volume, separate volumes, relative volume contributions, and the frequent use of respiratory phase transitions. Novice actor subjects' monologue performances are compared to the monologue performances of the professional actor subjects.     

Pressure-induced structural phase transition in transition metal carbides TMC (TM = Ru,Rh, Pd,Os, Ir,Pt): a DFT study

First-principles calculations based on density functional theory was performed to analyse the structural stability of transition metal carbides TMC (TM = Ru, Rh, Pd, Os, Ir, Pt). It is observed that zinc-blende phase is the most stable one for these carbides. Pressure-induced structural phase transition from zinc blende to NiAs phase is predicted at the pressures of 248.5 GPa, 127 GPa and 142 GPa for OsC, IrC and PtC, respectively. The electronic structure reveals that RuC exhibits a semiconducting behaviour with an energy gap of 0.7056 eV. The high bulk modulus values of these carbides indicate that these metal carbides are super hard materials. The high B/G value predicts that the carbides are ductile in their most stable phase.     

Charge transfer transitions in the transition metal oxides ABO4:Ln and APO4:ln (A=La, Gd, Y, Lu, Sc; B=V, Nb, Ta; Ln=lanthanide)

We have compiled and analyzed optical and structural properties of lanthanide doped non-metal oxides of the form APO₄:Ln³⁺ with A a rare earth and of transition metal oxides with formula ABO₄:Ln³⁺ with B a transition metal. The main objective is to understand better the interrelationships between the band gap energy, the O²⁻→Ln³⁺ charge transfer energy, and the Ln³⁺→B⁵⁺ inter-valence charge transfer energy. Various models exist for each of these three types of electron transitions in inorganic compounds that appear highly related to each other. When properly interpreted, these optically excited transitions provide the locations of the lanthanide electron donating and electron accepting states relative to the conduction band and the valence band of the hosting compound. These locations in turn determine the luminescent properties and charge carrier trapping properties of that host. Hence, understanding the relationship between the different types of charge transfer processes and its implication for lanthanide level location in the band gap is of technological interest.     

A theoretical study of magnetic phase transitions in ultra-thin films: Application to NiO

Phase diagrams and critical temperatures of projected onto fcc (1 0 0) layers, which is believed to be applicable to first-row transition metal oxides such as VO, MnO and NiO, are obtained from mean field theory and Monte Carlo simulations. Within the regime, J_se > 0, which includes MnO and NiO, both approaches predict bicritical behaviour of the AF₂ and AF₃ antiferromagnetic spin alignments for odd numbers of layers greater than one and monocritical behaviour for even numbers of layers, even when films are described by single values of J_d and J_se. The ferromagnetic alignment, on the other hand, exhibits monocritical behaviour for all thicknesses from the monolayer through to the bulk. For values of (x = J_d/J_se) which are close to those obtained from first principles calculations for NiO and also those derived from measured magnon spectra, estimates of the thickness dependence of the critical temperature from Monte Carlo simulations are similar to that derived from linear polarised X-ray absorption spectra of NiO(1 0 0) ultra-thin films grown epitaxially on MgO(1 0 0) [D. Alders, L.H. Tjeng, F.C. Voogt, T. Hibma, G.A. Sawatzky, J. Vogel, M. Sacchi, S. Iacobucci, Phys. Rev. B 57 (1998) 11623].     

Surface and bulk phenomena in the process of GdHx (0.01 < x < 3) formation in thin Gd films: Transition from metal to transparent semiconductor

The aim of this work was to answer the question whether in the process of gadolinium hydride formation the negatively charged hydrogen adspecies arise directly on the surface at some coverage, or a transition from protonic to anionic hydrogen occurs in the bulk. Thin gadolinium films were deposited on glass under UHV conditions and transformed “in situ” into GdH_x (0.01 < x < 3) by introducing H₂ in successive calibrated doses. Work function changes ΔΦ and pressure P were recorded continuously. Knowing the weight of the thin Gd film and the amount of hydrogen consumed, the atomic ratio H/Gd could be determined and correlated with ΔΦ and P at every step of the process. Parallel experiments were performed measuring the resistance and optical transparency of thin gadolinium films deposited under identical conditions during their transition into GdH_x (0.01 < x < 3). It was found that in the process of GdH_x formation, light-reflecting metallic thin Gd film is transferred into transparent trihydride while its resistance increases by several orders of magnitude. At low coverage, positively polarized hydrogen adspecies arise, penetrating quickly into the bulk. When the average H/Gd concentration approaches 1, negatively charged hydrogen adspecies appear directly on the surface, slowly penetrating into the bulk.     

Exchange bias mechanism in FM/FM/AF spin valve systems in the presence of random unidirectional anisotropy field at the AF interface: The role played by the interface roughness due to randomness

We propose an atomistic model and present Monte Carlo simulation results regarding the influence of FM/AF interface structure on the hysteresis mechanism and exchange bias behavior for a spin valve type FM/FM/AF magnetic junction. We simulate perfectly flat and roughened interface structures both with uncompensated interfacial AF moments. In order to simulate rough interface effect, we introduce the concept of random exchange anisotropy field induced at the interface, and acting on the interface AF spins. Our results yield that different types of the random field distributions of anisotropy field may lead to different behavior of exchange bias.