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Sample records for metallic target theory

  1. Targeting the Teaching of Theory.

    ERIC Educational Resources Information Center

    Walton, Charles W.

    1981-01-01

    Suggests that six target areas in the teaching of theory and musicianship need more attention and emphasis: listening, analysis, music reading, creativity, music writing, and keyboard harmony. Discusses content and sequence in music theory and presents two sample applications. (SJL)

  2. String theory in target space

    NASA Astrophysics Data System (ADS)

    Boels, Rutger H.; Hansen, Tobias

    2014-06-01

    It is argued that the complete S-matrix of string theory at tree level in a flat background can be obtained from a small set of target space properties, without recourse to the worldsheet description. The main non-standard inputs are (generalised) Britto-Cachazo-Feng-Witten shifts, as well as the monodromy relations for open string theory and the Kawai-Lewellen-Tye relations for closed string theory. The roots of the scattering amplitudes and especially their appearance in the residues at the kinematic poles are central to the story. These residues determine the amplitudes through on-shell recursion relations. Several checks of the formalism are presented, including a computation of the Koba-Nielsen amplitude in the bosonic string. Furthermore the question of target space unitarity is (re-)investigated. For the Veneziano amplitude this question is reduced by Poincaré invariance, unitarity and locality to that of positivity of a particular numerical sum. Interestingly, this analysis produces the main conditions of the no-ghost theorem on dimension and intercept from the first three poles of this amplitude.

  3. Alkali Metal Cluster Theory.

    NASA Astrophysics Data System (ADS)

    Chen, Jian

    Available from UMI in association with The British Library. Requires signed TDF. In this thesis, we apply the tight-binding Hubbard model to alkali metal clusters with Hartree-Fock self-consistent methods and perturbation methods for the numerical calculations. We have studied the relation between the equilibrium structures and the range of the hopping matrix elements in the Hubbard Hamiltonian. The results show that the structures are not sensitive to the interaction range but are determined by the number of valence electrons each atom has. Inertia tensors are used to analyse the symmetries of the clusters. The principal axes of the clusters are determined and they are the axes of rotational symmetries of clusters if the clusters have any. The eigenvalues of inertia tensors which are the indication of the deformation of clusters are compared between our model and the ellipsoidal jellium model. The agreement is good for large clusters. At a finite temperature, the thermal motion fluctuates the structures. We defined a fluctuation function with the distance matrix of a cluster. The fluctuation has been studied with the Monte-Carlo simulation method. Our studies show that the clusters remain in the solid state when temperature is low. The small values of fluctuation functions indicates the thermal vibration of atoms around their equilibrium positions. If the temperature is high, the atoms are delocalized. The cluster melts and enters the liquid region. The cluster melting is simulated by the Monte-Carlo simulation with the fluctuation function we defined. Energy levels of clusters are calculated from the Hubbard model. Ionization potentials and magic numbers are also obtained from these energy levels. The results confirm that the Hubbard model is a good approximation for a small cluster. The excitation energy is presented by the difference between the original level and excited level, and the electron-hole interactions. We also have studied cooling of clusters

  4. Metal-mediated targeting in the body.

    PubMed

    Tang, Xuan; Liang, Xiangyang

    2013-03-01

    Metal ions are important for many biological processes and are steadily available in the human body. Metal concentrations can be extremely high in diseased areas of various pathological conditions. Some synthetic and natural drugs need to be activated by metal ions as prodrugs. In this review, we provide a few examples to illustrate how metal ions activate and mediate drug targeting in the body. This knowledge may be helpful for the development of more effective drugs and pharmaceutical formulations.

  5. Group target tracking using game theory

    NASA Astrophysics Data System (ADS)

    Sadjadi, Firooz A.; Kober, Wolfgang

    2001-10-01

    The problem of tracking of a group of targets is considered in this paper. We will present an overview of an investigation into this problem by first using the targets velocity state vectors covariance matrix to establish target grouping and then by exploiting concepts derived from game theory, in particular the leader-follower techniques, and graph theory to represent and establish relationships that influence the tracking of objects that belong to a group formation.

  6. Automatic target recognition via classical detection theory

    NASA Astrophysics Data System (ADS)

    Morgan, Douglas R.

    1995-07-01

    Classical Bayesian detection and decision theory applies to arbitrary problems with underlying probabilistic models. When the models describe uncertainties in target type, pose, geometry, surround, scattering phenomena, sensor behavior, and feature extraction, then classical theory directly yields detailed model-based automatic target recognition (ATR) techniques. This paper reviews options and considerations arising under a general Bayesian framework for model- based ATR, including approaches to the major problems of acquiring probabilistic models and of carrying out the indicated Bayesian computations.

  7. Fuel cells and the theory of metals.

    NASA Technical Reports Server (NTRS)

    Bocciarelli, C. V.

    1972-01-01

    Metal theory is used to study the role of metal catalysts in electrocatalysis, with particular reference to alkaline hydrogen-oxygen fuel cells. Use is made of a simple model, analogous to that used to interpret field emission in vacuum. Theoretical values for all the quantities in the Tafel equation are obtained in terms of bulk properties of the metal catalysts (such as free electron densities and Fermi level). The reasons why some processes are reversible (H-electrodes) and some irreversible (O-electrodes) are identified. Selection rules for desirable properties of catalytic materials are established.

  8. Optical transmission theory for metal-insulator-metal periodic nanostructures

    NASA Astrophysics Data System (ADS)

    Blanchard-Dionne, Andre-Pierre; Meunier, Michel

    2017-01-01

    A semi-analytical formalism for the optical properties of a metal-insulator-metal periodic nanostructure using coupled-mode theory is presented. This structure consists in a dielectric layer in between two metallic layers with periodic one-dimensional nanoslit corrugation. The model is developed using multiple-scattering formalism, which defines transmission and reflection coefficients for each of the interface as a semi-infinite medium. Total transmission is then calculated using a summation of the multiple paths of light inside the structure. This method allows finding an exact solution for the transmission problem in every dimension regime, as long as a sufficient number of diffraction orders and guided modes are considered for the structure. The resonant modes of the structure are found to be related to the metallic slab only and to a combination of both the metallic slab and dielectric layer. This model also allows describing the resonant behavior of the system in the limit of a small dielectric layer, for which discontinuities in the dispersion curves are found. These discontinuities result from the out-of-phase interference of the different diffraction orders of the system, which account for field interaction for both inner interfaces of the structure.

  9. Optical transmission theory for metal-insulator-metal periodic nanostructures

    NASA Astrophysics Data System (ADS)

    Blanchard-Dionne, Andre-Pierre; Meunier, Michel

    2016-11-01

    A semi-analytical formalism for the optical properties of a metal-insulator-metal periodic nanostructure using coupled-mode theory is presented. This structure consists in a dielectric layer in between two metallic layers with periodic one-dimensional nanoslit corrugation. The model is developed using multiple-scattering formalism, which defines transmission and reflection coefficients for each of the interface as a semi-infinite medium. Total transmission is then calculated using a summation of the multiple paths of light inside the structure. This method allows finding an exact solution for the transmission problem in every dimension regime, as long as a sufficient number of diffraction orders and guided modes are considered for the structure. The resonant modes of the structure are found to be related to the metallic slab only and to a combination of both the metallic slab and dielectric layer. This model also allows describing the resonant behavior of the system in the limit of a small dielectric layer, for which discontinuities in the dispersion curves are found. These discontinuities result from the out-of-phase interference of the different diffraction orders of the system, which account for field interaction for both inner interfaces of the structure.

  10. Theory of spin relaxation at metallic interfaces

    NASA Astrophysics Data System (ADS)

    Belashchenko, K. D.; Kovalev, Alexey A.; van Schilfgaarde, Mark

    Spin-flip scattering at metallic interfaces affects transport phenomena in nanostructures, such as magnetoresistance, spin injection, spin pumping, and spin torques. It has been characterized for many material combinations by an empirical parameter δ, which is obtained by matching magnetoresistance data for multilayers to the Valet-Fert model [J. Bass and W. P. Pratt, J. Phys.: Condens. Matter 19, 183201 (2007)]. However, the relation of the parameter δ to the scattering properties of the interface remains unclear. Here we establish this relation using the scattering theory approach and confirm it using a generalization of the magnetoelectronic circuit theory, which includes interfacial spin relaxation. The results of first-principles calculations of spin-flip scattering at the Cu/Pd and Cu/Pt interfaces are found to be in reasonable agreement with experimental data. Supported by NSF Grant DMR-1308751.

  11. Weak crystallization theory of metallic alloys

    NASA Astrophysics Data System (ADS)

    Martin, Ivar; Gopalakrishnan, Sarang; Demler, Eugene A.

    2016-06-01

    Crystallization is one of the most familiar, but hardest to analyze, phase transitions. The principal reason is that crystallization typically occurs via a strongly first-order phase transition, and thus rigorous treatment would require comparing energies of an infinite number of possible crystalline states with the energy of liquid. A great simplification occurs when crystallization transition happens to be weakly first order. In this case, weak crystallization theory, based on unbiased Ginzburg-Landau expansion, can be applied. Even beyond its strict range of validity, it has been a useful qualitative tool for understanding crystallization. In its standard form, however, weak crystallization theory cannot explain the existence of a majority of observed crystalline and quasicrystalline states. Here we extend the weak crystallization theory to the case of metallic alloys. We identify a singular effect of itinerant electrons on the form of weak crystallization free energy. It is geometric in nature, generating strong dependence of free energy on the angles between ordering wave vectors of ionic density. That leads to stabilization of fcc, rhombohedral, and icosahedral quasicrystalline (iQC) phases, which are absent in the generic theory with only local interactions. As an application, we find the condition for stability of iQC that is consistent with the Hume-Rothery rules known empirically for the majority of stable iQC; namely, the length of the primary Bragg-peak wave vector is approximately equal to the diameter of the Fermi sphere.

  12. Liquid Metal Target for NLC Positron Source

    SciTech Connect

    Sheppard, John C.

    2002-08-19

    Possibility of creating the liquid lead target with parameters, optimum for the NLC positron source, is investigated. Target has a form of titanium vessel, filled with liquid lead, pumped through. The energy deposition in target is characterized by 35 kW average power and up to 250 J/g specific energy at optimum beam sigma 0.6 mm. The use of pumped through liquid lead as target material solves both the problems of power evacuation and target survival. The window for beam exit is made of both temperature and pressure resistive material--the diamond-like ceramic BN.

  13. Theory of spoof plasmons in real metals

    NASA Astrophysics Data System (ADS)

    Rusina, Anastasia; Durach, Maxim; Stockman, Mark I.

    2010-08-01

    In this Letter we develop a theory of spoof plasmons propagating on real metals perforated with planar periodic grooves. Deviation from the spoof plasmons on perfect conductor due to finite skin depth has been analytically described. This allowed us to investigate important propagation characteristics of spoof plasmons such as quality factor and propagation length as the function of the geometrical parameters of the structure. We have also considered THz field confinement by adiabatic increase of the depth of the grooves. It is shown that the finite skin depth limits the propagation length of spoof plasmons as well as a possibility to localize THz field. Geometrical parameters of the structure are found which provide optimal guiding and localization of THz energy.

  14. Theory of Spin Loss at Metallic Interfaces

    NASA Astrophysics Data System (ADS)

    Belashchenko, K. D.; Kovalev, Alexey A.; van Schilfgaarde, M.

    2016-11-01

    Interfacial spin-flip scattering plays an important role in magnetoelectronic devices. Spin loss at metallic interfaces is usually quantified by matching the magnetoresistance data for multilayers to the Valet-Fert model, while treating each interface as a fictitious bulk layer whose thickness is δ times the spin-diffusion length. By employing the properly generalized circuit theory and the scattering matrix approaches, we derive the relation of the parameter δ to the spin-flip transmission and reflection probabilities at an individual interface. It is found that δ is proportional to the square root of the probability of spin-flip scattering. We calculate the spin-flip scattering probabilities for flat and rough Cu /Pd interfaces using the Landauer-Büttiker method based on the first-principles electronic structure and find δ to be in reasonable agreement with experiment.

  15. Webinar Presentation: The MATCH Study (Metals Assessment Targeting Community Health)

    EPA Pesticide Factsheets

    This presentation, The MATCH Study (Metals Assessment Targeting Community Health), was given at the NIEHS/EPA Children's Centers 2015 Webinar Series: Historical Perspectives and Research Updates from Previously Funded Children's Centers held on 11/18/15.

  16. Mitochondrial metals as a potential therapeutic target in neurodegeneration

    PubMed Central

    Grubman, A; White, A R; Liddell, J R

    2014-01-01

    Transition metals are critical for enzyme function and protein folding, but in excess can mediate neurotoxic oxidative processes. As mitochondria are particularly vulnerable to oxidative damage due to radicals generated during ATP production, mitochondrial biometal homeostasis must therefore be tightly controlled to safely harness the redox potential of metal enzyme cofactors. Dysregulation of metal functions is evident in numerous neurological disorders including Alzheimer's disease, stroke, Parkinson's disease, Huntington's disease, amyotrophic lateral sclerosis and Friedrich's ataxia. This review describes the mitochondrial metal defects in these disorders and highlights novel metal-based therapeutic approaches that target mitochondrial metal homeostasis in neurological disorders. Linked Articles This article is part of a themed issue on Mitochondrial Pharmacology: Energy, Injury & Beyond. To view the other articles in this issue visit http://dx.doi.org/10.1111/bph.2014.171.issue-8 PMID:24206195

  17. Metallic and nonmetallic coatings for ICF targets

    SciTech Connect

    Hendricks, C.D.; Crane, J.K.; Hsieh, E.J.; Meyer, S.F.

    1981-04-17

    Some fusion targets designed to be driven by 0.35 to 1 ..mu..m laser light are glass spheres coated with layers of various materials such as hydrocarbons, fluorocarbons, beryllium, copper, gold, platinum, etc. The glass shell, which is filled with gas, liquid or solid deuterium-tritium fuel, must have remarkably good surface and wall thickness uniformity. Methods for depositing the various materials will be discussed. They include plasma polymerization, electro-deposition, sputtering and evaporation. Many of the difficulties encountered in the coating processes are the result of coating on free spheres with very small radii - 35 to 500 micrometers. Several means of overcoming the problems will be described and experimental results presented.

  18. Magnetism of metals in the dynamic spin-fluctuation theory

    NASA Astrophysics Data System (ADS)

    Melnikov, N. B.; Reser, B. I.

    2016-12-01

    We overview new developments in spin-fluctuation theory, which describes magnetic properties of ferromagnetic metals at finite temperatures. We present a detailed analysis of the underlying techniques and compare numerical results with experiment.

  19. Incorporating metal into polarized 3He target cells

    NASA Astrophysics Data System (ADS)

    Katugampola, Sumudu K.; Matyas, Daniel J.; Wang, Yunxiao; Tobias, William A.; Nelyubin, Vladimir; Cates, Gordon D.

    2017-01-01

    An upcoming measurement at Jefferson Laboratory (JLab) of the electric form factor of the neutron will utilize a polarized 3He target at high luminosity. While polarized 3He targets at JLab have previously been made entirely of glass, we describe progress toward incorporating metal windows for the electron beam. Under the conditions of our targets, very few studies have been done on the spin-relaxation of nuclear-polarized 3He on metal surfaces. We have found good performance by using Oxygen Free High Conductivity (OFHC) copper substrates electroplated with gold. The glass-to-metal transitions within our test cells were based on Housekeeper seals. We have further established that Uranium glass (Canary glass) has excellent spin-relaxation properties, and can serve as a transition glass from Pyrex to Aluminosilicate glass (GE180). Another finding was that spin-relaxation properties were sensitive to the manner in which cells were annealed, an important issue because of constraints when annealing cells containing both metal and glass.

  20. Dislocation Theory of the Fatigue of Metals

    NASA Technical Reports Server (NTRS)

    Machlin, E S

    1949-01-01

    A dislocation theory of fatigue failure for annealed solid solutions is presented. On the basis of this theory, an equation giving the dependence of the number of cycles for failure on the stress, the temperature, the material parameters, and the frequency is derived for uniformly stressed specimens. The equation is in quantitative agreement with the data. Inasmuch as one material parameter is indicated to be temperature-dependent and its temperature dependence is unknown, it is impossible to predict the temperature dependence of the number of cycles for failure. A predicted quantitative correlation between fatigue and creep was found to exist, which suggests the practical possibility of obtaining fatigue data for annealed solid solutions and elements from steady-state creep-rate data for these materials. As a result of this investigation, a modification of the equation for the steady-state creep rate previously developed on the basis of the dislocation theory is suggested. Additional data are required to verify completely the dislocation theory of fatigue.

  1. Analytical theory of extraordinary optical transmission through realistic metallic screens.

    PubMed

    Delgado, V; Marqués, R; Jelinek, L

    2010-03-29

    An analytical theory of extraordinary optical transmission (EOT) through realistic metallic screens perforated by a periodic array of subwavelength holes is presented. The theory is based on our previous work on EOT through perfect conducting screens and on the surface impedance concept. The proposed theory is valid for the complete frequency range where EOT has been reported, including microwaves and optics. A reasonably good agreement with electromagnetic simulations is shown in all this frequency range. We feel that the proposed theory may help to clarify the physics underlying EOT and serve as a first step to more accurate analysis.

  2. Infrared small target detection based on Danger Theory

    NASA Astrophysics Data System (ADS)

    Lan, Jinhui; Yang, Xiao

    2009-11-01

    To solve the problem that traditional method can't detect the small objects whose local SNR is less than 2 in IR images, a Danger Theory-based model to detect infrared small target is presented in this paper. First, on the analog with immunology, the definition is given, in this paper, to such terms as dangerous signal, antigens, APC, antibodies. Besides, matching rule between antigen and antibody is improved. Prior to training the detection model and detecting the targets, the IR images are processed utilizing adaptive smooth filter to decrease the stochastic noise. Then at the training process, deleting rule, generating rule, crossover rule and the mutation rule are established after a large number of experiments in order to realize immediate convergence and obtain good antibodies. The Danger Theory-based model is built after the training process, and this model can detect the target whose local SNR is only 1.5.

  3. Thermodynamic perturbation theory in studies of metal melts

    NASA Astrophysics Data System (ADS)

    Dubinin, N. E.; Vatolin, N. A.; Filippov, V. V.

    2014-11-01

    The review concerns methods of the thermodynamic perturbation theory (TPT) used to study liquid metals and alloys. Basic relations of the TPT are presented. Various reference systems are analyzed, their advantages and drawbacks are described. The results of calculations of the structure and thermodynamic properties of metal melts by various methods are discussed. Promising avenues of research in the title field are outlined. The bibliography includes 272 references.

  4. Laser backwriting process on glass via ablation of metal targets

    NASA Astrophysics Data System (ADS)

    Castelo, A.; Nieto, D.; Bao, C.; Flores-Arias, M. T.; Pérez, M. V.; Gómez-Reino, C.; López-Gascón, C.; de la Fuente, G. F.

    2007-05-01

    Ablation of metal targets onto pyrex glass substrates, using a Q-switched Nd:YAG laser working at 355 nm, was used to study the potential of a laser backwriting process for the fabrication of optical waveguides via an index of refraction change. Metal foils of stainless steel, aluminum, copper, brass and gold have been used as blanks and irradiated by focusing the laser beam through a cylindrical lens under continuous movement in a direction perpendicular to the irradiation. An horizontal setup was found suitable to improve the effect of the plume in the sample. Results were obtained for two different configurations. Transversal profiles were analysed using a contact profilometer, comparing results obtained for the different configurations, traverse speeds and metal targets used. Two ablation regimes were identified, which are related to a critical laser fluence value of 2.7 J/cm 2. Surface micrographs obtained by scanning electron microscopy are discussed, together with the characteristics of the structures attained, taking into account the optical and thermal properties of the ablated metal blanks.

  5. Compatibility of materials with liquid metal targets for SNS

    SciTech Connect

    DiStefano, J.R.; Pawel, S.J.; DeVan, J.H.

    1996-06-01

    Several heavy liquid metals are candidates as the target in a spallation neutron source: Hg, Pb, Bi, and Pb-Bi eutectic. Systems with these liquid metals have been used in the past and a data-base on compatibility already exists. Two major compatibility issues have been identified when selecting a container material for these liquid metals: temperature gradient mass transfer and liquid metal embrittlement or LME. Temperature gradient mass transfer refers to dissolution of material from the high temperature portions of a system and its deposition in the lower temperature areas. Solution and deposition rate constants along with temperature, {Delta}T, and velocity are usually the most important parameters. For most candidate materials mass transfer corrosion has been found to be proportionately worse in Bi compared with Hg and Pb. For temperatures to {approx}550{degrees}C, ferritic/martensitic steels have been satisfactory in Pb or Hg systems and the maximum temperature can be extended to {approx}650{degrees}C with additions of inhibitors to the liquid metal, e.g. Mg, Ti, Zr. Above {approx}600{degrees}C, austenitic stainless steels have been reported to be unsatisfactory, largely because of the mass transfer of nickel. Blockage of flow from deposition of material is usually the life-limiting effect of this type of corrosion. However, mass transfer corrosion at lower temperatures has not been studied. At low temperatures (usually < 150{degrees}C), LME has been reported for some liquid metal/container alloy combinations. Liquid metal embrittlement, like hydrogen embrittlement, results in brittle fracture of a normally ductile material.

  6. Biological metals and metal-targeting compounds in major neurodegenerative diseases.

    PubMed

    Barnham, Kevin J; Bush, Ashley I

    2014-10-07

    Multiple abnormalities occur in the homeostasis of essential endogenous brain biometals in age-related neurodegenerative disorders, Alzheimer's disease, Parkinson's disease, Huntington's disease and amyotrophic lateral sclerosis. As a result, metals both accumulate in microscopic proteinopathies, and can be deficient in cells or cellular compartments. Therefore, bulk measurement of metal content in brain tissue samples reveal only the "tip of the iceberg", with most of the important changes occurring on a microscopic and biochemical level. Each of the major proteins implicated in these disorders interacts with biological transition metals. Tau and the amyloid protein precursor have important roles in normal neuronal iron homeostasis. Changes in metal distribution, cellular deficiencies, or sequestration in proteinopathies all present abnormalities that can be corrected in animal models by small molecules. These biochemical targets are more complex than the simple excess of metals that are targeted by chelators. In this review we illustrate some of the richness in the science that has developed in the study of metals in neurodegeneration, and explore its novel pharmacology.

  7. Circuit theory of transport in ferromagnet - normal metal systems

    NASA Astrophysics Data System (ADS)

    Brataas, Arne

    2001-03-01

    Electrons have spin as well as charge. At low-temperatures the spin relaxation time can be much longer than other time scales. Non-equilibrium spins may therefore affect the transport properties of small ferromagnet-normal metal systems. Unlike the scalar charge, the spin has a direction. The electron transport properties can be manipulated by the magnetization direction of the ferromagnets. We will demonstrate how the transport through hybrid ferromagnet-normal metal devices can be understood in terms of a circuit theory in the spirit of the conventional analysis of conventional electronic circuits. This spin-circuit theory is based on elements like spin-resistance and spin-capacitance and simplifies the understanding of transport through complicated ferromagnet-normal metal systems.

  8. Nanostructured target fabrication with metal and semiconductor nanoparticles

    NASA Astrophysics Data System (ADS)

    Barberio, M.; Antici, P.

    2015-10-01

    The development of ultra-intense high-energy (≫1 J) short (<1 ps) laser pulses in the last decade has enabled the acceleration of high-energy short-pulse proton beams. A key parameter for enhancing the acceleration regime is the laser-to-target absorption, which heavily depends on the target structure and material. In this work, we present the realization of a nanostructured target with a sub-laser wavelength nano-layer in the front surface as a possible candidate for improving the absorption. The nanostructured film was realized by a simpler and cheaper method than using conventional lithographic techniques: A colloidal solution of metallic or semiconductor nanoparticles (NPs) was produced by laser ablation and, after a heating and sonication process, was spray-dried on the front surface of an aluminum target. The obtained nanostructured film with a thickness of 1 μm appears, at morphological and chemical analysis, uniformly nanostructured and distributed on the target surface without the presence of oxides or external contaminants. Finally, the size of the NPs can be tuned from tens to hundreds of nanometers simply by varying the growth parameters (i.e., irradiation time, fluence, and laser beam energy).

  9. Laser induced heating and emission of electrons from metallic targets

    NASA Astrophysics Data System (ADS)

    Bharuthram, R.; Tripathi, V. K.

    1999-08-01

    A high power laser incident on a metallic target heats the electrons in the skin layer within a few ps. For a specific dependence of electron-phonon collision frequency on electron temperature, ν∝ Te1/2, the steady state electron temperature profile turns out to be an exponential function of depth. The heated electrons raise the rate of thermionic emission. When the laser is significantly converted into a surface plasma wave the rate of heating and emission is considerably enhanced.

  10. Nonlocal microscopic theory of quantum friction between parallel metallic slabs

    SciTech Connect

    Despoja, Vito

    2011-05-15

    We present a new derivation of the friction force between two metallic slabs moving with constant relative parallel velocity, based on T=0 quantum-field theory formalism. By including a fully nonlocal description of dynamically screened electron fluctuations in the slab, and avoiding the usual matching-condition procedure, we generalize previous expressions for the friction force, to which our results reduce in the local limit. Analyzing the friction force calculated in the two local models and in the nonlocal theory, we show that for physically relevant velocities local theories using the plasmon and Drude models of dielectric response are inappropriate to describe friction, which is due to excitation of low-energy electron-hole pairs, which are properly included in nonlocal theory. We also show that inclusion of dissipation in the nonlocal electronic response has negligible influence on friction.

  11. Shock Compression of Metal Crystals: A Comparison of Eulerian and Lagrangian Elastic-Plastic Theories

    DTIC Science & Technology

    2014-11-01

    Shock Compression of Metal Crystals: A Comparison of Eulerian and Lagrangian Elastic- Plastic Theories by JD Clayton ARL-RP-0513...of Metal Crystals: A Comparison of Eulerian and Lagrangian Elastic- Plastic Theories JD Clayton Weapons and Materials Research Directorate, ARL...SUBTITLE Shock Compression of Metal Crystals: A Comparison of Eulerian and Lagrangian Elastic- Plastic Theories 5a. CONTRACT NUMBER 5b. GRANT

  12. Energy balance in laser ablation of metal targets

    SciTech Connect

    Sobral, H.; Villagran-Muniz, M.; Bredice, F.

    2005-10-15

    Laser-generated plasma was induced on metallic targets glued to a piezoelectric microphone and placed between the plates of a planar charged capacitor. The plasma generates a temporal redistribution of electric charge on the plates that can easily be measured by a resistor connected to the ground plate; this signal is proportional to the total number of ions removed by breakdown. Both the absorbed and scattered energies were simultaneously monitored by the photoacoustic signal and an energy meter. From these signals it was possible to determine the energy involved in each of the processes. Just above the ablation threshold most of the delivered energy is absorbed and the acoustic signal prevails compared to other contributions. Above this region, the electric signal, which is proportional to the energy involved in the ablation process, becomes dominant.

  13. Investigation of G4 theory for tansition metal thermochemistry.

    SciTech Connect

    Mayhall, N. J.; Raghavachari, K.; Redfern, P. C.; Curtiss, L. A.; Indiana Univ.

    2009-01-01

    An investigation of the performance of Gaussian-4 (G4) methods for the prediction of 3d transition metal thermochemistry is presented. Using the recently developed G3Large basis sets for atoms Sc-Zn, the G4 and G4(MP2) methods with scalar relativistic effects included are evaluated on a test set of 20 enthalpies of formation of transition metal-containing molecules. The G4(MP2) method is found to perform significantly better than the G4 method. The G4 method fails due to the poor convergence of the Moeller-Plesset perturbation theory at fourth-order in one case. The overall error for G4(MP2) of 2.84 kcal/mol is significantly larger than its previously reported performance for molecules containing main-group elements in the G3/05 test set. However, considering the relatively large uncertainties in the experimental enthalpies, the G4(MP2) method performs reasonably well. The performance of other composite methods based on G3 theory [G3(CCSD)//B3LYP and G3(MP2,CCSD)//B3LYP], as well as several density functional methods, are also presented in this paper. The results presented here will assist future development of composite model techniques suitable for use in transition metal-containing systems.

  14. Process for the fabrication of aluminum metallized pyrolytic graphite sputtering targets

    DOEpatents

    Makowiecki, Daniel M.; Ramsey, Philip B.; Juntz, Robert S.

    1995-01-01

    An improved method for fabricating pyrolytic graphite sputtering targets with superior heat transfer ability, longer life, and maximum energy transmission. Anisotropic pyrolytic graphite is contoured and/or segmented to match the erosion profile of the sputter target and then oriented such that the graphite's high thermal conductivity planes are in maximum contact with a thermally conductive metal backing. The graphite contact surface is metallized, using high rate physical vapor deposition (HRPVD), with an aluminum coating and the thermally conductive metal backing is joined to the metallized graphite target by one of four low-temperature bonding methods; liquid-metal casting, powder metallurgy compaction, eutectic brazing, and laser welding.

  15. Theory of the pairbreaking superconductor-metal transition in nanowires

    NASA Astrophysics Data System (ADS)

    Del Maestro, Adrian; Rosenow, Bernd; Sachdev, Subir

    2009-03-01

    We present a detailed description of a zero temperature phase transition between superconducting and diffusive metallic states in very thin wires due to a Cooper pair breaking mechanism. The dissipative critical theory contains current reducing fluctuations in the guise of both quantum and thermally activated phase slips. A full cross-over phase diagram is computed via an expansion in the inverse number of complex components of the superconducting order parameter (one in the physical case). The fluctuation corrections to the electrical ( σ) and thermal ( κ) conductivities are determined, and we find that σ has a non-monotonic temperature dependence in the metallic phase which may be consistent with recent experimental results on ultra-narrow wires. In the quantum critical regime, the ratio of the thermal to electrical conductivity displays a linear temperature dependence and thus the Wiedemann-Franz law is obeyed, with a new universal experimentally verifiable Lorenz number.

  16. The photochemistry of transition metal complexes using density functional theory.

    PubMed

    Garino, Claudio; Salassa, Luca

    2013-07-28

    The use of density functional theory (DFT) and time-dependent DFT (TD-DFT) to study the photochemistry of metal complexes is becoming increasingly important among chemists. Computational methods provide unique information on the electronic nature of excited states and their atomic structure, integrating spectroscopy observations on transient species and excited-state dynamics. In this contribution, we present an overview on photochemically active transition metal complexes investigated by DFT. In particular, we discuss a representative range of systems studied up to now, which include CO- and NO-releasing inorganic and organometallic complexes, haem and haem-like complexes dissociating small diatomic molecules, photoactive anti-cancer Pt and Ru complexes, Ru polypyridyls and diphosphino Pt derivatives.

  17. Theory of half-metallic ferrimagnetism in double perovskites.

    PubMed

    Erten, Onur; Meetei, O Nganba; Mukherjee, Anamitra; Randeria, Mohit; Trivedi, Nandini; Woodward, Patrick

    2011-12-16

    Double perovskites such as Sr(2)FeMoO(6) are rare examples of materials with half-metallic ground states and a ferrimagnetic T(c) above room temperature. We present a comprehensive theory of the temperature and disorder dependence of their magnetic properties by deriving and validating a new effective spin Hamiltonian for these materials, amenable to large-scale three-dimensional simulations. We show how disorder, ubiquitous in these materials, affects T(c), the magnetization, and the conduction electron polarization. We conclude with a novel proposal to enhance T(c) without sacrificing polarization.

  18. Application of Density Functional Theory to Systems Containing Metal Atoms

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.

    2006-01-01

    The accuracy of density functional theory (DFT) for problems involving metal atoms is considered. The DFT results are compared with experiment as well as results obtained using the coupled cluster approach. The comparisons include geometries, frequencies, and bond energies. The systems considered include MO2, M(OH)+n, MNO+, and MCO+2. The DFT works well for frequencies and geometries, even in case with symmetry breaking; however, some examples have been found where the symmetry breaking is quite severe and the DFT methods do not work well. The calculation of bond energies is more difficult and examples of successes as well as failures of DFT will be given.

  19. Industrial recovered-materials-utilization targets for the metals and metal-products industry

    SciTech Connect

    1980-03-01

    The National Energy Conservation Policy Act of 1978 directs DOE to set targets for increased utilization of energy-saving recovered materials for certain industries. These targets are to be established at levels representing the maximum feasible increase in utilization of recovered materials that can be achieved progressively by January 1, 1987 and is consistent with technical and economic factors. A benefit to be derived from the increased use of recoverable materials is in energy savings, as state in the Act. Therefore, emhasis on different industries in the metals sector has been related to their energy consumption. The ferrous industry (iron and steel, ferrour foundries and ferralloys), as defined here, accounts for approximately 3%, and all others for the remaining 3%. Energy consumed in the lead and zinc segments is less than 1% each. Emphasis is placed on the ferrous scrap users, followed by the aluminum and copper industries. A bibliography with 209 citations is included.

  20. Growing Fixed With Age: Lay Theories of Malleability Are Target Age-Specific.

    PubMed

    Neel, Rebecca; Lassetter, Bethany

    2015-11-01

    Beliefs about whether people can change ("lay theories" of malleability) are known to have wide-ranging effects on social motivation, cognition, and judgment. Yet rather than holding an overarching belief that people can or cannot change, perceivers may hold independent beliefs about whether different people are malleable-that is, lay theories may be target-specific. Seven studies demonstrate that lay theories are target-specific with respect to age: Perceivers hold distinct, uncorrelated lay theories of people at different ages, and younger targets are considered to be more malleable than older targets. Both forms of target-specificity are consequential, as target age-specific lay theories predict policy support for learning-based senior services and the rehabilitation of old and young drug users. The implications of target age-specific lay theories for a number of psychological processes, the social psychology of aging, and theoretical frameworks of malleability beliefs are discussed.

  1. Theory of the pairbreaking superconductor-metal transition in nanowires

    NASA Astrophysics Data System (ADS)

    Sachdev, Subir

    2009-03-01

    We present a detailed description of a zero temperature phase transition between superconducting and diffusive metallic states in very thin wires due to a Cooper pair breaking mechanism. The dissipative critical theory contains current reducing fluctuations in the guise of both quantum and thermally activated phase slips. A full cross-over phase diagram is computed via an expansion in the inverse number of complex components of the superconducting order parameter (one in the physical case). The fluctuation corrections to the electrical (σ) and thermal (κ) conductivities are determined, and we find that σ has a non-monotonic temperature dependence in the metallic phase which may be consistent with recent experimental results on ultra-narrow wires. In the quantum critical regime, the ratio of the thermal to electrical conductivity displays a linear temperature dependence and thus the Wiedemann-Franz law is obeyed, with a new universal experimentally verifiable Lorenz number. We also examined the influence of quenched disorder on the superconductor-metal transition. The self-consistent pairing eigenmodes of a quasi-one dimensional wire were determined numerically. Our results support the proposal by Hoyos et al./ (Phys. Rev. Lett. 99, 230601 (2007)) that the transition is described by the same strong disorder fixed point describing the onset of ferromagnetism in the quantum Ising model in a transverse field.

  2. A Theory of Eye Movements during Target Acquisition

    ERIC Educational Resources Information Center

    Zelinsky, Gregory J.

    2008-01-01

    The gaze movements accompanying target localization were examined via human observers and a computational model (target acquisition model [TAM]). Search contexts ranged from fully realistic scenes to toys in a crib to Os and Qs, and manipulations included set size, target eccentricity, and target-distractor similarity. Observers and the model…

  3. Uranium fluoride and metallic uranium as target materials for heavy-element experiments at SHIP

    NASA Astrophysics Data System (ADS)

    Kindler, Birgit; Ackermann, Dieter; Hartmann, Willi; Heßberger, Fritz Peter; Hofmann, Sigurd; Hübner, Annett; Lommel, Bettina; Mann, Rido; Steiner, Jutta

    2008-06-01

    In this contribution we describe the production and application of uranium targets for synthesis of heavy elements. The targets are prepared from uranium fluoride (UF 4) and from metallic uranium with thin carbon foils as backing. Targets of UF 4 were produced by thermal evaporation in a similar way as the frequently applied targets out of Bi, Bi 2O 3, Pb, PbS, SmF 3, and NdF 3, prepared mostly from isotopically enriched material [Birgit Kindler, et al., Nucl. Instr. and Meth. A 561 (2006) 107; Bettina Lommel, et al., Nucl. Instr. and Meth. A 561 (2006) 100]. In order to use more intensive beams and to avoid scattering of the reaction products in the target, metallic uranium is favorable. However, evaporation of metallic uranium is not feasible at a sustainable yield. Therefore, we established magnetron sputtering of metallic uranium. We describe production and properties of these targets. First irradiation tests show promising results.

  4. Nonlinear hyperbolic theory of thermal waves in metals

    NASA Technical Reports Server (NTRS)

    Wilhelm, H. E.; Choi, S. H.

    1975-01-01

    A closed-form solution for cylindrical thermal waves in metals is given based on the nonlinear hyperbolic system of energy-conservation and heat-flux relaxation equations. It is shown that heat released from a line source propagates radially outward with finite speed in the form of a thermal wave which exhibits a discontinuous wave front. Unique nonlinear thermal-wave solutions exist up to a critical amount of driving energy, i.e., for larger energy releases, the thermal flow becomes multivalued (occurrence of shock waves). By comparison, it is demonstrated that the parabolic thermal-wave theory gives, in general, a misleading picture of the profile and propagation of thermal waves and leads to physical (infinite speed of heat propagation) and mathematical (divergent energy integrals) difficulties. Attention is drawn to the importance of temporal heat-flux relaxation for the physical understanding of fast transient processes such as thermal waves and more general explosions and implosions.

  5. Theory of the spin-1 bosonic liquid metal - Equilibrium properties of liquid metallic deuterium

    NASA Technical Reports Server (NTRS)

    Oliva, J.; Ashcroft, N. W.

    1984-01-01

    The theory of a two-component quantum fluid comprised of spin-1/2 fermions and nonzero spin bosons is examined. This system is of interest because it embodies a possible quantum liquid metallic phase of highly compressed deuterium. Bose condensation is assumed present and the two cases of nuclear-spin-polarized and -unpolarized systems are considered. A significant feature in the unpolarized case is the presence of a nonmagnetic mode with quadratic dispersion owing its existence to nonzero boson spin. The physical character of this mode is examined in detail within a Bogoliubov approach. The specific heat, bulk modulus, spin susceptibility, and thermal expansion are all determined. Striking contrasts in the specific heats and thermal-expansion coefficients of the liquid and corresponding normal solid metallic phase are predicted.

  6. A Theory of Eye Movements during Target Acquisition

    PubMed Central

    Zelinsky, Gregory J.

    2008-01-01

    The gaze movements accompanying target localization were examined via human observers and a computational model (Target Acquisition Model, TAM). Search contexts ranged from fully realistic scenes, to toys in a crib, to Os and Qs, and manipulations included set size, target eccentricity, and target-distractor similarity. Observers and the model always previewed the same targets and searched the identical displays. Behavioral and simulated eye movements were analyzed for acquisition accuracy, efficiency, and target guidance. TAM's behavior generally fell within the behavioral mean's 95% confidence interval for all measures in each experiment/condition. This agreement suggests that a fixed-parameter model using spatio-chromatic filters and a simulated retina, when driven by the correct visual routines, can be a good general purpose predictor of human target acquisition behavior. PMID:18954205

  7. Assessing the performance of density functional theory for the electronic structure of metal-salens: the 3d(0)-metals.

    PubMed

    Sears, John S; Sherrill, C David

    2008-04-17

    A series of metal-salen complexes of the 3d(0) metals Sc(III), Ti(IV), V(V), Cr(VI), and Mn(VII) have been explored using high-level electronic structure methods including coupled-cluster theory with singles, doubles, and perturbative triples as well as complete active-space third-order perturbation theory. The performance of three common density functional theory approaches has been assessed for both the geometries and the relative energies of the low-lying electronic states. The nondynamical correlation effects are demonstrated to be extremely large in all of the systems examined. Although density functional theory provides reasonable results for some of the systems, the overall agreement is quite poor. This said, the density functional theory approaches are shown to outperform the single-reference perturbation theory and coupled-cluster theory approaches for cases of strong nondynamical correlation.

  8. The Contributions of Felix Bloch and W. V. Houston to the Electron Theory of Metals

    ERIC Educational Resources Information Center

    Rorschach, H. E., Jr.

    1970-01-01

    Discusses the contributions of Bloch and Houston to the electron theory of metals. Contains (1) a biographical note on W. V. Houston, (2) a review of the development of the electron theory of metals, and (3) a discussion of gravitationally induced electric fields. Bibliography. (LC)

  9. Analysis of Laser-Target Interaction. Volume 1. Theory

    DTIC Science & Technology

    1979-03-01

    Previously, a model was constructed to describe energy transfer to an aluminum alloy target A12024 by a plasma ignited over the target surface. 1,2 The...intensity absorbed by the three non- aluminum alloys is shown as a function of time. A similar plot for oxidized steel is given in Fig. 3. 5. Typical...such as aluminum or copper cover poorly con- ducting targets such as SS304 and Ti6Al4V. 347 For an aluminum target over an aluminum alloy , the substrate

  10. Process for the fabrication of aluminum metallized pyrolytic graphite sputtering targets

    DOEpatents

    Makowiecki, D.M.; Ramsey, P.B.; Juntz, R.S.

    1995-07-04

    An improved method is disclosed for fabricating pyrolytic graphite sputtering targets with superior heat transfer ability, longer life, and maximum energy transmission. Anisotropic pyrolytic graphite is contoured and/or segmented to match the erosion profile of the sputter target and then oriented such that the graphite`s high thermal conductivity planes are in maximum contact with a thermally conductive metal backing. The graphite contact surface is metallized, using high rate physical vapor deposition (HRPVD), with an aluminum coating and the thermally conductive metal backing is joined to the metallized graphite target by one of four low-temperature bonding methods; liquid-metal casting, powder metallurgy compaction, eutectic brazing, and laser welding. 11 figs.

  11. KNN classification of metallic targets using the magnetic polarizability tensor

    NASA Astrophysics Data System (ADS)

    Makkonen, J.; Marsh, L. A.; Vihonen, J.; Järvi, A.; Armitage, D. W.; Visa, A.; Peyton, A. J.

    2014-05-01

    Walk-through metal detectors are used at check points for preventing personnel and passengers from carrying threatening metallic objects, such as knives and guns, into a secure area. These systems are capable of detecting small metallic items, such as handcuff keys and blades, but are unable to distinguish accurately between threatening objects and innocuous items. This paper studies the extent to which a K-nearest-neighbour classifier can distinguish various kinds of metallic objects, such as knives, shoe shanks, belts and containers. The classifier uses features extracted from the magnetic polarizability tensor, which represents the electromagnetic properties of the object. The tests include distinguishing threatening objects from innocuous ones, classifying a set of objects into 13 classes, and distinguishing between several similar objects within an object class. A walk-through metal detection system is used as source for the test data, which consist of 835 scans and 67 objects. The results presented show a typical success rate of over 95% for recognizing threats, and over 85% for correct classification. In addition, we have shown that the system is capable of distinguishing between similar objects reliably. Overall, the method shows promise for the field of security screening and suggests the need for further research.

  12. Three-Dimensional Steerable Magnetic Field (3DSMF) Sensor System for Classification of Buried Metal Targets

    DTIC Science & Technology

    2006-07-01

    complex spatial magnetic field distributions With a conventional pulsed EMI metal detector , a current loop transmitter is placed in the vicinity of the...transmitter via a data acquisition and control system. The direction of the magnetic field and the field strength generated by a conventional loop EMI metal ... detector are a complex function of the distance of the antenna to the target. As the antenna is moved over the target, data are collected from

  13. Radiochemical Determination of Polonium in Liquid Metal Spallation Targets

    NASA Astrophysics Data System (ADS)

    Hammer, B.; Schumann, D.; Neuhausen, J.; Wohlmuther, M.; Türler, A.

    2014-05-01

    The MEGAPIE target, consisting of 82 litres of lead-bismuth eutectic (LBE), was irradiated close to the megawatt range (0.8 MW) from August to December 2006 in the SINQ facility at PSI. After a cooling period of 5 years, a post-irradiation examination (PIE) program was started and samples were taken from different positions in the target. In this paper we focus on the measurement of α-emitting 208-210Po in the MEGAPIE target. The experimental results are compared with theoretical predictions obtained by FLUKA and MCNPX calculations.

  14. Theory and modeling of light interactions with metallic nanostructures.

    SciTech Connect

    Montgomery, J. M.; Lee, T.-W.; Gray, S. K.; Louisiana State Univ.

    2008-08-13

    Metallic nanostructures such as systems containing metal nanoparticles or nanostructured metal films are intriguing systems of much current interest. Surface plasmons, i.e., special electronic excitations near the metallic surfaces, can then be excited in these systems. Surface plasmons can be intense and localized, and correctly describing their behavior in complex systems can require numerically rigorous modeling techniques. The finite-difference time-domain (FDTD) method is one such technique. This review discusses results obtained mostly with the FDTD method concerning (1) local surface plasmon excitations of metal nanoparticles, (2) surface plasmon polariton propagation on layered structures, and (3) periodic hole arrays in metal films.

  15. Sensory Perception: An Overlooked Target of Occupational Exposure to Metals

    PubMed Central

    Gobba, Fabriziomaria

    2003-01-01

    The effect of exposure to industrial metals on sensory perception of workers has received only modest interest from the medical community to date. Nevertheless, some experimental and epidemiological data exist showing that industrial metals can affect vision, hearing and olfactory function, and a similar effect is also suggested for touch and taste. In this review the main industrial metals involved are discussed. An important limit in available knowledge is that, to date, the number of chemicals studied is relatively small. Another is that the large majority of the studies have evaluated the effect of a single chemical on a single sense. As an example, we know that mercury can impair hearing, smell, taste, touch and also vision, but we have scant idea if, in the same worker, a relation exists between impairments in different senses, or if impairments are independent. Moreover, workers are frequently exposed to different chemicals; a few available results suggest that a co-exposure may have no effect, or result in both an increase and a decrease of the effect, as observed for hearing loss, but this aspect certainly deserves much more study. As a conclusion, exposure to industrial metals can affect sensory perception, but knowledge of this effect is yet incomplete, and is largely inadequate especially for an estimation of “safe” thresholds of exposure. These data support the desirability of further good quality studies in this field. PMID:18365054

  16. Three-Dimensional Steerable Magnetic Field (3DSMF)Sensor System for Classification of Buried Metal Targets

    DTIC Science & Technology

    2006-07-01

    metallic anomalies. A commonly used sensor for UXO detection is the EMI metal detector . Conventional EMI metal detectors , using either frequency-domain...spatial magnetic field distributions [1]. With a conventional pulsed EMI metal detector , a current loop transmitter is placed in the vicinity of the...loop EMI metal detector are a complex function of the distance of the antenna to the target. As the antenna is moved over the target, data are

  17. Postsynthetic Tuning of Metal-Organic Frameworks for Targeted Applications.

    PubMed

    Islamoglu, Timur; Goswami, Subhadip; Li, Zhanyong; Howarth, Ashlee J; Farha, Omar K; Hupp, Joseph T

    2017-02-08

    Metal-organic frameworks (MOFs) are periodic, hybrid, atomically well-defined porous materials that typically form by self-assembly and consist of inorganic nodes (metal ions or clusters) and multitopic organic linkers. MOFs as a whole offer many intriguing properties, including ultrahigh porosity, tunable chemical functionality, and low density. These properties point to numerous potential applications, including gas storage, chemical separations, catalysis, light harvesting, and chemical sensing, to name a few. Reticular chemistry, or the linking of molecular building blocks into predetermined network structures, has been employed to synthesize thousands of MOFs. Given the vast library of candidate nodes and linkers, the number of potentially synthetically accessible MOFs is enormous. Nevertheless, a powerful complementary approach to obtain specific structures with desired chemical functionality is to modify known MOFs after synthesis. This approach is particularly useful when incorporation of particular chemical functionalities via direct synthesis is challenging or impossible. The challenges may stem from limited stability or solubility of precursors, unwanted secondary reactivity of precursors, or incompatibility of functional groups with the conditions needed for direct synthesis. MOFs can be postsynthetically modified by replacing the metal nodes and/or organic linkers or via functionalization of the metal nodes and/or organic linkers. Here we describe some of our efforts toward the development and application of postsynthetic strategies for imparting desired chemical functionalities in MOFs of known topology. The techniques include methods for functionalizing MOF nodes, i.e., solvent-assisted ligand incorporation (SALI) and atomic layer deposition in MOFs (AIM) as well as a method to replace structural linkers, termed solvent-assisted linker exchange (SALE), also known as postsynthethic exchange (PSE). For each functionalization strategy, we first describe

  18. Simultaneous detection of multiple DNA targets based on encoding metal ions.

    PubMed

    Zheng, Lichun; Li, Xiaoyan; Liu, Panpan; Wu, Guofan; Lu, Xiaoquan; Liu, Xiuhui

    2014-02-15

    We present a novel strategy for simultaneous electrochemical detection of multiple DNA targets based on the use of different encoding metal ions as tags. The principle of this scheme is that metal ions bound to metallothionein (MT) molecules can be released down after hybridization with DNA targets and then be detected by stripping voltammetry. The novel detection probes, ssDNA/MT conjugates, covered with different metal ions were synthesized for the first time, then three encoding metal ions (Zn(2+), Cd(2+), and Pb(2+)) were used to differentiate the signals of three virus DNA due to their well-defined anodic stripping peaks at -1.13 V (Zn), -0.78 V (Cd), and -0.52 V (Pb) at BiFE, respectively. The anodic peak currents increased linearly with the concentrations of DNA targets in the range from 0.1 nM to 10nM with a detection limit of 33 pM. In addition, the one-base mismatched target was effectively discriminated from the complementary target. The described results demonstrated that this method possesses high sensitivity and selectivity for multi-target DNA assay and has great potential in applications for detection of even more targets in biological assays, particularly immunoassays.

  19. Air Force, Cyberpower, Targeting: Airpower Lessons for an Air Force Cyberpower Targeting Theory

    DTIC Science & Technology

    2013-06-01

    clarity of what to target still appears vague . An analysis of Air Force Doctrine Document (AFDD) 3-60, Targeting, yields no further explanation...resources to deprive their use, strike at “ nerve centers,” government buildings, railways, stock exchange, and attack the population itself to affect

  20. Precision Sheet Metal. Progress Record and Theory Outline.

    ERIC Educational Resources Information Center

    Connecticut State Dept. of Education, Hartford. Div. of Vocational-Technical Schools.

    This combination progress record and course outline is designed for use by individuals teaching a course in precision sheet metal. Included among the topics addressed in the course are the following: employment opportunities in metalworking, measurement and layout, orthographic projection, precision sheet metal drafting, simple layout, hand tools,…

  1. Targeted Removal of Bioavailable Metal as a Detoxification Strategy for Carbon Nanotubes

    PubMed Central

    Liu, Xinyuan; Guo, Lin; Morris, Daniel; Kane, Agnes B.; Hurt, Robert H.

    2008-01-01

    There is substantial evidence for toxicity and/or carcinogenicity upon inhalation of pure transition metals in fine particulate form. Carbon nanotube catalyst residues may trigger similar metal-mediated toxicity, but only if the metal is bioavailable and not fully encapsulated within fluid-protective carbon shells. Recent studies have documented the presence of bioavailable iron and nickel in a variety of commercial as-produced and vendor “purified” nanotubes, and the present article examines techniques to avoid or remove this bioavailable metal. First, data are presented on the mechanisms potentially responsible for free metal in “purified” samples, including kinetic limitations during metal dissolution, the re-deposition or adsorption of metal on nanotube outer surfaces, and carbon shell damage during last-step oxidation or one-pot purification. Optimized acid treatment protocols are presented for targeting the free metal, considering the effects of acid strength, composition, time, and conditions for post-treatment water washing. Finally, after optimized acid treatment, it is shown that the remaining, non-bioavailable (encapsulated) metal persists in a stable and biologically unavailable form up to two months in an in vitro biopersistence assay, suggesting that simple removal of bioavailable (free) metal is a promising strategy for reducing nanotube health risks. PMID:19255622

  2. Modelling of Surfaces. Part 1: Monatomic Metallic Surfaces Using Equivalent Crystal Theory

    NASA Technical Reports Server (NTRS)

    Bozzolo, Guillermo; Ferrante, John; Rodriguez, Agustin M.

    1994-01-01

    We present a detailed description of equivalent crystal theory focusing on its application to the study of surface structure. While the emphasis is in the structure of the algorithm and its computational aspects, we also present a comprehensive discussion on the calculation of surface energies of metallic systems with equivalent crystal theory and other approaches. Our results are compared to experiment and other semiempirical as well as first-principles calculations for a variety of fcc and bcc metals.

  3. Results of thermal test of metallic molybdenum disk target and fast-acting valve testing

    SciTech Connect

    Virgo, M.; Chemerisov, S.; Gromov, R.; Jonah, C.; Vandegrift, G. F.

    2016-12-01

    This report describes the irradiation conditions for thermal testing of helium-cooled metallic disk targets that was conducted on March 9, 2016, at the Argonne National Laboratory electron linac. The four disks in this irradiation were pressed and sintered by Oak Ridge National Laboratory from molybdenum metal powder. Two of those disks were instrumented with thermocouples. Also reported are results of testing a fast-acting-valve system, which was designed to protect the accelerator in case of a target-window failure.

  4. On the estimation of target depth using the single transmit multiple receive metal detector array

    NASA Astrophysics Data System (ADS)

    Ho, K. C.; Gader, P. D.

    2012-06-01

    This paper investigates the use of the Single Transmit Multiple Receive (STMR) metal detector (MD) array to estimate the depth of metal targets, such as 155mm shells. The depth estimation problem using MD has been investigated by a number of researchers and the processing was performed along the down-track. The proposed method takes a different approach by exploring the MD responses in cross-track to achieve the depth estimation. It is found that the normalized energy spread of the MD output is narrower for shallow targets and wider for deeper targets. Based on this observation, a method is derived to estimate the depth of a target. Experimental results from the data collected at an U.S. Army test site validate the performance of the proposed depth estimator.

  5. The dynamics of molecular interactions and chemical reactions at metal surfaces: testing the foundations of theory.

    PubMed

    Golibrzuch, Kai; Bartels, Nils; Auerbach, Daniel J; Wodtke, Alec M

    2015-04-01

    We review studies of molecular interactions and chemical reactions at metal surfaces, emphasizing progress toward a predictive theory of surface chemistry and catalysis. For chemistry at metal surfaces, a small number of central approximations are typically made: (a) the Born-Oppenheimer approximation of electronic adiabaticity, (b) the use of density functional theory at the generalized gradient approximation level, (c) the classical approximation for nuclear motion, and (d) various reduced-dimensionality approximations. Together, these approximations constitute a provisional model for surface chemical reactivity. We review work on some carefully studied examples of molecules interacting at metal surfaces that probe the validity of various aspects of the provisional model.

  6. The Dynamics of Molecular Interactions and Chemical Reactions at Metal Surfaces: Testing the Foundations of Theory

    NASA Astrophysics Data System (ADS)

    Golibrzuch, Kai; Bartels, Nils; Auerbach, Daniel J.; Wodtke, Alec M.

    2015-04-01

    We review studies of molecular interactions and chemical reactions at metal surfaces, emphasizing progress toward a predictive theory of surface chemistry and catalysis. For chemistry at metal surfaces, a small number of central approximations are typically made: (a) the Born-Oppenheimer approximation of electronic adiabaticity, (b) the use of density functional theory at the generalized gradient approximation level, (c) the classical approximation for nuclear motion, and (d) various reduced-dimensionality approximations. Together, these approximations constitute a provisional model for surface chemical reactivity. We review work on some carefully studied examples of molecules interacting at metal surfaces that probe the validity of various aspects of the provisional model.

  7. Progress in alkaline peroxide dissolution of low-enriched uranium metal and silicide targets

    SciTech Connect

    Chen, L.; Dong, D.; Buchholz, B.A.; Vandegrift, G.F.; Wu, D.

    1996-12-31

    This paper reports recent progress on two alkaline peroxide dissolution processes: the dissolution of low-enriched uranium metal and silicide (U{sub 3}Si{sub 2}) targets. These processes are being developed to substitute low-enriched for high-enriched uranium in targets used for production of fission-product {sup 99}Mo. Issues that are addressed include (1) dissolution kinetics of silicide targets, (2) {sup 99}Mo lost during aluminum dissolution, (3) modeling of hydrogen peroxide consumption, (4) optimization of the uranium foil dissolution process, and (5) selection of uranium foil barrier materials. Future work associated with these two processes is also briefly discussed.

  8. Formation of periodic structures upon laser ablation of metal targets in liquids

    SciTech Connect

    Kazakevich, Pavel V; Simakin, Aleksandr V; Shafeev, Georgii A

    2005-09-30

    Experimental data on the formation of ordered microstructures produced upon ablation of metal targets in liquids irradiated by a copper vapour laser or a pulsed Nd:YAG laser are presented. The structures were obtained on brass, bronze, copper, and tungsten substrates immersed in distilled water or ethanol. As a result of multiple-pulse laser ablation by a scanning beam, ordered microcones with pointed vertexes are formed on the target surface. The structures are separated by deep narrow channels. The structure period was experimentally shown to increase linearly with diameter of the laser spot on the target surface. (interaction of laser radiation with matter)

  9. Peptide-Metal Organic Framework Swimmers that Direct the Motion toward Chemical Targets.

    PubMed

    Ikezoe, Yasuhiro; Fang, Justin; Wasik, Tomasz L; Shi, Menglu; Uemura, Takashi; Kitagawa, Susumu; Matsui, Hiroshi

    2015-06-10

    Highly efficient and robust chemical motors are expected for the application in microbots that can selectively swim toward targets and accomplish their tasks in sensing, labeling, and delivering. However, one of major issues for such development is that current artificial swimmers have difficulty controlling their directional motion toward targets like bacterial chemotaxis. To program synthetic motors with sensing capability for the target-directed motion, we need to develop swimmers whose motions are sensitive to chemical gradients in environments. Here we create a new intelligent biochemical swimmer by integrating metal organic frameworks (MOFs) and peptides that can sense toxic heavy metals in solution and swim toward the targets. With the aid of Pb-binding enzymes, the peptide-MOF motor can directionally swim toward PbSe quantum dots (QD) by sensing pH gradient and eventually complete the motion as the swimmer reaches the highest gradient point at the target position in solution. This type of technology could be evolved to miniaturize chemical robotic systems that sense target chemicals and swim toward target locations.

  10. High heat flux accelerator targets cooling with liquid-metal jet impingement

    NASA Astrophysics Data System (ADS)

    Silverman, I.; Arenshtam, A.; Kijel, D.; Nagler, A.

    2005-12-01

    Accelerator targets for radioisotope production generate very high density of thermal energy in the target material, which absorbs the particles beam. The design of these targets requires efficient heat removal techniques in order to preserve the integrity of the target. Normal average heat fluxes from these targets are around 1 kW/cm2 and may reach order of magnitude higher values at hot spots. Few techniques exist to deal with such high heat fluxes. One of them is jet impingement that has been proved to be able to deal with heat fluxes as high as 40 kW/cm2 using water as coolant. However, this requires very high jet velocities of more than 100 m/s. A few theoretical and experimental studies indicate that liquid-metal coolants (e.g., gallium or gallium alloys) can improve the heat transfer efficiency in this configuration. Experimental cooling loops based on water and liquid-metal jet impingement have been designed and built at Soreq to evaluate this method. For the current liquid-metal system an eutectic alloy of gallium and indium (GaIn) is used. Initial experiments demonstrate that the GaIn cooling system can deal with heat flux of about 2 kW/cm2 over an area of 1 cm2. The jet velocity is less than 4 m/s and the required differential pressure from the pump is less than 1 bar.

  11. Modification of base-side {sup 99}MO production processes for LEU metal-foil targets.

    SciTech Connect

    Vandegrift, G. F.; Leonard, R. A.; Aase, S.; Sedlet, J.; Koma, Y.; Conner, C.; Clark, C. R.; Meyer, M. K.

    1999-09-30

    Argonne National Laboratory is cooperating with the National Atomic Energy Commission of the Argentine Republic (CNEA) to convert their {sup 99}Mo production process, which uses high enriched uranium (HEU), to low-enriched uranium (LEU), The program is multifaceted; however, discussed in this paper are (1) results of laboratory experiments to develop means for substituting LEU metal-foil targets into the current process and (2) preparation of uranium-alloy or uranium-metal/aluminum-dispersion targets. Although {sup 99}Mo production is a multi-step process, the first two steps (target dissolution and primary molybdenum recovery) are by far the most important in the conversion. Commonly, once molybdenum is separated from the bulk of the uranium, the remainder of the process need not be modified. Our results show that up to this point in our study, conversion of the CNEA process to LEU appears viable.

  12. A study on target recognition fusion algorithm based on fuzzy theory

    NASA Astrophysics Data System (ADS)

    Han, Feng; Yang, WanHai

    2008-03-01

    In the process of the multi-sensors target recognition fusion, focused on the problem that it is difficult to determine the reliability of each sensor and how the data measured by different sensors are fused, a multi-sensor target recognition fusion method based on fuzzy theory is proposed. The mutual supportability of multiple sensors is obtained from the correlation function. Then by the membership function, the reliability of information provide by each sensor is gained. Finally, the supposed fusion result of multi-sensors target recognition can be produced on the basis of fuzzy integration function. The method is simple computationally and can objectively reflect the reliability of each sensor and interrelationship between these sensors. By applying the method to the target recognition, the simulation experiment shows that it can identify the target accurately and is an effective and feasible multi-sensors target recognition fusion method.

  13. Control of Structure in Conventional Friction Stir Welds through a Kinematic Theory of Metal Flow

    NASA Technical Reports Server (NTRS)

    Rubisoff, H.A.; Schneider, J.A.; Nunes, A.C.

    2009-01-01

    In friction stir welding (FSW), a rotating pin is translated along a weld seam so as to stir the sides of the seam together. Metal is prevented from flowing up the pin, which would result in plowing/cutting instead of welding, by a shoulder on the pin. In conventional FSW, the weld metal rests on an "anvil", which supports the heavy "plunge" load on the tool. In this study, both embedded tungsten wires along and copper plating on the faying surfaces were used to trace the flow of AA2219 weld metal around the C-FSW tool. The effect of tool rotational speed, travel speed, plunge load, and pin thread pitch on the resulting weld metal flow was evaluated. Plan, longitudinal, and transverse section x-ray radiographs were examined to trace the metal flow paths. The results are interpreted in terms of a kinematic theory of metal flow in FSW.

  14. Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals

    USGS Publications Warehouse

    Sherman, David M.

    1987-01-01

    Electronic transitions between the Fe-Fe bonding and Fe-Fe antibonding orbitals results in the optically-induced intervalence charge transfer bands observed in the electronic spectra of mixed valence minerals. Such transitions are predicted to be polarized along the metal-metal bond direction, in agreement with experimental observations.

  15. Ab Initio Theory of Coherent Laser-Induced Magnetization in Metals

    NASA Astrophysics Data System (ADS)

    Berritta, Marco; Mondal, Ritwik; Carva, Karel; Oppeneer, Peter M.

    2016-09-01

    We present the first materials specific ab initio theory of the magnetization induced by circularly polarized laser light in metals. Our calculations are based on nonlinear density matrix theory and include the effect of absorption. We show that the induced magnetization, commonly referred to as inverse Faraday effect, is strongly materials and frequency dependent, and demonstrate the existence of both spin and orbital induced magnetizations which exhibit a surprisingly different behavior. We show that for nonmagnetic metals (such as Cu, Au, Pd, Pt) and antiferromagnetic metals the induced magnetization is antisymmetric in the light's helicity, whereas for ferromagnetic metals (Fe, Co, Ni, FePt) the imparted magnetization is only asymmetric in the helicity. We compute effective optomagnetic fields that correspond to the induced magnetizations and provide guidelines for achieving all-optical helicity-dependent switching.

  16. Reactor target from metal chromium for "pure" high-intensive artificial neutrino source

    NASA Astrophysics Data System (ADS)

    Gavrin, V. N.; Kozlova, Yu. P.; Veretenkin, E. P.; Logachev, A. V.; Logacheva, A. I.; Lednev, I. S.; Okunkova, A. A.

    2017-01-01

    The paper presents the first results of development of manufacturing technology of metallic chromium targets from highly enriched isotope 50Cr for irradiation in a high flux nuclear reactor to obtain a compact high intensity neutrino source with low content of radionuclide impurities and minimum losses of enriched isotope. The main technological stages are the hydrolysis of chromyl fluoride, the electrochemical reduction of metallic chromium, the hot isostatic pressing of chromium powder and the electrical discharge machining of chromium bars. The technological stages of hot isostatic pressing of chromium powder and of electrical discharge machining of Cr rods have been tested.

  17. Metal/dendrimer nanocomposites for enhanced optical breakdown: acoustic characterization and initial targeted cell uptake study

    NASA Astrophysics Data System (ADS)

    Tse, Christine; Lesniak, Wojciech; Balogh, Lajos P.; Ye, Jing Yong; O'Donnell, Matthew

    2007-02-01

    Metal/dendrimer nanocomposites (DNCs) uniquely combine the properties of metallic clusters and the biofriendly polymer host in a nanosized hybrid particle. DNCs can biochemically target tissues and locally reduce femtosecond optical breakdown thresholds, making highly precise and selective photodisruption possible. In this study, we have used high-frequency acoustic monitoring of bubble production dynamics to investigate how DNC properties, solution concentration, and optical parameters affect threshold reduction, actual waiting time, and mechanical characteristics of breakdown. Breakdown is defined here as bubble production with an onset of less than 20 seconds after laser exposure. DNC properties varied include metal content (silver, gold) and terminal group (amino-NH II, glycidol-OH, and carboxyl- COOH) which determine pH values. Results indicate that DNC metal content markedly influences solution threshold reduction, while DNC terminal group (and thus net surface charge) and solution concentration influence the details of breakdown at these reduced threshold fluences. {Ag(0)} DNCs reduce breakdown threshold fluence 1-2 orders of magnitude more than {Au(0)} DNCs. Furthermore, concentrated DNC solutions and DNCs carrying a net negative charge (carboxyl terminal groups) increase bubble production up to four times and shorten waiting time for breakdown from seconds to milliseconds. Increasing laser fluence for a given DNC solution concentration also shortens breakdown waiting time. Lastly, utilizing the fluorescence properties of silver nanocomposites, we use confocal microscopy to examine KB cell uptake of folate targeted silver DNCs. Cells incubated with folate targeted silver DNCs exhibit a measurable increase of intracellular fluorescence compared to control cells (no DNC incubation). However, while we observe a threshold reduction in KB cells incubated with 500nM folate-targeted DNC solution, there is no threshold reduction in cells incubated with 50nM folate-targeted

  18. Steam Reforming on Transition-metal Carbides from Density-functional Theory

    SciTech Connect

    Vojvodic, Aleksandra

    2012-05-11

    A screening study of the steam reforming reaction on clean and oxygen covered early transition-metal carbides surfaces is performed by means of density-functional theory calculations. It is found that carbides provide a wide spectrum of reactivities, from too reactive via suitable to too inert. Several molybdenum-based systems are identified as possible steam reforming catalysts. The findings suggest that carbides provide a playground for reactivity tuning, comparable to the one for pure metals.

  19. Catalytic and photocatalytic transformations on metal nanoparticles with targeted geometric and plasmonic properties.

    PubMed

    Linic, Suljo; Christopher, Phillip; Xin, Hongliang; Marimuthu, Andiappan

    2013-08-20

    Heterogeneous catalysis by metals was among the first enabling technologies that extensively relied on nanoscience. The early intersections of catalysis and nanoscience focused on the synthesis of catalytic materials with high surface to volume ratio. These synthesis strategies mainly involved the impregnation of metal salts on high surface area supports. This would usually yield quasi-spherical nanoparticles capped by low-energy surface facets, typically with closely packed metal atoms. These high density areas often function as the catalytically active surface sites. Unfortunately, strategies to control the functioning surface facet (i.e., the geometry of active sites that performs catalytic turnover) are rare and represent a significant challenge in our ability to fine-tune and optimize the reactive surfaces. Through recent developments in colloidal chemistry, chemists have been able to synthesize metallic nanoparticles of both targeted size and desired shape. This has opened new possibilities for the design of heterogeneous catalytic materials, since metal nanoparticles of different shapes are terminated with different surface facets. By controlling the surface facet exposed to reactants, we can start affecting the chemical transformations taking place on the metal particles and changing the outcome of catalytic processes. Controlling the size and shape of metal nanoparticles also allows us to control the optical properties of these materials. For example, noble metals nanoparticles (Au, Ag, Cu) interact with UV-vis light through an excitation of localized surface plasmon resonance (LSPR), which is highly sensitive to the size and shape of the nanostructures. This excitation is accompanied by the creation of short-lived energetic electrons on the surface of the nanostructure. We showed recently that these energetic electrons could drive photocatalytic transformations on these nanostructures. The photocatalytic, electron-driven processes on metal nanoparticles

  20. A ROTATING METAL BAND TARGET FOR PION PRODUCTION AT MUON COLLIDERS.

    SciTech Connect

    KING,B.J.; SIMOS,N.; WEGGEL,R.V.; MOKHOV,N.V.

    2002-01-18

    A conceptual design is presented for a high power pion production target for muon colliders that is based on a rotating metal band. Three candidate materials are considered for the target band: inconel alloy 718, titanium alloy 6Al-4V grade 5 and nickel. A pulsed proton beam tangentially intercepts a chord of the target band that is inside a 20 Tesla tapered solenoidal magnetic pion capture channel similar to designs previously considered for muon colliders and neutrino factories. The target band has a radius of 2.5 meters and is continuously rotated at approximately 1 m/s to carry heat away from the production region and through a water cooling tank. The mechanical layout and cooling setup of the target are described, including the procedure for the routine replacement of the target band. A rectangular band cross section is assumed, optionally with I-beam struts to enhance stiffness and minimize mechanical vibrations. Results are presented from realistic MARS Monte Carlo computer simulations of the pion yield and energy deposition in the target and from ANSYS finite element calculations for the corresponding shock heating stresses. The target scenario is found to perform satisfactorily and with conservative safety margins for multi-MW pulsed proton beams.

  1. Analysis of metal-matrix composite structures. I - Micromechanics constitutive theory. II - Laminate analyses

    NASA Technical Reports Server (NTRS)

    Arenburg, R. T.; Reddy, J. N.

    1991-01-01

    The micromechanical constitutive theory is used to examine the nonlinear behavior of continuous-fiber-reinforced metal-matrix composite structures. Effective lamina constitutive relations based on the Abouli micromechanics theory are presented. The inelastic matrix behavior is modeled by the unified viscoplasticity theory of Bodner and Partom. The laminate constitutive relations are incorporated into a first-order deformation plate theory. The resulting boundary value problem is solved by utilizing the finite element method. Attention is also given to computational aspects of the numerical solution, including the temporal integration of the inelastic strains and the spatial integration of bending moments. Numerical results the nonlinear response of metal matrix composites subjected to extensional and bending loads are presented.

  2. Resonances and circuit theory for the interaction of metallic disks and annuli with an electromagnetic field

    NASA Astrophysics Data System (ADS)

    Chui, S. T.; Du, J. J.; Yau, S. T.

    2014-11-01

    To understand the nature of the electromagnetic resonances of finite metallic surfaces, we formulate a rigorous and rapidly convergent circuit theory for the interaction of a metallic disk and a metallic annulus with an electromagnetic field. Expressions for the current induced and the resonance condition are derived. A new understanding of the nature of the resonances is obtained. For half of the resonances we find a divergent electric field at the edge of the disk, even though it is smooth in shape. For the disk, we compare with previous results using vector spheroidal wave functions and found good agreement for the resonance condition. Our approach can be generalized to other finite surfaces.

  3. Density functional theory optimized basis sets for gradient corrected functionals: 3d transition metal systems.

    PubMed

    Calaminici, Patrizia; Janetzko, Florian; Köster, Andreas M; Mejia-Olvera, Roberto; Zuniga-Gutierrez, Bernardo

    2007-01-28

    Density functional theory optimized basis sets for gradient corrected functionals for 3d transition metal atoms are presented. Double zeta valence polarization and triple zeta valence polarization basis sets are optimized with the PW86 functional. The performance of the newly optimized basis sets is tested in atomic and molecular calculations. Excitation energies of 3d transition metal atoms, as well as electronic configurations, structural parameters, dissociation energies, and harmonic vibrational frequencies of a large number of molecules containing 3d transition metal elements, are presented. The obtained results are compared with available experimental data as well as with other theoretical data from the literature.

  4. Perturbation theory of solid-liquid interfacial free energies of bcc metals.

    PubMed

    Warshavsky, Vadim B; Song, Xueyu

    2012-09-01

    A perturbation theory is used to calculate bcc solid-liquid interfacial free energies of metallic systems with embedded-atom model potentials. As a reference system for bcc crystals we used a single-occupancy cell, hard-sphere bcc system. Good agreements between the perturbation theory results and the corresponding results from simulations are found. The strategy to extract hard-sphere bcc solid-liquid interfacial free energies may have broader applications for other crystal lattices.

  5. Critical quasiparticle theory applied to heavy fermion metals near an antiferromagnetic quantum phase transition.

    PubMed

    Abrahams, Elihu; Wölfle, Peter

    2012-02-28

    We use the recently developed critical quasiparticle theory to derive the scaling behavior associated with a quantum critical point in a correlated metal. This is applied to the magnetic-field induced quantum critical point observed in YbRh(2)Si(2), for which we also derive the critical behavior of the specific heat, resistivity, thermopower, magnetization and susceptibility, the Grüneisen coefficient, and the thermal expansion coefficient. The theory accounts very well for the available experimental results.

  6. Theory for self-consistent interplay between light and nanomaterials strongly modified by metallic nanostructures.

    PubMed

    Ishikawa, Akira; Osono, Katsuya; Nobuhiro, Atsushi; Mizumoto, Yoshihiko; Torimoto, Tsukasa; Ishihara, Hajime

    2013-03-28

    The design of the interplay between light and nanomaterials by the effect of localized-surface-plasmon resonance in metallic nanostructures is a fascinating subject, and recently, a lot of research has been carried out from both fundamental and applicational points of view. In this paper, we demonstrate the theories for describing the self-consistent interplay between the electronic states in the nanomaterials, the localized surface plasmons in the metallic nanostructures, and the light field, which provides insight into how the photoexcitation processes are modified through microscopic energy exchanges. As examples of such demonstrations, we show two cases, i.e., the interaction between a single metallic nanosphere and a quantum dot, and that between metallic nanostructures forming a nanogap and dimer molecules, where a peculiar dependence of photoexcitation processes on the distance between the metallic nanostructure and the absorbers arises depending on the respective characteristics of their interplay.

  7. Morphology of meteoroid and space debris craters on LDEF metal targets

    NASA Technical Reports Server (NTRS)

    Love, S. G.; Brownlee, D. E.; King, N. L.; Hoerz, F.

    1994-01-01

    We measured the depths, average diameters, and circularity indices of over 600 micrometeoroid and space debris craters on various metal surfaces exposed to space on the Long Duration Exposure Facility (LDEF) satellite, as a test of some of the formalisms used to convert the diameters of craters on space-exposed surfaces into penetration depths for the purpose of calculating impactor sizes or masses. The topics covered include the following: targe materials orientation; crater measurements and sample populations; effects of oblique impacts; effects of projectile velocity; effects of crater size; effects of target hardness; effects of target density; and effects of projectile properties.

  8. Morphology of meteoroid and space debris craters on LDEF metal targets

    NASA Astrophysics Data System (ADS)

    Love, S. G.; Brownlee, D. E.; King, N. L.; Hoerz, F.

    1994-03-01

    We measured the depths, average diameters, and circularity indices of over 600 micrometeoroid and space debris craters on various metal surfaces exposed to space on the Long Duration Exposure Facility (LDEF) satellite, as a test of some of the formalisms used to convert the diameters of craters on space-exposed surfaces into penetration depths for the purpose of calculating impactor sizes or masses. The topics covered include the following: targe materials orientation; crater measurements and sample populations; effects of oblique impacts; effects of projectile velocity; effects of crater size; effects of target hardness; effects of target density; and effects of projectile properties.

  9. Thermally induced breakup of metallic nanowires: experiment and theory.

    PubMed

    Schnedlitz, Martin; Lasserus, Maximilian; Knez, Daniel; Hauser, Andreas W; Hofer, Ferdinand; Ernst, Wolfgang E

    2017-04-05

    We present time-resolved transmission electron microscopy studies of the degradation of Au, Ag, Cu and Ni nanowires deposited on a heated support. The wires are grown under fully inert conditions in superfluid helium droplets and deposited onto amorphous carbon. The inherent stability of these pristine metal nanowires with diameters below 10 nm is investigated in the absence of any stabilizers, templates or solvents. The phenomenon of Rayleigh-breakup, a consequence of diffusion processes along the wire surfaces, is analysed in situ via scans over time and support temperature. Our experimental efforts are combined with simulations based on a novel model featuring a cellular automaton to emulate surface diffusion. Based on this model, correlations between the material parameters and actual breakup behaviour are studied.

  10. Theory of strain in single-layer transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Rostami, Habib; Roldán, Rafael; Cappelluti, Emmanuele; Asgari, Reza; Guinea, Francisco

    2015-11-01

    Strain engineering has emerged as a powerful tool to modify the optical and electronic properties of two-dimensional crystals. Here we perform a systematic study of strained semiconducting transition metal dichalcogenides. The effect of strain is considered within a full Slater-Koster tight-binding model, which provides us with the band structure in the whole Brillouin zone (BZ). From this, we derive an effective low-energy model valid around the K point of the BZ, which includes terms up to second order in momentum and strain. For a generic profile of strain, we show that the solutions for this model can be expressed in terms of the harmonic oscillator and double quantum well models, for the valence and conduction bands respectively. We further study the shift of the position of the electron and hole band edges due to uniform strain. Finally, we discuss the importance of spin-strain coupling in these 2D semiconducting materials.

  11. Optical steering of thermally generated microbubbles in a liquid for targeted metallic nanoparticle delivery

    NASA Astrophysics Data System (ADS)

    Krishnappa, Arjun; Abeywickrema, Ujitha; Banerjee, Partha

    2016-09-01

    A novel mathematical model is developed to investigate the behavior of thermally generated microbubbles in the presence of optical radiation to understand the mechanism of their steering. Forces acting on a bubble are studied in detail using a general force model. It has been proposed that these microbubbles with agglomerated metallic nanoparticles can be used for targeted drug delivery. The model can be extended to include the steering of bubbles with agglomerated silver or gold nanoparticles on their surface.

  12. Changes in the emission properties of metallic targets upon exposure to repetitively pulsed laser radiation

    NASA Astrophysics Data System (ADS)

    Konov, V. I.; Pimenov, S. M.; Prokhorov, A. M.; Chapliev, N. I.

    1988-02-01

    A scanning electron microscope and a repetitively pulsed CO2 laser are used to reveal the relationships which govern the correlation of the transforming metal surface microrelief with the emission of charged particles and the surface luminescence upon exposure to multipulse laser focusing. It is shown that the effect of sorption and laser-stimulated desorption on the emission signals can manifest itself in different ways depending on the current oscillation mode in the target-vacuum chamber circuit.

  13. Theory of unidirectional spin Hall magnetoresistance in heavy-metal/ferromagnetic-metal bilayers

    NASA Astrophysics Data System (ADS)

    Zhang, Steven S.-L.; Vignale, Giovanni

    2016-10-01

    Recent experiments have revealed nonlinear features of the magnetoresistance in metallic bilayers consisting of a heavy metal (HM) and a ferromagnetic metal (FM). A small change in the longitudinal resistance of the bilayer has been observed when reversing the direction of either the applied in-plane current or the magnetization. We attribute such nonlinear transport behavior to the spin-polarization dependence of the electron mobility in the FM layer acting in concert with the spin accumulation induced in that layer by the spin Hall current originating in the bulk of the HM layer. An explicit expression for the nonlinear magnetoresistance is derived based on a simple drift-diffusion model, which shows that the nonlinear magnetoresistance appears at the first order of the spin Hall angle, and changes sign when the current is reversed, in agreement with the experimental observations. We also discuss possible ways to control sign of the nonlinear magnetoresistance and to enhance the magnitude of the effect.

  14. Generalized Rate Theory for Void and Bubble Swelling and its Application to Plutonium Metal Alloys

    SciTech Connect

    Allen, P. G.; Wolfer, W. G.

    2015-10-16

    In the classical rate theory for void swelling, vacancies and self-interstitials are produced by radiation in equal numbers, and in addition, thermal vacancies are also generated at the sinks, primarily at edge dislocations, at voids, and at grain boundaries. In contrast, due to the high formation energy of self-interstitials for normal metals and alloys, their thermal generation is negligible, as pointed out by Bullough and Perrin [1]. However, recent DFT calculations of the formation energy of self-interstitial atoms in bcc metals [2,3] have revealed that the sum of formation and migration energies for self-interstitials atoms (SIA) is of the same order of magnitude as for vacancies. This is illustrated in Fig. 1 that shows the ratio of the activation energies for thermal generation of SIA and vacancies. For fcc metals, this ratio is around three, but for bcc metals it is around 1.5. Reviewing theoretical predictions of point defect properties in δ-Pu [4], this ratio could possibly be less than one. As a result, thermal generation of SIA in bcc metals and in plutonium must be taken into considerations when modeling the growth of voids and of helium bubbles, and the classical rate theory (CRT) for void and bubble swelling must be extended to a generalized rate theory (GRT).

  15. Multilayer Relaxation and Surface Energies of FCC and BCC Metals Using Equivalent Crystal Theory

    NASA Technical Reports Server (NTRS)

    Rodriguez, Agustin M.; Bozzolo, Guillermo; Ferrante, John

    1993-01-01

    The multilayer relaxation of fcc and bcc metal surfaces is calculated using equivalent crystal theory. The results for changes in interplanar spacings of planes close to the surface and the ensuing surface energies are discussed in reference to other theoretical results and compared to available experimental data. The calculation includes high-index surfaces for which no other theoretical results are known.

  16. Asymmetric partitioning of metals among cluster anions and cations generated via laser ablation of mixed aluminum/Group 6 transition metal targets.

    PubMed

    Waller, Sarah E; Mann, Jennifer E; Jarrold, Caroline Chick

    2013-02-28

    While high-power laser ablation of metal alloys indiscriminately produces gas-phase atomic ions in proportion to the abundance of the various metals in the alloy, gas-phase ions produced by moderate-power laser ablation sources coupled with molecular beams are formed by more complicated mechanisms. A mass spectrometric study that directly compares the mass distributions of cluster anions and cations generated from laser ablation of pure aluminum, an aluminum/molybdenum mixed target, and an aluminum/tungsten mixed target is detailed. Mass spectra of anionic species generated from the mixed targets showed that both tungsten and molybdenum were in higher abundance in the negatively charged species than in the target material. Mass spectra of the cationic species showed primarily Al(+) and aluminum oxide and hydroxide cluster cations. No molybdenum- or tungsten-containing cluster cations were definitively assigned. The asymmetric distribution of aluminum and Group 6 transition metals in cation and anion cluster composition is attributed to the low ionization energy of atomic aluminum and aluminum suboxide clusters. In addition, the propensity of both molybdenum and tungsten to form metal oxide cluster anions under the same conditions that favor metallic aluminum cluster anions is attributed to differences in the optical properties of the surface oxide that is present in the metal powders used to prepare the ablation targets. Mechanisms of mixed metal oxide clusters are considered.

  17. Demonstration of {sup 99}MO production using LEU metal-foil targets in the cintichem process.

    SciTech Connect

    Vandegrift, G. F.; Conner, C.; Hofman, G. L.; Snelgrove, J. L.; Mutalib, A.; Purwadi, B.; Adang, H. G.; Hotman, L.; Kadarisman, Sukmana, A.; Dicky, T. J.; Sriyono, Suripto, A.; Lutfi, D.; Amin; Basiran, A.; Gogo, A.; Sarwani; Taryo, T.

    1999-09-30

    In March and September 1999, demonstrations of the irradiation, disassembly, and processing of LEU metal foil targets were performed in the Indonesian BATAN PUSPIPTEK Facilities. These demonstrations showed that (1) irradiation and disassembly can be performed so that the uranium foil can be easily removed from the target body, and (2) with only minor changes to the current process, the LEU foil can produce yield and purity of the {sup 99}Mo product at least as great as that obtained with the HEU target. Further, because of these modifications, two hours are cut from the processing time, and the liquid waste volume is reduced. Results of these demonstrations will be presented along with conclusions and plans for future work.

  18. Preparation of mixed metal thin films by a PVD method using several kinds of powder targets

    NASA Astrophysics Data System (ADS)

    Suda, Yoshiaki; Kawasaki, Hiroharu; Ohshima, Tamiko; Yagyu, Yoshihito; Ihara, Takeshi; Yamauchi, Makiko; Plasma process; application Team

    2015-09-01

    Bismuth iron garnet (Bi3Fe5O12) and aluminum doped zinc oxide (AZO) thin films were prepared by a physical vapor deposition method using mixed metal powder targets. The X-ray powder diffraction and X-ray photoelectron spectroscopy results suggest that crystalline thin films can be prepared using powder targets with quality similar to that of the films prepared using bulk targets. Bi3Fe5O12 films prepared using the pulsed laser deposition method were Bi rich, which may be due to the lower melting temperature of Bi (544 K) compared with that of Fe (1811 K). The mean transparency and resistivity of the AZO films prepared by the sputtering method were approximately 79%-84% and 0.5 - 1.4 ohm/cm, respectively.

  19. Screening of active metals for reactive adsorption desulfurization adsorbent using density functional theory

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Zhao, Liang; Xu, Chunming; Wang, Yuxian; Gao, Jinsen

    2017-03-01

    To explore characteristics of active metals for reactive adsorption desulfurization (RADS) technology, the adsorption of thiophene on M (100) (M = Cr, Mo, Co, Ni, Cu, Au, and Ag) surfaces was systematically studied by density functional theory with vdW correction (DFT + D3). We found that, in all case, the most stable molecular adsorption site was the hollow site and adsorptive capabilities of thiophene followed the order: Cr > Mo > Co ≈ Ni > Cu > Au ≈ Ag. By analyzing the nature of binding between thiophene and corresponding metals and the electronic structure of metals, the excessive activities of Cr and Mo were found to have a negative regeneration, the passive activities of Au and Ag were found to have an inactive adsorption for RADS adsorbent alone, while Ni and Co have appropriate characteristics as the active metals for RADS, followed by Cu.

  20. Toward understanding metal-binding specificity of porphyrin: a conceptual density functional theory study.

    PubMed

    Feng, Xin-Tian; Yu, Jian-Guo; Lei, Ming; Fang, Wei-Hai; Liu, Shubin

    2009-10-08

    Porphyrin is a key cofactor of hemoproteins. The complexes it forms with divalent metal cations such as Fe, Mg, and Mn compose an important category of compounds in biological systems, serving as a reaction center for a number of essential life processes. Employing density functional theory (DFT) and conceptual DFT approaches, the structural properties and reactivity of (pyridine)(n)-M-porphyrin complexes were systematically studied for the following selection of divalent metal cations: Mg, Ca, Cr, Mn, Co, Ni, Cu, Zn, Ru, and Cd with n varying from 0, 1, to 2. Metal selectivity and porphyrin specificity were investigated from the perspective of both structural and reactivity properties. Quantitative structural and reactivity relationships have been discovered between bonding interactions, charge distributions, and DFT chemical reactivity descriptors. These results are beneficial to our understanding of the chemical reactivity and metal cation specificity for heme-containing enzymes and other metalloproteins alike.

  1. Thermophysical properties of simple liquid metals: A brief review of theory

    NASA Technical Reports Server (NTRS)

    Stroud, David

    1993-01-01

    In this paper, we review the current theory of the thermophysical properties of simple liquid metals. The emphasis is on thermodynamic properties, but we also briefly discuss the nonequilibrium properties of liquid metals. We begin by defining a 'simple liquid metal' as one in which the valence electrons interact only weakly with the ionic cores, so that the interaction can be treated by perturbation theory. We then write down the equilibrium Hamiltonian of a liquid metal as a sum of five terms: the bare ion-ion interaction, the electron-electron interaction, the bare electron-ion interaction, and the kinetic energies of electrons and ions. Since the electron-ion interaction can be treated by perturbation, the electronic part contributes in two ways to the Helmholtz free energy: it gives a density-dependent term which is independent of the arrangement of ions, and it acts to screen the ion-ion interaction, giving rise to effective ion-ion pair potentials which are density-dependent, in general. After sketching the form of a typical pair potential, we briefly enumerate some methods for calculating the ionic distribution function and hence the Helmholtz free energy of the liquid: monte Carlo simulations, molecular dynamics simulations, and thermodynamic perturbation theory. The final result is a general expression for the Helmholtz free energy of the liquid metal. It can be used to calculate a wide range of thermodynamic properties of simple metal liquids, which we enumerate. They include not only a range of thermodynamic coefficients of both metals and alloys, but also many aspects of the phase diagram, including freezing curves of pure elements and phase diagrams of liquid alloys (including liquidus and solidus curves). We briefly mention some key discoveries resulting from previous applications of this method, and point out that the same methods work for other materials not normally considered to be liquid metals (such as colloidal suspensions, in which the

  2. Theory of transmission of light by sub-wavelength cylindrical holes in metallic films.

    PubMed

    García, N; Bai, Ming

    2006-10-16

    This paper presents theory and finite-difference time-domain (FDTD) calculations for a single and arrays of sub-wavelength cylindrical holes in metallic films presenting large transmission. These calculations are in excellent agreement with experimental measurements. This effect has to be understood in terms of the properties exhibited by the dielectric constant of metals which cannot be treated as ideal metals for the purpose of transmission and diffraction of light. We discuss the cases of well-differentiated metals silver and tungsten. It is found that the effect of surface plasmons or other surface wave excitations due to a periodical set of holes or other roughness at the surface is marginal. The effect can enhance but also can depress the transmission of the arrays as shown by theory and experiments. The peak structure observed in experiments is a consequence of the interference of the wavefronts transmitted by each hole and is determined by the surface array period independently of the material. Without large transmission through a single hole there is no large transmission through the array. We found that in the case of Ag which at the discussed frequencies is a metal there are cylindrical plasmons at the wall of the hole, as reported by Economu et al 30 years ago, that enhanced the transmission. But it turns out, as will be explained, that for the case of W which behaves as a dielectric, there is also a large transmission when compared with that of an ideal metal waveguide at large wavelengths. To deal with this problem one has to use the measured dielectric function of the metals. We discuss thoroughly all these cases and compare with the data. We notice that to discuss these data, for a single hole's transmission, in terms of the Bethe approximation of ideal metals is misleading. Therefore, the extraordinary enhancement of the transmission for the holes arrays versus the single hole does not exist.

  3. CO adsorption on transition metal clusters: Trends from density functional theory

    NASA Astrophysics Data System (ADS)

    Zeinalipour-Yazdi, Constantinos D.; Cooksy, Andrew L.; Efstathiou, Angelos M.

    2008-05-01

    This work reports for the first time the trends for carbon monoxide (CO) chemisorption on transition metal clusters present in supported metal catalysts. In particular, the energetic, structural and infrared adsorption characteristics of linearly (atop) CO adsorbed on transition metal nano-clusters of less than 10 Å in size were explored. Spin-unrestricted density functional theory (DFT) calculations were employed to explore the trends of CO adsorption energy (AM-CO) and C-O vibrational frequency (νCO) for clusters composed of Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt and Au. The effects of the transition metal electronic structure onto the adsorption energy of CO and the vibrational stretching frequency of C-O, and how these chemical parameters can be correlated to the catalytic activity of transition supported metal catalysts that involve the adsorption, surface diffusion, and C-O bond dissociation elementary steps in heterogeneous catalytic surface reactions, are discussed. Our findings show that an increase of the electronic d-shell occupancy and the principal quantum number (n) in transition metals causes an increase in the vibrational stretching frequency of the C-O bond. This trend is inconsistent with the classical Blyholder model for the metal-carbonyl bond.

  4. Sensor Reliability Evaluation Scheme for Target Classification Using Belief Function Theory

    PubMed Central

    Zhu, Jing; Luo, Yupin; Zhou, Jianjun

    2013-01-01

    In the target classification based on belief function theory, sensor reliability evaluation has two basic issues: reasonable dissimilarity measure among evidences, and adaptive combination of static and dynamic discounting. One solution to the two issues has been proposed here. Firstly, an improved dissimilarity measure based on dualistic exponential function has been designed. We assess the static reliability from a training set by the local decision of each sensor and the dissimilarity measure among evidences. The dynamic reliability factors are obtained from each test target using the dissimilarity measure between the output information of each sensor and the consensus. Secondly, an adaptive combination method of static and dynamic discounting has been introduced. We adopt Parzen-window to estimate the matching degree of current performance and static performance for the sensor. Through fuzzy theory, the fusion system can realize self-learning and self-adapting with the sensor performance changing. Experiments conducted on real databases demonstrate that our proposed scheme performs better in target classification under different target conditions compared with other methods. PMID:24351632

  5. Fast approximate EM induction modeling of metallic and UXO targets using a permeable prism

    NASA Astrophysics Data System (ADS)

    Asten, Michael W.; Duncan, Andrew C.

    2007-03-01

    The time-domain EM induction response of non-magnetic and magnetic targets can be approximated using a conductive permeable prism composed of six faces of conductive plates, each face being composed of a set of conductive ribbons. The effect of magnetic permeability is included by the use of two "apparent flux gathering" coefficients, and two "effective magnetic permeability" coefficients, in the axial and transverse directions. These four magnetic property coefficients are a function of physical properties and geometry of the target, but are independent of prism orientation relative to a transmitter. The approximation algorithm is computationally fast, allowing inversions for target parameters to be achieved in seconds. The model is tested on profiles acquired with a Geonics EM63 time-domain EM metal detector over a non-magnetic copper pipe target, and a steel artillery shell in horizontal and vertical orientations. Results show that this approximation to a permeable prism has a capability of fitting geometric, conductivity and magnetic parameters at both early and late sample times. The magnetic parameters show strong change from early to late times on the EMI decay curve, indicating that the magnetic properties of the target have non-linear characteristics. It is proposed that these magnetic parameters and the nature of their non-linearity may carry additional discrimination information for distinguishing between intact munitions and scrap in UXO studies.

  6. Bifunctional Coupling Agents for Radiolabeling of Biomolecules and Target-Specific Delivery of Metallic Radionuclides

    PubMed Central

    Liu, Shuang

    2008-01-01

    Receptor-based radiopharmaceuticals are of great current interest in early molecular imaging and radiotherapy of cancers, and provide a unique tool for target-specific delivery of radionuclides to the diseased tissues. In general, a target-specific radiopharmaceutical can be divided into four parts: targeting biomolecule (BM), pharmacokinetic modifying (PKM) linker, bifunctional coupling or chelating agent (BFC), and radionuclide. The targeting biomolecule serves as a “carrier” for specific delivery of the radionuclide. PKM linkers are used to modify radiotracer excretion kinetics. BFC is needed for radiolabeling of biomolecules with a metallic radionuclide. Different radiometals have significant difference in their coordination chemistry, and require BFCs with different donor atoms and chelator frameworks. Since the radiometal chelate can have a significant impact on physical and biological properties of the target-specific radiopharmaceutical, its excretion kinetics can be altered by modifying the coordination environment with various chelators or coligand, if needed. This review will focus on the design of BFCs and their coordination chemistry with technetium, copper, gallium, indium, yttrium and lanthanide radiometals. PMID:18538888

  7. Characteristics of flows of energetic atoms reflected from metal targets during ion bombardment

    NASA Astrophysics Data System (ADS)

    Kuzmichev, A.; Perevertaylo, V.; Tsybulsky, L.; Volpian, O.

    2016-07-01

    Particle number and energy reflection coefficients for energetic neutralized gas ions (Ar and O atoms) backscattered from metal targets during ion bombardment have been calculated using TRIM code. The energy distributions of reflected atoms are computed, too, and their dependence on the primary ion energy and the angle of ion incidence is determined. The obtained data confirm the possibility of employing energetic atoms reflection for generation of high energy neutral beams and point out to take this phenomenon into account under analysis of the ion technology for coating deposition.

  8. Release from ISOLDE molten metal targets under pulsed proton beam conditions

    NASA Astrophysics Data System (ADS)

    Lettry, J.; Catherall, R.; Cyvoct, G.; Evensen, A. H. M.; Lindroos, M.; Jonsson, O. C.; Kugler, E.; Schindl, K.; Ravn, H.; Wildner, E.; Drumm, P.; Obert, J.; Putaux, J. C.; Sauvage, J.

    1996-04-01

    By moving the ISOLDE mass separators from the 600 MeV Synchrocyclotron (SC) to the 1 GeV Proton-Synchrotron-Booster (PS) the instantaneous energy density of the proton beam went up by 3 orders of magnitude. The developments of the molten metal target units and the optimization of the PS proton beam to cope with the effects of the thermal shocks induced by the proton beam are described. The energy density of the PS proton beam was reduced by spatial defocusing and time staggered extraction of the four PS-accelerators. The release from lanthanum, lead and tin targets is discussed for different settings of the proton beam and compared to the release observed at ISOLDE-SC. The yields of Hg isotopes are presented.

  9. Chemical fractionation resulting from the hypervelocity impact process on metallic targets

    NASA Astrophysics Data System (ADS)

    Libourel, Guy; Ganino, Clément; Michel, Patrick; Nakamura, Akiko

    2016-10-01

    In a regime of hypervelocity impact cratering, the internal energy deposited in target + projectile region is large enough to melt and/or vaporize part of the material involved, which expands rapidly away from the impact site. Fast and energetic impact processes have therefore important chemical consequences on the projectile and target rock transformations during major impact events. Several physical and chemical processes occurred indeed in the short duration of the impact, e.g., melting, coating, mixing, condensation, crystallization, redox reactions, quenching, etc., all concurring to alter both projectile and target composition on the irreversible way.In order to document such hypervelocity impact chemical fractionation, we have started a program of impact experiments by shooting doped (27 trace elements) millimeter-sized basalt projectiles on metallic target using a two stages light gas gun. With impact velocity in the range from 0.25 to 7 km.s-1, these experiments are aimed i) to characterize chemically and texturally all the post-mortem materials (e.g., target, crater, impact melt, condensates, and ejectas), in order ii) to make a chemical mass balance budget of the process, and iii) to relate it to the kinetic energy involved in the hypervelocity impacts for scaling law purpose. Irrespective of the incident velocities, our preliminary results show the importance of redox processes, the significant changes in the ejecta composition (e.g., iron enrichment) and the systematic coating of the crater by the impact melt [1]. On the target side, characterizations of the microstructure of the shocked iron alloys to better constrain the shielding processes. We also show how these results have great implications in our understanding on the current surface properties of small bodies, and chiefly in the case of M-type asteroids. [1] Ganino C, Libourel G, Nakamura AM & Michel P (2015) Goldschmidt Abstracts, 2015 990.

  10. Irving Langmuir Prize Lecture - A predictive theory of transition metal surface catalysis

    NASA Astrophysics Data System (ADS)

    Norskov, Jens

    2015-03-01

    The lecture will outline a theory of heterogeneous catalysis that allows a detailed understanding of elementary chemical processes at transition metal surfaces and singles out the most important parameters determining catalytic activity and selectivity. It will be shown how scaling relations allow the identification of descriptors of catalytic activity and how they can be used to construct activity and selectivity maps. The maps can be used to define catalyst design rules and examples of their use will be given.

  11. Phishing for suitable targets in the Netherlands: routine activity theory and phishing victimization.

    PubMed

    Leukfeldt, E Rutger

    2014-08-01

    This article investigates phishing victims, especially the increased or decreased risk of victimization, using data from a cybercrime victim survey in the Netherlands (n=10,316). Routine activity theory provides the theoretical perspective. According to routine activity theory, several factors influence the risk of victimization. A multivariate analysis was conducted to assess which factors actually lead to increased risk of victimization. The model included background and financial data of victims, their Internet activities, and the degree to which they were "digitally accessible" to an offender. The analysis showed that personal background and financial characteristics play no role in phishing victimization. Among eight Internet activities, only "targeted browsing" led to increased risk. As for accessibility, using popular operating systems and web browsers does not lead to greater risk, while having up-to-date antivirus software as a technically capable guardian has no effect. The analysis showed no one, clearly defined group has an increased chance of becoming a victim. Target hardening may help, but opportunities for prevention campaigns aimed at a specific target group or dangerous online activities are limited. Therefore, situational crime prevention will have to come from a different angle. Banks could play the role of capable guardian.

  12. Theory and computation of hot carriers generated by surface plasmon polaritons in noble metals

    PubMed Central

    Bernardi, Marco; Mustafa, Jamal; Neaton, Jeffrey B.; Louie, Steven G.

    2015-01-01

    Hot carriers (HC) generated by surface plasmon polaritons (SPPs) in noble metals are promising for application in optoelectronics, plasmonics and renewable energy. However, existing models fail to explain key quantitative details of SPP-to-HC conversion experiments. Here we develop a quantum mechanical framework and apply first-principles calculations to study the energy distribution and scattering processes of HCs generated by SPPs in Au and Ag. We find that the relative positions of the s and d bands of noble metals regulate the energy distribution and mean free path of the HCs, and that the electron–phonon interaction controls HC energy loss and transport. Our results prescribe optimal conditions for HC generation and extraction, and invalidate previously employed free-electron-like models. Our work combines density functional theory, GW and electron–phonon calculations to provide microscopic insight into HC generation and ultrafast dynamics in noble metals. PMID:26033445

  13. Multiconfiguration pair-density functional theory: barrier heights and main group and transition metal energetics.

    PubMed

    Carlson, Rebecca K; Li Manni, Giovanni; Sonnenberger, Andrew L; Truhlar, Donald G; Gagliardi, Laura

    2015-01-13

    Kohn-Sham density functional theory, resting on the representation of the electronic density and kinetic energy by a single Slater determinant, has revolutionized chemistry, but for open-shell systems, the Kohn-Sham Slater determinant has the wrong symmetry properties as compared to an accurate wave function. We have recently proposed a theory, called multiconfiguration pair-density functional theory (MC-PDFT), in which the electronic kinetic energy and classical Coulomb energy are calculated from a multiconfiguration wave function with the correct symmetry properties, and the rest of the energy is calculated from a density functional, called the on-top density functional, that depends on the density and the on-top pair density calculated from this wave function. We also proposed a simple way to approximate the on-top density functional by translation of Kohn-Sham exchange-correlation functionals. The method is much less expensive than other post-SCF methods for calculating the dynamical correlation energy starting with a multiconfiguration self-consistent-field wave function as the reference wave function, and initial tests of the theory were quite encouraging. Here, we provide a broader test of the theory by applying it to bond energies of main-group molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy. Averaged over 56 data points, the mean unsigned error is 3.2 kcal/mol for MC-PDFT, as compared to 6.9 kcal/mol for Kohn-Sham theory with a comparable density functional. MC-PDFT is more accurate on average than complete active space second-order perturbation theory (CASPT2) for main-group small-molecule bond energies, alkyl bond dissociation energies, transition-metal-ligand bond energies, proton affinities, and the water dimerization energy.

  14. Photoactivatable metal complexes: from theory to applications in biotechnology and medicine

    PubMed Central

    Smith, Nichola A.; Sadler, Peter J.

    2013-01-01

    This short review highlights some of the exciting new experimental and theoretical developments in the field of photoactivatable metal complexes and their applications in biotechnology and medicine. The examples chosen are based on some of the presentations at the Royal Society Discussion Meeting in June 2012, many of which are featured in more detail in other articles in this issue. This is a young field. Even the photochemistry of well-known systems such as metal–carbonyl complexes is still being elucidated. Striking are the recent developments in theory and computation (e.g. time-dependent density functional theory) and in ultrafast-pulsed radiation techniques which allow photochemical reactions to be followed and their mechanisms to be revealed on picosecond/nanosecond time scales. Not only do some metal complexes (e.g. those of Ru and Ir) possess favourable emission properties which allow functional imaging of cells and tissues (e.g. DNA interactions), but metal complexes can also provide spatially controlled photorelease of bioactive small molecules (e.g. CO and NO)—a novel strategy for site-directed therapy. This extends to cancer therapy, where metal-based precursors offer the prospect of generating excited-state drugs with new mechanisms of action that complement and augment those of current organic photosensitizers. PMID:23776303

  15. Fighting Cancer with Transition Metal Complexes: From Naked DNA to Protein and Chromatin Targeting Strategies

    PubMed Central

    Palermo, Giulia; Magistrato, Alessandra; Riedel, Tina; von Erlach, Thibaud; Davey, Curt A.; Dyson, Paul J.

    2015-01-01

    Abstract Many transition metal complexes have unique physicochemical properties that can be efficiently exploited in medicinal chemistry for cancer treatment. Traditionally, double‐stranded DNA has been assumed to be the main binding target; however, recent studies have shown that nucleosomal DNA as well as proteins can act as dominant molecular binding partners. This has raised new questions about the molecular determinants that govern DNA versus protein binding selectivity, and has offered new ways to rationalize their biological activity and possible side effects. To address these questions, molecular simulations at an atomistic level of detail have been used to complement, support, and rationalize experimental data. Herein we review some relevant studies—focused on platinum and ruthenium compounds—to illustrate the power of state‐of‐the‐art molecular simulation techniques and to demonstrate how the interplay between molecular simulations and experiments can make important contributions to elucidating the target preferences of some promising transition metal anticancer agents. This contribution aims at providing relevant information that may help in the rational design of novel drug‐discovery strategies. PMID:26634638

  16. Live Site Demonstrations: Former Pole Mountain Target and Maneuver Area, Laramie, WY. MetalMapper Data Analysis for Pole Mountain Target and Maneuver Area

    DTIC Science & Technology

    2012-03-08

    FINAL REPORT Live Site Demonstrations: Former Pole Mountain Target and Maneuver Area, Laramie, WY MetalMapper Data Analysis for Pole...Mountain Target and Maneuver Area ESTCP Project MR-201157 March 2012 John Baptiste Parsons Standard Form 298 (Rev. 8/98) REPORT ...DOCUMENTATION PAGE Prescribed by ANSI Std. Z39.18 Form Approved OMB No. 0704-0188 The public reporting burden for this collection of information is

  17. Convection in molten pool created by a concentrated energy flux on a solid metal target

    SciTech Connect

    Dikshit, B.; Zende, G. R.; Bhatia, M. S.; Suri, B. M.

    2009-08-15

    During surface evaporation of metals by use of a concentrated energy flux such as electron beam or lasers, a liquid metal pool having a very high temperature gradient is formed around the hot zone created by the beam. Due to temperature dependence of surface tension, density, and depression of the evaporating surface caused by back pressure of the emitted vapor in this molten pool, a strong convective current sets in the molten pool. A proposition is made that this convection may pass through three different stages during increase in the electron beam power depending upon dominance of the various driving forces. To confirm this, convective heat transfer is quantified in terms of dimensionless Nusselt number and its evolution with power is studied in an experiment using aluminum, copper, and zirconium as targets. These experimentally determined values are also compared to the theoretical values predicted by earlier researchers to test the validity of their assumptions and to know about the type of flow in the melt pool. Thus, conclusion about the physical characteristics of flow in the molten pool of metals could be drawn by considering the roles of surface tension and curvature of the evaporating surface on the evolution of convective heat transfer.

  18. Design of antibody-functionalized carbon nanotubes filled with radioactivable metals towards a targeted anticancer therapy

    NASA Astrophysics Data System (ADS)

    Spinato, Cinzia; Perez Ruiz de Garibay, Aritz; Kierkowicz, Magdalena; Pach, Elzbieta; Martincic, Markus; Klippstein, Rebecca; Bourgognon, Maxime; Wang, Julie Tzu-Wen; Ménard-Moyon, Cécilia; Al-Jamal, Khuloud T.; Ballesteros, Belén; Tobias, Gerard; Bianco, Alberto

    2016-06-01

    In the present work we have devised the synthesis of a novel promising carbon nanotube carrier for the targeted delivery of radioactivity, through a combination of endohedral and exohedral functionalization. Steam-purified single-walled carbon nanotubes (SWCNTs) have been initially filled with radioactive analogues (i.e. metal halides) and sealed by high temperature treatment, affording closed-ended CNTs with the filling material confined in the inner cavity. The external functionalization of these filled CNTs was then achieved by nitrene cycloaddition and followed by the derivatization with a monoclonal antibody (Cetuximab) targeting the epidermal growth factor receptor (EGFR), overexpressed by several cancer cells. The targeting efficiency of the so-obtained conjugate was evaluated by immunostaining with a secondary antibody and by incubation of the CNTs with EGFR positive cells (U87-EGFR+), followed by flow cytometry, confocal microscopy or elemental analyses. We demonstrated that our filled and functionalized CNTs can internalize more efficiently in EGFR positive cancer cells.In the present work we have devised the synthesis of a novel promising carbon nanotube carrier for the targeted delivery of radioactivity, through a combination of endohedral and exohedral functionalization. Steam-purified single-walled carbon nanotubes (SWCNTs) have been initially filled with radioactive analogues (i.e. metal halides) and sealed by high temperature treatment, affording closed-ended CNTs with the filling material confined in the inner cavity. The external functionalization of these filled CNTs was then achieved by nitrene cycloaddition and followed by the derivatization with a monoclonal antibody (Cetuximab) targeting the epidermal growth factor receptor (EGFR), overexpressed by several cancer cells. The targeting efficiency of the so-obtained conjugate was evaluated by immunostaining with a secondary antibody and by incubation of the CNTs with EGFR positive cells (U87

  19. Coarse-grained density functional theories for metallic alloys: Generalized coherent-potential approximations and charge-excess functional theory

    NASA Astrophysics Data System (ADS)

    Bruno, Ezio; Mammano, Francesco; Fiorino, Antonino; Morabito, Emanuela V.

    2008-04-01

    The class of the generalized coherent-potential approximations (GCPAs) to the density functional theory (DFT) is introduced within the multiple scattering theory formalism with the aim of dealing with ordered or disordered metallic alloys. All GCPA theories are based on a common ansatz for the kinetic part of the Hohenberg-Kohn functional and each theory of the class is specified by an external model concerning the potential reconstruction. Most existing DFT implementations of CPA-based theories belong to the GCPA class. The analysis of the formal properties of the density functional defined by GCPA theories shows that it consists of marginally coupled local contributions. Furthermore, it is shown that the GCPA functional does not depend on the details of the charge density and that it can be exactly rewritten as a function of the appropriate charge multipole moments to be associated with each lattice site. A general procedure based on the integration of the qV laws is described that allows for the explicit construction of the same function. The coarse-grained nature of the GCPA density functional implies a great deal of computational advantages and is connected with the O(N) scalability of GCPA algorithms. Moreover, it is shown that a convenient truncated series expansion of the GCPA functional leads to the charge-excess functional (CEF) theory [E. Bruno , Phys. Rev. Lett. 91, 166401 (2003)], which here is offered in a generalized version that includes multipolar interactions. CEF and the GCPA numerical results are compared with status of art linearized augmented plane wave (LAPW) full-potential density functional calculations for 62 bcc- and fcc-based ordered CuZn alloys, in all the range of concentrations. Two facts clearly emerge from these extensive tests. In the first place, the discrepancies between GCPA and CEF results are always within the numerical accuracy of the calculations, both for the site charges and the total energies. In the second place, the

  20. Surveillance theory applied to virus detection: a case for targeted discovery

    USGS Publications Warehouse

    Bogich, Tiffany L.; Anthony, Simon J.; Nichols, James D.

    2013-01-01

    Virus detection and mathematical modeling have gone through rapid developments in the past decade. Both offer new insights into the epidemiology of infectious disease and characterization of future risk; however, modeling has not yet been applied to designing the best surveillance strategies for viral and pathogen discovery. We review recent developments and propose methods to integrate viral and pathogen discovery and mathematical modeling through optimal surveillance theory, arguing for a more targeted approach to novel virus detection guided by the principles of adaptive management and structured decision-making.

  1. Michel Borghini as a Mentor and Father of the Theory of Polarization in Polarized Targets

    NASA Astrophysics Data System (ADS)

    de Boer, Wim

    2016-02-01

    This paper is a contribution to the memorial session for Michel Borghini at the Spin 2014 conference in Bejing, honoring his pivotal role for the development of polarized targets in high energy physics. Borghini proposed for the first time the correct mechanism for dynamic polarization in polarized targets using organic materials doped with free radicals. In these amorphous materials the spin levels are broadened by spin-spin interactions and g-factor anisotropy, which allows a high dynamic polarization of nuclei by cooling of the spin-spin interaction reservoir. In this contribution I summarize the experimental evidence for this mechanism. These pertinent experiments were done at CERN in the years 1971 - 1974, when I was a graduate student under the guidance of Michel Borghini. I finish by shortly describing how Borghini’s spin temperature theory is now applied in cancer therapy.

  2. A brief perspective on the diverging theories of lymphatic targeting with colloids

    PubMed Central

    Siram, Karthik; Marslin, Gregory; Raghavan, Chellan Vijaya; Balakumar, Krishnamoorthy; Rahman, Habibur; Franklin, Gregory

    2016-01-01

    For targeted delivery of colloids to the lymphatic system, the colloids should efficiently reach and remain in the lymphatics for a considerable period of time. As per the current knowledge, diffusion and phagocytosis are the two mechanisms through which colloids reach the lymphatic system. Several parameters including particle size and charge have been shown to affect the direct uptake of colloids by the lymphatic system. Although many researchers attached ligands on the surface of colloids to promote phagocytosis-mediated lymphatic delivery, another school of thought suggests avoidance of phagocytosis by use of carriers like polyethylene glycol (PEG)ylated colloids to impart stealth attributes and evade phagocytosis. In this perspective, we weigh up the paradoxical theories and approaches available in the literature to draw conclusions on the conditions favorable for achieving efficient lymphatic targeting of colloids. PMID:27366065

  3. A brief perspective on the diverging theories of lymphatic targeting with colloids.

    PubMed

    Siram, Karthik; Marslin, Gregory; Raghavan, Chellan Vijaya; Balakumar, Krishnamoorthy; Rahman, Habibur; Franklin, Gregory

    2016-01-01

    For targeted delivery of colloids to the lymphatic system, the colloids should efficiently reach and remain in the lymphatics for a considerable period of time. As per the current knowledge, diffusion and phagocytosis are the two mechanisms through which colloids reach the lymphatic system. Several parameters including particle size and charge have been shown to affect the direct uptake of colloids by the lymphatic system. Although many researchers attached ligands on the surface of colloids to promote phagocytosis-mediated lymphatic delivery, another school of thought suggests avoidance of phagocytosis by use of carriers like polyethylene glycol (PEG)ylated colloids to impart stealth attributes and evade phagocytosis. In this perspective, we weigh up the paradoxical theories and approaches available in the literature to draw conclusions on the conditions favorable for achieving efficient lymphatic targeting of colloids.

  4. FFLO strange metal and quantum criticality in two dimensions: Theory and application to organic superconductors

    NASA Astrophysics Data System (ADS)

    Piazza, Francesco; Zwerger, Wilhelm; Strack, Philipp

    2016-02-01

    Increasing the spin imbalance in superconductors can spatially modulate the gap by forming Cooper pairs with finite momentum. For large imbalances compared to the Fermi energy, the inhomogeneous FFLO superconductor ultimately becomes a normal metal. There is mounting experimental evidence for this scenario in two-dimensional (2D) organic superconductors in large in-plane magnetic fields; this is complemented by ongoing efforts to realize this scenario in coupled tubes of atomic Fermi gases with spin imbalance. Yet, a theory for the phase transition from a metal to an FFLO superconductor has not been developed so far and the universality class has remained unknown. Here we propose and analyze a spin imbalance driven quantum critical point between a 2D metal and an FFLO phase in anisotropic electron systems. We derive the effective action for electrons and bosonic FFLO pairs at this quantum phase transition. Using this action, we predict non-Fermi-liquid behavior and the absence of quasiparticles at a discrete set of hot spots on the Fermi surfaces. This results in strange power laws in thermodynamics and response functions, which are testable with existing experimental setups on 2D organic superconductors and may also serve as signatures of the elusive FFLO phase itself. The proposed universality class is distinct from previously known quantum critical metals and, because its critical fluctuations appear already in the pairing channel, a promising candidate for naked metallic quantum criticality over extended temperature ranges.

  5. Theory of quantum metal to superconductor transitions in highly conducting systems

    SciTech Connect

    Spivak, B.

    2010-04-06

    We derive the theory of the quantum (zero temperature) superconductor to metal transition in disordered materials when the resistance of the normal metal near criticality is small compared to the quantum of resistivity. This can occur most readily in situations in which 'Anderson's theorem' does not apply. We explicitly study the transition in superconductor-metal composites, in an swave superconducting film in the presence of a magnetic field, and in a low temperature disordered d-wave superconductor. Near the point of the transition, the distribution of the superconducting order parameter is highly inhomogeneous. To describe this situation we employ a procedure which is similar to that introduced by Mott for description of the temperature dependence of the variable range hopping conduction. As the system approaches the point of the transition from the metal to the superconductor, the conductivity of the system diverges, and the Wiedemann-Franz law is violated. In the case of d-wave (or other exotic) superconductors we predict the existence of (at least) two sequential transitions as a function of increasing disorder: a d-wave to s-wave, and then an s-wave to metal transition.

  6. Adsorptive desulfurization with metal-organic frameworks: A density functional theory investigation

    NASA Astrophysics Data System (ADS)

    Chen, Zhiping; Ling, Lixia; Wang, Baojun; Fan, Huiling; Shangguan, Ju; Mi, Jie

    2016-11-01

    The contribution of each fragment of metal-organic frameworks (MOFs) to the adsorption of sulfur compounds were investigated using density functional theory (DFT). The involved sulfur compounds are dimethyl sulfide (CH3SCH3), ethyl mercaptan (CH3CH2SH) and hydrogen sulfide (H2S). MOFs with different organic ligands (NH2-BDC, BDC and NDC), metal centers structures (M, M-M and M3O) and metal ions (Zn, Cu and Fe) were used to study their effects on sulfur species adsorption. The results revealed that, MOFs with coordinatively unsaturated sites (CUS) have the strongest binding strength with sulfur compounds, MOFs with NH2-BDC substituent group ligand comes second, followed by that with saturated metal center, and the organic ligands without substituent group has the weakest adsorption strength. Moreover, it was also found that, among different metal ions (Fe, Zn and Cu), MOFs with unsaturated Fe has the strongest adsorption strength for sulfur compounds. These results are consistent with our previous experimental observations, and therefore provide insights on the better design of MOFs for desulfurization application.

  7. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan

    2016-12-01

    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

  8. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells.

    PubMed

    Setzler, Brian P; Zhuang, Zhongbin; Wittkopf, Jarrid A; Yan, Yushan

    2016-12-06

    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW(-1) in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

  9. Time-domain response of a metal detector to a target buried in soil with frequency-dependent magnetic susceptibility

    NASA Astrophysics Data System (ADS)

    Das, Y.

    2006-05-01

    The work reported in this paper is a part of on-going studies to clarify how and to what extent soil electromagnetic properties affect the performance of induction metal detectors widely used in humanitarian demining. This paper studies the specific case of the time-domain response of a small metallic sphere buried in a non-conducting soil half-space with frequency-dependent complex magnetic susceptibility. The sphere is chosen as a simple prototype for the small metal parts in low-metal landmines, while soil with dispersive magnetic susceptibility is a good model for some soils that are known to adversely affect the performance of metal detectors. The included analysis and computations extend previous work which has been done mostly in the frequency domain. Approximate theoretical expressions for weakly magnetic soils are found to fit the experimental data very well, which allowed the estimation of soil model parameters, albeit in an ad hoc manner. Soil signal is found to exceed target signal (due to an aluminum sphere of radius 0.0127 m) in many cases, even for the weakly magnetic Cambodian laterite used in the experiments. How deep a buried target is detected depends on many other factors in addition to the relative strength of soil and target signals. A general statement cannot thus be made regarding detectability of a target in soil based on the presented results. However, computational results complemented with experimental data extend the understanding of the effect that soil has on metal detectors.

  10. s-wave elastic scattering of antihydrogen off atomic alkali-metal targets

    SciTech Connect

    Sinha, Prabal K.; Ghosh, A. S.

    2006-03-15

    We have investigated the s-wave elastic scattering of antihydrogen atoms off atomic alkali-metal targets (Li, Na, K, and Rb) at thermal energies (10{sup -16}-10{sup -4} a.u.) using an atomic orbital expansion technique. The elastic cross sections of these systems at thermal energies are found to be very high compared to H-H and H-He systems. The theoretical models employed in this study are so chosen to consider long-range forces dynamically in the calculation. The mechanism of cooling suggests that Li may be considered to be a good candidate as a buffer gas for enhanced cooling of antihydrogen atoms to ultracold temperature.

  11. Supersonic Propagation of a K-Shell Ionization Front in Metal Targets

    NASA Astrophysics Data System (ADS)

    Nilson, P. M.; Fiksel, G.; Solodov, A. A.; Stoeckl, C.; Mileham, C.; Theobald, W.; Davies, J. R.; Froula, D. H.; Betti, R.; Meyerhofer, D. D.

    2015-11-01

    The supersonic propagation of a K-shell ionization front has been measured in high-energy-density metal targets using 1-D monochromatic streaked x-ray imaging. The ionization front was driven by hot electrons generated by a 10-ps laser pulse focused to an intensity of 1018 W/cm2. The data show the ionization front travelling at 0 . 11 c +/- 0 . 02 c . The measurements are in good agreement with implicit-hybrid particle-in-cell and collisional-radiative code calculations that predict the hot-electron transport and the K-shell ionization front dynamics. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

  12. APPLICATION OF THE HARD AND SOFT, ACIDS AND BASES (HSAB) THEORY TO TOXICANT-TARGET INTERACTIONS

    PubMed Central

    LoPachin, Richard M.; Gavin, Terrence; DeCaprio, Anthony; Barber, David S.

    2011-01-01

    Many chemical toxicants and/or their active metabolites are electrophiles that cause cell injury by forming covalent bonds with nucleophilic targets on biological macromolecules. Covalent reactions between nucleophilic and electrophilic reagents are however discriminatory, since there is a significant degree of selectivity associated with these interactions. Over the course of the past few decades, the theory of Hard and Soft, Acid and Bases (HSAB) has proven to be a useful tool in predicting the outcome of such reactions. This concept utilizes the inherent electronic characteristic of polarizability to define, for example, reacting electrophiles and nucleophiles as either hard or soft. These HSAB definitions have been successfully applied to chemical-induced toxicity in biological systems. Thus, according to this principle, a toxic electrophile reacts preferentially with biological targets of similar hardness or softness. The soft/hard classification of a xenobiotic electrophile has obvious utility in discerning plausible biological targets and molecular mechanisms of toxicity. The purpose of this Perspective is to discuss the HSAB theory of electrophiles and nucleophiles within a toxicological framework. In principle, covalent bond formation can be described by using the properties of their outermost or frontier orbitals. Because these orbital energies for most chemicals can be calculated using quantum mechanical models, it is possible to quantify the relative softness (σ) or hardness (η) of electrophiles or nucleophiles and to subsequently convert this information into useful indices of reactivity. This atomic level information can provide insight into the design of corroborative laboratory research and thereby help investigators discern corresponding molecular sites and mechanisms of toxicant action. The use of HSAB parameters has also been instrumental in the development and identification of potential nucleophilic cytoprotectants that can scavenge toxic

  13. Application of the Hard and Soft, Acids and Bases (HSAB) theory to toxicant--target interactions.

    PubMed

    Lopachin, Richard M; Gavin, Terrence; Decaprio, Anthony; Barber, David S

    2012-02-20

    Many chemical toxicants and/or their active metabolites are electrophiles that cause cell injury by forming covalent bonds with nucleophilic targets on biological macromolecules. Covalent reactions between nucleophilic and electrophilic reagents are, however, discriminatory since there is a significant degree of selectivity associated with these interactions. Over the course of the past few decades, the theory of Hard and Soft, Acids and Bases (HSAB) has proven to be a useful tool in predicting the outcome of such reactions. This concept utilizes the inherent electronic characteristic of polarizability to define, for example, reacting electrophiles and nucleophiles as either hard or soft. These HSAB definitions have been successfully applied to chemical-induced toxicity in biological systems. Thus, according to this principle, a toxic electrophile reacts preferentially with biological targets of similar hardness or softness. The soft/hard classification of a xenobiotic electrophile has obvious utility in discerning plausible biological targets and molecular mechanisms of toxicity. The purpose of this perspective is to discuss the HSAB theory of electrophiles and nucleophiles within a toxicological framework. In principle, covalent bond formation can be described by using the properties of their outermost or frontier orbitals. Because these orbital energies for most chemicals can be calculated using quantum mechanical models, it is possible to quantify the relative softness (σ) or hardness (η) of electrophiles or nucleophiles and to subsequently convert this information into useful indices of reactivity. This atomic level information can provide insight into the design of corroborative laboratory research and thereby help investigators discern corresponding molecular sites and mechanisms of toxicant action. The use of HSAB parameters has also been instrumental in the development and identification of potential nucleophilic cytoprotectants that can scavenge toxic

  14. Theory and Modeling of RNA Structure and Interactions with Metal Ions and Small Molecules.

    PubMed

    Sun, Li-Zhen; Zhang, Dong; Chen, Shi-Jie

    2017-03-15

    In addition to continuous rapid progress in RNA structure determination, probing, and biophysical studies, the past decade has seen remarkable advances in the development of a new generation of RNA folding theories and models. In this article, we review RNA structure prediction models and models for ion-RNA and ligand-RNA interactions. These new models are becoming increasingly important for a mechanistic understanding of RNA function and quantitative design of RNA nanotechnology. We focus on new methods for physics-based, knowledge-based, and experimental data-directed modeling for RNA structures and explore the new theories for the predictions of metal ion and ligand binding sites and metal iondependent RNA stabilities. The integration of these new methods with theories about the cellular environment effects in RNA folding, such as molecular crowding and cotranscriptional kinetic effects, may ultimately lead to an all-encompassing RNA folding model. Expected final online publication date for the Annual Review of Biophysics Volume 46 is May 20, 2017. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

  15. Theory of the reaction dynamics of small molecules on metal surfaces

    SciTech Connect

    Jackson, Bret

    2016-09-09

    The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H2, H2O and CH4 on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimental data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).

  16. A multifunctional metal-organic framework based tumor targeting drug delivery system for cancer therapy

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-Gang; Dong, Zhi-Yue; Cheng, Hong; Wan, Shuang-Shuang; Chen, Wei-Hai; Zou, Mei-Zhen; Huo, Jia-Wei; Deng, He-Xiang; Zhang, Xian-Zheng

    2015-09-01

    Drug delivery systems (DDSs) with biocompatibility and precise drug delivery are eagerly needed to overcome the paradox in chemotherapy that high drug doses are required to compensate for the poor biodistribution of drugs with frequent dose-related side effects. In this work, we reported a metal-organic framework (MOF) based tumor targeting DDS developed by a one-pot, and organic solvent-free ``green'' post-synthetic surface modification procedure, starting from the nanoscale MOF MIL-101. Owing to the multifunctional surface coating, premature drug release from this DDS was prevented. Due to the pH responsive benzoic imine bond and the redox responsive disulfide bond at the modified surface, this DDS exhibited tumor acid environment enhanced cellular uptake and intracellular reducing environment triggered drug release. In vitro and in vivo results showed that DOX loaded into this DDS exhibited effective cancer cell inhibition with much reduced side effects.Drug delivery systems (DDSs) with biocompatibility and precise drug delivery are eagerly needed to overcome the paradox in chemotherapy that high drug doses are required to compensate for the poor biodistribution of drugs with frequent dose-related side effects. In this work, we reported a metal-organic framework (MOF) based tumor targeting DDS developed by a one-pot, and organic solvent-free ``green'' post-synthetic surface modification procedure, starting from the nanoscale MOF MIL-101. Owing to the multifunctional surface coating, premature drug release from this DDS was prevented. Due to the pH responsive benzoic imine bond and the redox responsive disulfide bond at the modified surface, this DDS exhibited tumor acid environment enhanced cellular uptake and intracellular reducing environment triggered drug release. In vitro and in vivo results showed that DOX loaded into this DDS exhibited effective cancer cell inhibition with much reduced side effects. Electronic supplementary information (ESI) available

  17. Application of the theory of optimal experiments to adaptive electromagnetic-induction sensing of buried targets.

    PubMed

    Liao, Xuejun; Carin, Lawrence

    2004-08-01

    A mobile electromagnetic-induction (EMI) sensor is considered for detection and characterization of buried conducting and/or ferrous targets. The sensor may be placed on a robot and, here, we consider design of an optimal adaptive-search strategy. A frequency-dependent magnetic-dipole model is used to characterize the target at EMI frequencies. The goal of the search is accurate characterization of the dipole-model parameters, denoted bythe vector theta; the target position and orientation are a subset of theta. The sensor position and operating frequency are denoted by the parameter vector p and a measurement is represented by the pair (p, O), where O denotes the observed data. The parametersp are fixed for a given measurement, but, in the context of a sequence of measurements p may be changed adaptively. In a locally optimal sequence of measurements, we desire the optimal sensor parameters, P(N+1) for estimation of theta, based on the previous measurements (p(n), On)n=1,N. The search strategy is based on the theory of optimal experiments, as discussed in detail and demonstrated via several numerical examples.

  18. Bone as target organ for metals: the case of f-elements.

    PubMed

    Vidaud, Claude; Bourgeois, Damien; Meyer, Daniel

    2012-06-18

    The skeleton is a target organ for most metals. This leads to their bioaccumulation, either as storage of useful oligoelements or as a protection against damage by toxic elements. The different events leading to their accumulation in this organ, under constant remodeling, are not fully understood, nor the full subsequent impact on bone metabolism. This lack of knowledge is particularly true for lanthanides and actinides, whose use has been increasing over recent decades. These metals, known as f-elements, present chemical similarities and differences. After a comparison of the biologically relevant physicochemical properties of lanthanides and actinides, and a brief reminder of the main events of bone metabolism, this review considers the results published over the past decade regarding the interaction between bones and f-elements. Emphasis will be given to the molecular events, which constitute the basis of the most recent toxicological studies in this domain but still need further investigation. Ionic exchanges with the inorganic matrix, interactions with bone proteins, and cellular mechanism disturbances are mainly considered in this review.

  19. Plasma and liquid-metal resistivity calculations using the Ziman theory

    NASA Astrophysics Data System (ADS)

    Nardi, Eran

    1996-08-01

    Liquid-metal and dense plasma resistivities are calculated for some transition metals and for Al using the Ziman theory together with the self-consistent average atom INFERNO code. The hypernetted-chain equation is used for calculating the structure factors when no experimental data are available. Attempts are made to improve upon previous calculations by including more accurate electron densities of states as well as the second and third order terms in the multiple scattering expansion of the T matrix. Calculated resistivities with the exception of low density Cu plasma are up to a factor of 4 higher than the experiment for transition metals and between three to four times smaller for Al liquid metal and plasma. The results of the model used in this paper do not seem to agree with the recent experimental data for Cu at a density of the order of a gram and temperatures of several eV as recently obtained by DeSilva and Kunze [Phys. Rev. E 49, 4448 (1994)].

  20. Two-component Fermi-liquid theory - Equilibrium properties of liquid metallic hydrogen

    NASA Technical Reports Server (NTRS)

    Oliva, J.; Ashcroft, N. W.

    1981-01-01

    It is reported that the transition of condensed hydrogen from an insulating molecular crystal phase to a metallic liquid phase, at zero temperature and high pressure, appears possible. Liquid metallic hydrogen (LMH), comprising interpenetrating proton and electron fluids, would constitute a two-component Fermi liquid with both a very high component-mass ratio and long-range, species-dependent bare interactions. The low-temperature equilibrium properties of LMH are examined by means of a generalization to the case of two components of the phenomenological Landau Fermi-liquid theory, and the low-temperature specific heat, compressibility, thermal expansion coefficient and spin susceptibility are given. It is found that the specific heat and the thermal expansion coefficient are vastly greater in the liquid than in the corresponding solid, due to the presence of proton quasiparticle excitations in the liquid.

  1. A new thermo-elasto-plasticity constitutive theory for polycrystalline metals

    NASA Astrophysics Data System (ADS)

    Chen, Cen; Tang, Qiheng; Wang, Tzuchiang

    2015-06-01

    In this study, the behavior of polycrystalline metals at different temperatures is investigated by a new thermo-elasto-plasticity constitutive theory. Based on solid mechanical and interatomic potential, the constitutive equation is established using a new decomposition of the deformation gradient. For polycrystalline copper and magnesium, the stress-strain curves from 77 to 764 K (copper), and 77 to 870 K (magnesium) under quasi-static uniaxial loading are calculated, and then the calculated results are compared with the experiment results. Also, it is determined that the present model has the capacity to describe the decrease of the elastic modulus and yield stress with the increasing temperature, as well as the change of hardening behaviors of the polycrystalline metals. The calculation process is simple and explicit, which makes it easy to implement into the applications.

  2. Reliable Energy Level Alignment at Physisorbed Molecule–Metal Interfaces from Density Functional Theory

    PubMed Central

    2015-01-01

    A key quantity for molecule–metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal–molecule interfaces. The method builds on the “DFT+Σ” approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways: first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule–metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors. PMID:25741626

  3. Density Functional Theory Study on the Interactions of Metal Ions with Long Chain Deprotonated Carboxylic Acids.

    PubMed

    Mehandzhiyski, Aleksandar Y; Riccardi, Enrico; van Erp, Titus S; Koch, Henrik; Åstrand, Per-Olof; Trinh, Thuat T; Grimes, Brian A

    2015-10-08

    In this work, interactions between carboxylate ions and calcium or sodium ions are investigated via density functional theory (DFT). Despite the ubiquitous presence of these interactions in natural and industrial chemical processes, few DFT studies on these systems exist in the literature. Special focus has been placed on determining the influence of the multibody interactions (with up to 4 carboxylates and one metal ion) on an effective pair-interaction potential, such as those used in molecular mechanics (MM). Specifically, DFT calculations are employed to quantify an effective pair-potential that implicitly includes multibody interactions to construct potential energy curves for carboxylate-metal ion pairs. The DFT calculated potential curves are compared to a widely used molecular mechanics force field (OPLS-AA). The calculations indicate that multibody effects do influence the energetic behavior of these ionic pairs and the extent of this influence is determined by a balance between (a) charge transfer from the carboxylate to the metal ions which stabilizes the complex and (b) repulsion between carboxylates, which destabilizes the complex. Additionally, the potential curves of the complexes with 1 and 2 carboxylates and one counterion have been examined to higher separation distance (20 Å) by the use of relaxed scan optimization and constrained density functional theory (CDFT). The results from the relaxed scan optimization indicate that near the equilibrium distance, the charge transfer between the metal ion and the deprotonated carboxylic acid group is significant and leads to non-negligible differences between the DFT and MM potential curves, especially for calcium. However, at longer separation distances the MM calculated interaction potential functions converge to those calculated with CDFT, effectively indicating the approximate domain of the separation distance coordinate where charge transfer between the ions is occurring.

  4. Thermohydraulic behavior of the liquid metal target of a spallation neutron source

    SciTech Connect

    Takeda, Y.

    1996-06-01

    The author presents work done on three main problems. (1) Natural circulation in double coaxial cylindircal container: The thermohydraulic behaviour of the liquid metal target of the spallation neutron source at PSI has been investigated. The configuration is a natural-circulation loop in a concentric double-tube-type container. The results show that the natural-circulation loop concept is valid for the design phase of the target construction, and the current specified design criteria will be fulfilled with the proposed parameter values. (2) Flow around the window: Water experiments were performed for geometry optimisation of the window shape of the SINQ container for avoiding generating recirculation zones at peripheral area and the optimal cooling of the central part of the beam entrance window. Flow visualisation technique was mainly used for various window shapes, gap distance between the window and the guide tube edge. (3) Flow in window cooling channels: Flows in narrow gaps of cooling channels of two different types of windows were studied by flow visualisation techniques. One type is a slightly curved round cooling channel and the other is hemispherical shape, both of which have only 2 mm gap distance and the water inlet is located on one side and flows out from the opposite side. In both cases, the central part of the flow area has lower velocity than peripheral area.

  5. CO2 laser pulse shortening by laser ablation of a metal target.

    PubMed

    Donnelly, T; Mazoyer, M; Lynch, A; O'Sullivan, G; O'Reilly, F; Dunne, P; Cummins, T

    2012-03-01

    A repeatable and flexible technique for pulse shortening of laser pulses has been applied to transversely excited atmospheric (TEA) CO(2) laser pulses. The technique involves focusing the laser output onto a highly reflective metal target so that plasma is formed, which then operates as a shutter due to strong laser absorption and scattering. Precise control of the focused laser intensity allows for timing of the shutter so that different temporal portions of the pulse can be reflected from the target surface before plasma formation occurs. This type of shutter enables one to reduce the pulse duration down to ~2 ns and to remove the low power, long duration tails that are present in TEA CO(2) pulses. The transmitted energy is reduced as the pulse duration is decreased but the reflected power is ~10 MW for all pulse durations. A simple laser heating model verifies that the pulse shortening depends directly on the plasma formation time, which in turn is dependent on the applied laser intensity. It is envisaged that this plasma shutter will be used as a tool for pulse shaping in the search for laser pulse conditions to optimize conversion efficiency from laser energy to useable extreme ultraviolet (EUV) radiation for EUV source development.

  6. CO2 laser pulse shortening by laser ablation of a metal target

    NASA Astrophysics Data System (ADS)

    Donnelly, T.; Mazoyer, M.; Lynch, A.; O'Sullivan, G.; O'Reilly, F.; Dunne, P.; Cummins, T.

    2012-03-01

    A repeatable and flexible technique for pulse shortening of laser pulses has been applied to transversely excited atmospheric (TEA) CO2 laser pulses. The technique involves focusing the laser output onto a highly reflective metal target so that plasma is formed, which then operates as a shutter due to strong laser absorption and scattering. Precise control of the focused laser intensity allows for timing of the shutter so that different temporal portions of the pulse can be reflected from the target surface before plasma formation occurs. This type of shutter enables one to reduce the pulse duration down to ˜2 ns and to remove the low power, long duration tails that are present in TEA CO2 pulses. The transmitted energy is reduced as the pulse duration is decreased but the reflected power is ˜10 MW for all pulse durations. A simple laser heating model verifies that the pulse shortening depends directly on the plasma formation time, which in turn is dependent on the applied laser intensity. It is envisaged that this plasma shutter will be used as a tool for pulse shaping in the search for laser pulse conditions to optimize conversion efficiency from laser energy to useable extreme ultraviolet (EUV) radiation for EUV source development.

  7. A continuum deformation theory for metal-matrix composites at high temperature

    NASA Technical Reports Server (NTRS)

    Robinson, D. N.

    1987-01-01

    A continuum theory is presented for representing the high temperature, time dependent, hereditary deformation behavior of metallic composites that can be idealized as pseudohomogeneous continua with locally definable directional characteristics. Homogenization of textured materials (molecular, granular, fibrous) and applicability of continuum mechanics in structural applications depends on characteristic body dimensions, the severity of gradients (stress, temperature, etc.) in the structure and the relative size of the internal structure (cell size) of the material. The point of view taken here is that the composite is a material in its own right, with its own properties that can be measured and specified for the composite as a whole.

  8. Theory and experiment of submonolayer quantum-dot metal-cavity surface-emitting microlasers.

    PubMed

    Qiao, Pengfei; Lu, Chien-Yao; Bimberg, Dieter; Chuang, Shun Lien

    2013-12-16

    We present a theoretical model for metal-cavity submonolayer quantum-dot surface-emitting microlasers, which operate at room temperature under electrical injection. Size-dependent lasing characteristics are investigated experimentally and theoretically with device radius ranging from 5 μm to 0.5 μm. The quantum dot emission and cavity optical properties are used in a rate-equation model to study the laser light output power vs. current behavior. Our theory explains the observed size-dependent physics and provides a guide for future device size reduction.

  9. Application of the strain invariant failure theory (SIFT) to metals and fiber-polymer composites

    NASA Astrophysics Data System (ADS)

    Hart-Smith, L. J.

    2010-11-01

    The strain invariant failure theory (SIFT) model, developed to predict the onset of irreversible damage of fiber-polymer composite laminates, may be also applied to metals. Indeed, it can be applied to all solid materials. Two initial failure mechanisms are considered - distortion and dilatation. The author's experiences are confined to the structures of transport aircraft; phase changes in metals and self-destruction of laminates during curing are not covered. Doing so would need additional material properties, and probably a different failure theory. SIFT does not cover environmental attack on the interface between fibers and resin; it covers only cohesive failures within the fibers or resin, or within a homogeneous piece of metal. In the SIFT model, each damage mechanism is characterized by its own critical value of a strain invariant. Each mechanism dominates its own portion of the strain domain; there is no interaction between them. Application of SIFT to metals is explained first. Fiber-polymer composites contain two discrete constituents; each material must be characterized independently by its own two invariants. This is why fiber-polymer composites need four invariants whereas metals require only two. There is no such thing as a composite material, only composites of materials. The "composite materials" must not be modeled as homogeneous anisotropic solids because it is then not even possible to differentiate between fiber and matrix failures. The SIFT model uses measured material properties; it does not require that half of them be arbitrarily replaced by unmeasurable properties to fit laminate test data, as so many earlier composite failure criteria have. The biggest difference in using SIFT for metals and fiber-reinforced materials is internal residual thermal and moisture absorption stresses created by the gross dissimilarity in properties between embedded fibers and thermoset resin matrices. These residual stresses consume so much of the strength of

  10. "Complex" Targeting: A Complexity-Based Theory of Targeting and Its Application to Radical Islamic Terrorism

    DTIC Science & Technology

    2002-06-01

    Lilienfeld, The Rise of Systems Theory: An Ideological Analysis (New York: John Wiley & Sons, Inc., 1978), 247-280. 8 Power Journal4 with the current...Theory: An Ideological Analysis . New York: John Wiley & Sons, Inc., 1978. Luchsinger, Vincent P. and V. Thomas Dock. The Systems Approach: A

  11. A simple laminate theory using the orthotropic viscoplasticity theory based on overstress. I - In-plane stress-strain relationships for metal matrix composites

    NASA Technical Reports Server (NTRS)

    Krempl, Erhard; Hong, Bor Zen

    1989-01-01

    A macromechanics analysis is presented for the in-plane, anisotropic time-dependent behavior of metal matrix laminates. The small deformation, orthotropic viscoplasticity theory based on overstress represents lamina behavior in a modified simple laminate theory. Material functions and constants can be identified in principle from experiments with laminae. Orthotropic invariants can be repositories for tension-compression asymmetry and for linear elasticity in one direction while the other directions behave in a viscoplastic manner. Computer programs are generated and tested for either unidirectional or symmetric laminates under in-plane loading. Correlations with the experimental results on metal matrix composites are presented.

  12. Dim target detection in IR image sequences based on fractal and rough set theory

    NASA Astrophysics Data System (ADS)

    Yan, Xiaoke; Shi, Caicheng; He, Peikun

    2005-11-01

    This paper addresses the problem of detecting small, moving, low amplitude in image sequences that also contain moving nuisance objects and background noise. Rough sets (RS) theory is applied in similarity relation instead of equivalence relation to solve clustering issue. We propose fractal-based texture analysis to describe texture coarseness and locally adaptive threshold technique to seek latent object point. Finally, according to temporal and spatial correlations between different frames, the singular points can be filtered. We demonstrate the effectiveness of the technique by applying it to real infrared image sequences containing targets of opportunity and evolving cloud clutter. The experimental results show that the algorithm can effectively increase detection probability and has robustness.

  13. Theory of Quantum Hopping In Metallic Polymers and Applications in Electronics

    NASA Astrophysics Data System (ADS)

    Prigodin, Vladimir

    2005-03-01

    The low frequency electromagnetic response of highly conducting polymers (e.g., polyaniline and polypyrrole) in a metallic state^1, when analyzed within the standard theory of metals, is provided by an extremely small fraction of the total number of available electrons ˜ 0.1 % (in contrast to ˜ 100 % for common metals such as Cu, Ag, or Ni) but with anomalous long scattering time > 10-13 s (˜ 100 times longer than for common metals). We show that a chain-linked network of metallic grains (the polymer's crystalline domains) connected by resonance quantum tunneling through strongly localized states in surrounding disordered medium produces this behavior. The small fraction of electrons is assigned to the low density of resonance states and the long scattering time is related to the narrow width of energy levels in resonance. Recently a new interesting phenomenon, an electric field effect, was reported for the doped highly conducting polymers. Upon applying the gate voltage of a few volts the conductivity of the polymer film drops by a several orders of magnitude^2. This observation is in conflict with the fact that the electric field cannot penetrate into a conductor further that the `lattice constant', and therefore its effect on the polymer film of ˜ 100 nm thickness should be negligible. We suggest that the field effect in doped conducting polymers is an electric field induced conductor-nonconductor transition described by the chain-linked granular model in the presence of mobile ions. The ion motion under the gate voltage is breaking the interdot percolation network by removing critical hoping sites and as a result producing the conductor-nonconductor transition. The experimental evidences for the present mechanism of field effect in conducting polymers are presented. *R.S. Kohlman et al., Phys. Rev. Lett. 78, 3915 (1997). *A.J. Epstein et al., Curr. Appl. Phys. 2, 339 (2002).

  14. Binding Energy of d¹º Transition Metals to Alkenes By Wave Function Theory and Density Functional Theory

    SciTech Connect

    Averkiev, Boris B; Zhao, Yan; Truhlar, Donald G

    2010-06-01

    The structures of Pd(PH₃)₂ and Pt(PH₃)₂ complexes with ethene and conjugated CnHn+2 systems (n=4, 6, 8, and 10) were studied. Their binding energies were calculated using both wave function theory (WFT) and density functional theory (DFT). Previously it was reported that the binding energy of the alkene to the transition metal does not depend strongly on the size of the conjugated CnHn+2 ligand, but that DFT methods systematically underestimate the binding energy more and more significantly as the size of the conjugated system is increased. Our results show that recently developed density functionals predict the binding energy for these systems much more accurately. New benchmark calculations carried out by the coupled cluster method based on Brueckner orbitals with double excitations and a quasiperturbative treatment of connected triple excitations (BCCD(T)) with a very large basis set agree even better with the DFT predictions than do the previous best estimates. The mean unsigned error in absolute and relative binding energies of the alkene ligands to Pd(PH₃)₂ is 2.5 kcal/mol for the ωB97 and M06 density functionals and 2.9 kcal/mol for the M06-L functional. Adding molecular mechanical damped dispersion yields even smaller mean unsigned errors: 1.3 kcal/mol for the M06-D functional, 1.5 kcal/mol for M06- L-D, and 1.8 kcal/mol for B97-D and ωB97X-D. The new functionals also lead to improved accuracy for the analogous Pt complexes. These results show that recently developed density functionals may be very useful for studying catalytic systems involving Pd d¹º centers and alkenes.

  15. A computational theory for the classification of natural biosonar targets based on a spike code.

    PubMed

    Müller, Rolf

    2003-08-01

    A computational theory for the classification of natural biosonar targets is developed based on the properties of an example stimulus ensemble. An extensive set of echoes (84 800) from four different foliages was transcribed into a spike code using a parsimonious model (linear filtering, half-wave rectification, thresholding). The spike code is assumed to consist of time differences (interspike intervals) between threshold crossings. Among the elementary interspike intervals flanked by exceedances of adjacent thresholds, a few intervals triggered by disjoint half-cycles of the carrier oscillation stand out in terms of resolvability, visibility across resolution scales and a simple stochastic structure (uncorrelatedness). They are therefore argued to be a stochastic analogue to edges in vision. A three-dimensional feature vector representing these interspike intervals sustained a reliable target classification performance (0.06% classification error) in a sequential probability ratio test, which models sequential processing of echo trains by biological sonar systems. The dimensions of the representation are the first moments of duration and amplitude location of these interspike intervals as well as their number. All three quantities are readily reconciled with known principles of neural signal representation, since they correspond to the centre of gravity of excitation on a neural map and the total amount of excitation.

  16. Ground-state properties of rare-earth metals: an evaluation of density-functional theory.

    PubMed

    Söderlind, Per; Turchi, P E A; Landa, A; Lordi, V

    2014-10-15

    The rare-earth metals have important technological applications due to their magnetic properties, but are scarce and expensive. Development of high-performance magnetic materials with less rare-earth content is desired, but theoretical modeling is hampered by complexities of the rare earths electronic structure. The existence of correlated (atomic-like) 4f electrons in the vicinity of the valence band makes any first-principles theory challenging. Here, we apply and evaluate the efficacy of density-functional theory for the series of lanthanides (rare earths), investigating the influence of the electron exchange and correlation functional, spin-orbit interaction, and orbital polarization. As a reference, the results are compared with those of the so-called 'standard model' of the lanthanides in which electrons are constrained to occupy 4f core states with no hybridization with the valence electrons. Some comparisons are also made with models designed for strong electron correlations. Our results suggest that spin-orbit coupling and orbital polarization are important, particularly for the magnitude of the magnetic moments, and that calculated equilibrium volumes, bulk moduli, and magnetic moments show correct trends overall. However, the precision of the calculated properties is not at the level of that found for simpler metals in the Periodic Table of Elements, and the electronic structures do not accurately reproduce x-ray photoemission spectra.

  17. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms.

    PubMed

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J; Vegge, Tejs

    2014-09-28

    Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) - almost 27,000 combinations, and have identified novel mixtures, with significantly improved storage capacities. The size of the search space and the chosen fitness function make it possible to verify that the found candidates are the best possible candidates in the search space, proving that the GA implementation is ideal for this kind of computational materials design, requiring calculations on less than two percent of the candidates to identify the global optimum.

  18. Understanding the NMR shifts in paramagnetic transition metal oxides using density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Carlier, D.; Ménétrier, M.; Grey, C. P.; Delmas, C.; Ceder, G.

    2003-05-01

    The 6,7Li MAS NMR spectra of lithium ions in paramagnetic host materials are extremely sensitive to number and nature of the paramagnetic cations in the Li local environments and large shifts (Fermi contact shifts) are often observed. The work presented in this paper aims to provide a rational basis for the interpretation of the 6,7Li NMR shifts, as a function of the lithium local environment and electronic configuration of the transition metal ions. We focus on the layered rocksalts often found for LiMO2 compounds and on materials that are isostructural with the K2NiF4 structure. In order to understand the spin-density transfer mechanism from the transition metal ion to the lithium nucleus, which gives rise to the hyperfine shifts observed by NMR, we have performed density functional theory (DFT) calculations in the generalized gradient approximation. For each compound, we calculate the spin densities values on the transition metal, oxygen and lithium ions and map the spin density in the M-O-Li plane. Predictions of the calculations are in good agreement with several experimental results. We show that DFT calculations are a useful tool with which to interpret the observed paramagnetic shifts in layered oxides and to understand the major spin-density transfer processes. This information should help us to predict the magnitudes and signs of the Li hyperfine shifts for different Li local environments and t2g vs eg electrons in other compounds.

  19. Density-Functional Theory Studies of Correlation Energy Effects at Metallic Surfaces.

    NASA Astrophysics Data System (ADS)

    Mohammed, Abdel-Raouf Eid

    In this thesis we study the effects of correlation in the inhomogeneous electron gas at metallic surfaces. These studies are performed within the context of density-functional theory (DFT). Using accurate representations of the electronic density profile, we have estimated variationally the surface correlation energy of jellium metal. The accuracy of these estimates is founded in the assumption that the exchange -correlation energy functional of the density is approximated accurately by the wave-vector analysis method, and by the fact that the non-local exchange energy contributions are treated exactly. In contrast to the previously accepted conclusion that for surfaces correlation effects are as significant as exchange, our results indicate the ratio of these energies to lie between 34% - 97% over the metallic density range, the smaller ratios corresponding to the higher density metals. In this work we have also examined the local density (LDA) and gradient expansion approximations (GEA) (to O((DEL)('2))) for the correlation energy. We have demonstrated for realistic metal surface densities the cancellation of the errors in the LDA for exchange and correlation, and shown that the density profiles at surfaces would have to be unphysically slowly varying for the correlation energy GEA to converge. We have also studied the effects of correlation at surfaces by screening the exchange, and observe that the surface exchange energy for screened-Coulomb interaction decreases as the screening length is reduced. Thus, the more short-ranged the interaction, the easier it is to split the crystal in two. In addition we have derived the DFT first gradient correction coefficient in the GEA for the screened-Coulomb exchange energy, and shown it to be the same as that obtained within Hartree -Fock theory (HFT) for finite screening. This coefficient reduces to the DFT bare-Coulomb interaction value in the limit of no screening in which limit the HFT coefficient is singular. The GEA

  20. INTERACTION OF LASER RADIATION WITH MATTER: Formation of periodic structures upon laser ablation of metal targets in liquids

    NASA Astrophysics Data System (ADS)

    Kazakevich, Pavel V.; Simakin, Aleksandr V.; Shafeev, Georgii A.

    2005-09-01

    Experimental data on the formation of ordered microstructures produced upon ablation of metal targets in liquids irradiated by a copper vapour laser or a pulsed Nd:YAG laser are presented. The structures were obtained on brass, bronze, copper, and tungsten substrates immersed in distilled water or ethanol. As a result of multiple-pulse laser ablation by a scanning beam, ordered microcones with pointed vertexes are formed on the target surface. The structures are separated by deep narrow channels. The structure period was experimentally shown to increase linearly with diameter of the laser spot on the target surface.

  1. THE DEPENDENCE OF BROWN DWARF RADII ON ATMOSPHERIC METALLICITY AND CLOUDS: THEORY AND COMPARISON WITH OBSERVATIONS

    SciTech Connect

    Burrows, Adam; Nampaisarn, Thane; Heng, Kevin E-mail: tnampais@astro.princeton.edu

    2011-07-20

    Employing realistic and consistent atmosphere boundary conditions, we have generated evolutionary models for brown dwarfs and very low mass stars (VLMs) for different atmospheric metallicities ([Fe/H]), with and without clouds. We find that the spread in radius at a given mass and age can be as large as {approx}10% to {approx}25%, with higher-metallicity, higher-cloud-thickness atmospheres resulting quite naturally in larger radii. For each 0.1 dex increase in [Fe/H], radii increase by {approx}1% to {approx}2.5%, depending upon the age and mass. We also find that, while for smaller masses and older ages brown dwarf radii decrease with increasing helium fraction (Y, as expected), for more massive brown dwarfs and a wide range of ages they increase with helium fraction. The increase in radius in going from Y = 0.25 to Y = 0.28 can be as large as {approx}0.025 R{sub J} ({approx}2.5%). Furthermore, we find that for VLMs an increase in atmospheric metallicity from 0.0 to 0.5 dex, increases radii by {approx}4%, and from -0.5 to 0.5 dex by {approx}10%. Therefore, we suggest that opacity due to higher metallicity might naturally account for the apparent radius anomalies in some eclipsing VLM systems. Ten to twenty-five percent variations in radius exceed errors stemming from uncertainties in the equation of state alone. This serves to emphasize that transit and eclipse measurements of brown dwarf radii constrain numerous effects collectively, importantly including the atmosphere and condensate cloud models, and not just the equation of state. At all times, one is testing a multi-parameter theory, and not a universal radius-mass relation.

  2. Influence of electronic stopping on sputtering induced by cluster impact on metallic targets

    SciTech Connect

    Sandoval, Luis; Urbassek, Herbert M.

    2009-04-01

    Using molecular-dynamics simulation, we model the sputtering of a Au (111) crystallite induced by the impact of Au{sub 13} projectiles with total energies up to 500 keV. Due to the uncertainty of the electronic stopping of Au moving in particular at small velocities, we performed several simulations, in which the electronic stopping parameters are systematically changed. Our results demonstrate the dominating influence of the cut-off energy E{sub c}, below which the high-velocity electronic stopping of atoms is switched off in the simulation. If E{sub c} is smaller than roughly one half the cohesive energy of the target, sputtering ceases after a few ps; the spike contribution to sputtering (also called phase explosion or gas-flow contribution) is entirely quenched and the sputtering yield is up to an order of magnitude smaller than when electronic stopping is taken into account only at higher atom energies. Our results demonstrate the importance of a careful modeling of electronic stopping in simulations of spike sputtering from metals.

  3. Mitochondria as an important target in heavy metal toxicity in rat hepatoma AS-30D cells.

    PubMed

    Belyaeva, Elena A; Dymkowska, Dorota; Wieckowski, Mariusz R; Wojtczak, Lech

    2008-08-15

    The mechanisms of toxic effects of divalent cations of three heavy metals Hg, Cd and Cu in rat ascites hepatoma AS-30D cells cultivated in vitro were compared. It was found that the toxicity of these ions, applied in the micromolar range (10-500 microM), decreased from Hg(2+) (most toxic) to Cu(2+) (least toxic). Hg(2+) and Cd(2+) produced a high percentage of cell death by both necrosis and apoptosis, whereas Cu(2+) at concentrations up to 500 microM was weakly effective. Hg(2+) at concentration of 10 microM appeared slightly uncoupling (i.e., stimulated resting state respiration and decreased the mitochondrial transmembrane potential), whereas it exerted a strong inhibitory effect on the respiratory chain and rapid dissipation of the membrane potential at higher concentrations. Cu(2+) had inhibitory effect on cell respiration only at 500 microM concentration and after incubation of 48 h but produced a significant uncoupling effect at lower concentrations. Cu(2+) induced an early and sharp increase of intracellular production of reactive oxygen species (ROS). The action of Hg(2+) and Cd(2+) on ROS generation was biphasic. They stimulated ROS generation within the cells at low concentrations and at short incubation times but decreased ROS generation at higher concentrations and at longer incubation. It is concluded that mitochondria are an important target for toxic effects of Hg(2+), Cd(2+) and Cu(2+) in AS-30D rat hepatoma cells.

  4. Selective pressures for accurate altruism targeting: evidence from digital evolution for difficult-to-test aspects of inclusive fitness theory.

    PubMed

    Clune, Jeff; Goldsby, Heather J; Ofria, Charles; Pennock, Robert T

    2011-03-07

    Inclusive fitness theory predicts that natural selection will favour altruist genes that are more accurate in targeting altruism only to copies of themselves. In this paper, we provide evidence from digital evolution in support of this prediction by competing multiple altruist-targeting mechanisms that vary in their accuracy in determining whether a potential target for altruism carries a copy of the altruist gene. We compete altruism-targeting mechanisms based on (i) kinship (kin targeting), (ii) genetic similarity at a level greater than that expected of kin (similarity targeting), and (iii) perfect knowledge of the presence of an altruist gene (green beard targeting). Natural selection always favoured the most accurate targeting mechanism available. Our investigations also revealed that evolution did not increase the altruism level when all green beard altruists used the same phenotypic marker. The green beard altruism levels stably increased only when mutations that changed the altruism level also changed the marker (e.g. beard colour), such that beard colour reliably indicated the altruism level. For kin- and similarity-targeting mechanisms, we found that evolution was able to stably adjust altruism levels. Our results confirm that natural selection favours altruist genes that are increasingly accurate in targeting altruism to only their copies. Our work also emphasizes that the concept of targeting accuracy must include both the presence of an altruist gene and the level of altruism it produces.

  5. Cyclotron production of ⁹⁹mTc: recycling of enriched ¹⁰⁰Mo metal targets.

    PubMed

    Gagnon, K; Wilson, J S; Holt, C M B; Abrams, D N; McEwan, A J B; Mitlin, D; McQuarrie, S A

    2012-08-01

    There is growing interest in the large scale cyclotron production of (99m)Tc via the (100)Mo(p,2n)(99m)Tc reaction. While the use and recycling of cyclotron-irradiated enriched molybdenum targets has been reported previously in the context of (94m)Tc production, to the best of our knowledge, previous recycling studies have been limited to the use of oxide targets. To facilitate reuse of high-power enriched (100)Mo targets, this work presents and evaluates a strategy for recycling of enriched metallic molybdenum. For the irradiated (100)Mo targets in this study, an overall metal to metal recovery of 87% is reported. Evaluation of "new" and "recycled" (100)Mo revealed no changes in the molybdenum isotopic composition (as measured via ICP-MS). For similar irradiation conditions of "new" and "recycled" (100)Mo, (i.e. target thicknesses, irradiation time, and energy), comparable levels of (94g)Tc, (95g)Tc, and (96g)Tc contaminants were observed. Comparable QC specifications (i.e. aluminum ion concentration, pH, and radiochemical purity) were also reported. We finally note that [(99m)Tc]-MDP images obtained by comparing MDP labelled with generator-based (99m)Tc vs. (99m)Tc obtained following the irradiation of recycled (100)Mo demonstrated comparable biodistribution. With the goal of producing large quantities of (99m)Tc, the proposed methodology demonstrates that efficient recycling of enriched metallic (100)Mo targets is feasible and effective.

  6. Covalency in Metal-Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

    SciTech Connect

    Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Bradley, Joseph A.; Daly, Scott R.; Kozimor, Stosh A.; Lukens, Wayne W.; Martin, Richard L.; Nordlund, Dennis; Seidler, Gerald T.; Shuh, David K.; Sokaras, Dimosthenis; Tyliszczak, Tolek; Wagner, Gregory L.; Weng, Tsu-Chein; Yang, Ping

    2014-01-01

    Advancing theories of how metal oxygen bonding influences metal oxo properties can expose new avenues for innovation in materials science, catalysis, and biochemistry. Historically, spectroscopic analyses of the transition metal peroxyanions, MO4x-, have formed the basis for new M O bonding theories. Herein, relative changes in M O orbital mixing in MO42- (M = Cr, Mo, W) and MO41- (M = Mn, Tc, Re) are evaluated for the first time by non-resonant inelastic X-ray scattering, X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and linear-response density functional theory. The results suggest that moving from Group 6 to Group 7 or down the triads increases M O e () mixing. Meanwhile, t2 mixing ( + ) remains relatively constant within the same Group. These unexpected changes in frontier orbital energy and composition are evaluated in terms of periodic trends in d orbital energy and radial extension.

  7. Evaluation of metal biouptake from the analysis of bulk metal depletion kinetics at various cell concentrations: theory and application.

    PubMed

    Rotureau, Elise; Billard, Patrick; Duval, Jérôme F L

    2015-01-20

    Bioavailability of trace metals is a key parameter for assessment of toxicity on living organisms. Proper evaluation of metal bioavailability requires monitoring the various interfacial processes that control metal partitioning dynamics at the biointerface, which includes metal transport from solution to cell membrane, adsorption at the biosurface, internalization, and possible excretion. In this work, a methodology is proposed to quantitatively describe the dynamics of Cd(II) uptake by Pseudomonas putida. The analysis is based on the kinetic measurement of Cd(II) depletion from bulk solution at various initial cell concentrations using electroanalytical probes. On the basis of a recent formalism on the dynamics of metal uptake by complex biointerphases, the cell concentration-dependent depletion time scales and plateau values reached by metal concentrations at long exposure times (>3 h) are successfully rationalized in terms of limiting metal uptake flux, rate of excretion, and metal affinity to internalization sites. The analysis shows the limits of approximate depletion models valid in the extremes of high and weak metal affinities. The contribution of conductive diffusion transfer of metals from the solution to the cell membrane in governing the rate of Cd(II) uptake is further discussed on the basis of estimated resistances for metal membrane transfer and extracellular mass transport.

  8. Face-centered-cubic B80 metal: Density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Yan, Qing-Bo; Zheng, Qing-Rong; Su, Gang

    2008-06-01

    By means of ab initio calculations within the density functional theory, we have found that B80 fullerenes can condense to form stable face-centered-cubic (fcc) solids. It is shown that when forming a crystal, B80 cages are geometrically distorted, the Ih symmetry is lowered to Th , and four boron-boron chemical bonds are formed between every two nearest neighbor B80 cages. The cohesive energy of B80 fcc solid is 0.23 eV/atom with respect to the isolated B80 fullerene. The calculated electronic structure reveals that the fcc B80 solid is a metal. The predicted solid phase would constitute a form of pure boron and might have diverse implications. In addition, a simple electron counting rule is proposed, which could explain the stability of B80 fullerene and the recently predicted stable boron sheet.

  9. Self-interaction correction in multiple scattering theory: application to transition metal oxides

    SciTech Connect

    Daene, Markus W; Lueders, Martin; Ernst, Arthur; Diemo, Koedderitzsch; Temmerman, Walter M; Szotek, Zdzislawa; Wolfam, Hergert

    2009-01-01

    We apply to transition metal monoxides the self-interaction corrected (SIC) local spin density (LSD) approximation, implemented locally in the multiple scattering theory within the Korringa-Kohn-Rostoker (KKR) band structure method. The calculated electronic structure and in particular magnetic moments and energy gaps are discussed in reference to the earlier SIC results obtained within the LMTO-ASA band structure method, involving transformations between Bloch and Wannier representations to solve the eigenvalue problem and calculate the SIC charge and potential. Since the KKR can be easily extended to treat disordered alloys, by invoking the coherent potential approximation (CPA), in this paper we compare the CPA approach and supercell calculations to study the electronic structure of NiO with cation vacancies.

  10. Exploring the surface reactivity of 3d metal endofullerenes: a density-functional theory study.

    PubMed

    Estrada-Salas, Rubén E; Valladares, Ariel A

    2009-09-24

    Changes in the preferential sites of electrophilic, nucleophilic, and radical attacks on the pristine C60 surface with endohedral doping using 3d transition metal atoms were studied via two useful reactivity indices, namely the Fukui functions and the molecular electrostatic potential. Both of these were calculated at the density functional BPW91 level of theory with the DNP basis set. Our results clearly show changes in the preferential reactivity sites on the fullerene surface when it is doped with Mn, Fe, Co, or Ni atoms, whereas there are no significant changes in the preferential reactivity sites on the C60 surface upon endohedral doping with Cu and Zn atoms. Electron affinities (EA), ionization potentials (IP), and HOMO-LUMO gaps (Eg) were also calculated to complete the study of the endofullerene's surface reactivity. These findings provide insight into endofullerene functionalization, an important issue in their application.

  11. A micromechanical theory of grain-size dependence in metal plasticity

    NASA Astrophysics Data System (ADS)

    Weng, G. J.

    T HE EFFECT of grain-size on the elastoplastic behavior of metals is investigated from the micromechanics standpoint. First, based on the observations that dislocation pile-ups, formation of cell structures, and other inelastic activities influenced by the presence of grain boundary actually take place transcrystallinely, a grain-size dependent constitutive equation is proposed for the slip deformation of slip systems. By means of a modified Hill's self-consistent relation the local stress of a grain is calculated, and used in conjunction with this constitutive equation to evaluate the plastic strain of each constituent grain. The grain-size effect on the plastic flow of polycrystals then can be determined by an averaging process. To check the validity of the proposed theory it was finally applied to predict the stress-strain curves and flow stresses of a copper at various grain-sizes. The obtained results were found to be in good agreement with experimental data.

  12. Targeting triple negative breast cancer cells by N3-substituted 9,10-Phenanthrenequinone thiosemicarbazones and their metal complexes

    NASA Astrophysics Data System (ADS)

    Afrasiabi, Zahra; Stovall, Preston; Finley, Kristen; Choudhury, Amitava; Barnes, Charles; Ahmad, Aamir; Sarkar, Fazlul; Vyas, Alok; Padhye, Subhash

    2013-10-01

    Novel N3-substituted 9,10-Phenanthrenequinone thiosemicarbazones and their copper, nickel and palladium complexes are structurally characterized and reported along with the single crystal X-ray structures of three ligands and one nickel complex. All compounds were evaluated for their antiproliferative potential against Triple Negative Breast Cancer (TNBC) cells which have poor prognosis and no effective drugs to treat with. All compounds exhibited antiproliferative activity against these cells. Among the metal complexes evaluated, redox active copper complexes were found to be more potent. The possible mechanism for such enhanced activity can be attributed to the generation of oxidative stress, which was amenable for targeting through metal complexation.

  13. Theory of passive mode locking of solid-state lasers using metal nanocomposites as slow saturable absorbers.

    PubMed

    Kim, Kwang-Hyon; Griebner, Uwe; Herrmann, Joachim

    2012-05-01

    Mode locking of solid-state lasers using metal nanocomposites as slow saturable absorbers (SAs) is studied theoretically. The derived equation for the transient nonlinear response of metal nanocomposites is based on the semiclassical two-temperature model. The model is confirmed experimentally by pump-probe measurements on Au nanoparticles (NPs). The theory was applied to study passive mode locking of a solid-state laser containing Au NPs as SA in the green spectral range. Pulse durations as short as 100 fs are predicted, and design criteria of metal NP SAs are derived.

  14. Atomic collisions in suprafluid helium-nanodroplets: timescales for metal-cluster formation derived from He-density functional theory.

    PubMed

    Hauser, Andreas W; Volk, Alexander; Thaler, Philipp; Ernst, Wolfgang E

    2015-04-28

    Collision times for the coinage metal atoms Cu, Ag and Au in He-droplets are derived from helium density functional theory and molecular dynamics simulations. The strength of the attractive interaction between the metal atoms turns out to be less important than the mass of the propagating metal atoms. Even for small droplets consisting of a few thousand helium atoms, the collision times are shortest for Cu, followed by Ag and Au, despite the higher binding energy of Au2 compared to Cu2.

  15. Atomic collisions in suprafluid helium-nanodroplets: timescales for metal-cluster formation derived from He-density functional theory

    PubMed Central

    Volk, Alexander; Thaler, Philipp

    2015-01-01

    Collision times for the coinage metal atoms Cu, Ag and Au in He-droplets are derived from helium density functional theory and molecular dynamics simulations. The strength of the attractive interaction between the metal atoms turns out to be less important than the mass of the propagating metal atoms. Even for small droplets consisting of a few thousand helium atoms, the collision times are shortest for Cu, followed by Ag and Au, despite the higher binding energy of Au2 compared to Cu2. PMID:25812719

  16. Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory Study

    SciTech Connect

    Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter A.; Li, Sha; Mavrikakis, Manos

    2014-12-05

    We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxyl-mediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.

  17. A generalized equivalent circuit theory for the electric and magnetic resonances of metallic wire networks

    NASA Astrophysics Data System (ADS)

    Zhang, Weiyi; Chui, S. T.

    2009-06-01

    We generalize Kirchoff's law for multiply connected wire networks to finite frequencies. We focus on the boundary conditions not present in the conventional Kirchoff's law at joints when more than three wires come together, which is absent in our previous "circuit theory" for the finite frequency properties of metallic wire networks for singly connected structures. These boundary conditions at the joints involve introducing localized boundary electric fields, in addition to the electric fields of inductive and capacitive origins. The boundary fields act as natural "Lagrange multipliers" for imposing the boundary conditions on the circuit currents. In this way the number of equations is the same as the number of unknowns. The eigenmodes determine not only the circuit current and charge profiles, but also the boundary electric fields which supplement such profiles. The application to T- and H-shape metallic wire networks suggests that the basic types of resonances are mainly controlled by the symmetry and the wire dimensions of the networks. The low frequency modes form along the longest connected paths of the wire network while the high frequency modes can be generated via succeedingly adding more nodes along these various wire paths. The characteristic behavior of the electric and magnetic responses can be inferred from the circuit current profile of a given mode, which offers a simple physical picture on circuit design with particular electromagnetic parameters.

  18. Adsorption structures and energetics of molecules on metal surfaces: Bridging experiment and theory

    NASA Astrophysics Data System (ADS)

    Maurer, Reinhard J.; Ruiz, Victor G.; Camarillo-Cisneros, Javier; Liu, Wei; Ferri, Nicola; Reuter, Karsten; Tkatchenko, Alexandre

    2016-05-01

    Adsorption geometry and stability of organic molecules on surfaces are key parameters that determine the observable properties and functions of hybrid inorganic/organic systems (HIOSs). Despite many recent advances in precise experimental characterization and improvements in first-principles electronic structure methods, reliable databases of structures and energetics for large adsorbed molecules are largely amiss. In this review, we present such a database for a range of molecules adsorbed on metal single-crystal surfaces. The systems we analyze include noble-gas atoms, conjugated aromatic molecules, carbon nanostructures, and heteroaromatic compounds adsorbed on five different metal surfaces. The overall objective is to establish a diverse benchmark dataset that enables an assessment of current and future electronic structure methods, and motivates further experimental studies that provide ever more reliable data. Specifically, the benchmark structures and energetics from experiment are here compared with the recently developed van der Waals (vdW) inclusive density-functional theory (DFT) method, DFT + vdWsurf. In comparison to 23 adsorption heights and 17 adsorption energies from experiment we find a mean average deviation of 0.06 Å and 0.16 eV, respectively. This confirms the DFT + vdWsurf method as an accurate and efficient approach to treat HIOSs. A detailed discussion identifies remaining challenges to be addressed in future development of electronic structure methods, for which the here presented benchmark database may serve as an important reference.

  19. A variational method for density functional theory calculations on metallic systems with thousands of atoms.

    PubMed

    Ruiz-Serrano, Álvaro; Skylaris, Chris-Kriton

    2013-08-07

    A new method for finite-temperature density functional theory calculations which significantly increases the number of atoms that can be simulated in metallic systems is presented. A self-consistent, direct minimization technique is used to obtain the Helmholtz free energy of the electronic system, described in terms of a set of non-orthogonal, localized functions which are optimized in situ using a periodic-sinc basis set, equivalent to plane waves. Most parts of the calculation, including the demanding operation of building the Hamiltonian matrix, have a computational cost that scales linearly with the number of atoms in the system. Also, this approach ensures that the Hamiltonian matrix has a minimal size, which reduces the computational overhead due to diagonalization, a cubic-scaling operation that is still required. Large basis set accuracy is retained via the optimization of the localized functions. This method allows accurate simulations of entire metallic nanostructures, demonstrated with calculations on a supercell of bulk copper with 500 atoms and on gold nanoparticles with up to 2057 atoms.

  20. Nondestructive evaluation of metal and composite targets using an infrared line-scanning technique

    NASA Astrophysics Data System (ADS)

    Smith, Christopher; Rowley, Matthew; Dvonch, Curt; Fulton, Mary

    2005-03-01

    A thermal, non-destructive evaluation (NDE) technique has been employed by ThermTech Services, Inc. in cooperation with NASA Langley Research Center that allows for quantitative measurements of wall thickness in steam boilers. By determining the thickness of the walls, one can easily determine how much thinning has occurred due to corrosion. This type of NDE can be applied to the inspection of wings and fuselages on aircraft and spaceflight vehicles including the shuttle. The NDE technique employs the linear movement of a heat source (lamp) and an infrared imager that is situated at a fixed distance behind the heat source. The instruments are aligned on a platform that moves up and down across the outer surface of a test sample. By analyzing the induced surface temperature variations, and processing images collected with the infrared imager, it can be determined where material loss of the tubes has occurred. After an image sequence has been collected, a line-by-line subtraction methodology is utilized to discard irrelevant information so that defects are displayed in a re-created image. The overall goal of this project is to provide a proof of concept for a portable, hand-operated thermographic line scanner that would provide an alternative to the existing mass- and power-intensive instrument that utilizes a cooled infrared imager. In this project, two different microbolometers are first analyzed using different metal- and carbon epoxy-based targets to determine which provides better resolution for detection of subsurface, manufactured defects. The feasibility of using uncooled bolometer technology to support the development of a portable instrument to conduct this type of NDE technique was proven.

  1. Experimental and computational results for 1054-nm laser-induced shock effects in confined meteorite and metallic targets

    NASA Astrophysics Data System (ADS)

    Remo, John L.; Hammerling, Peter X.

    2000-08-01

    When a single-pulse high-power laser irradiates a surface at atmospheric pressure, a laser supported detonation (LSD) wave can form above the target surface. The high-pressure gas behind the LSD wave transfers momentum to the target. The laser target coupling is substantially reduced in vacuum, the coupling coefficient typically being an order of magnitude less than that when an atmosphere is present. Another pressure enhancement technique is to confine the laser-target interface. Confinement or 'tamping' also can substantially increase the momentum coupling to the target. Experiments tend to differ from one another based on the target size (thickness) and confinement geometry. This work describes and compares some experimental results for metallic targets irradiated by 1054 nm radiation in the GW/cm2 range and interprets them in terms of simple models. As will be discussed in this paper, such models predict a weak sensitivity to target materials but results are likely to be different for inhomogeneous materials as has been seen in recent experiments on iron-nickel and stony meteorites.

  2. The Elastic Behaviour of Sintered Metallic Fibre Networks: A Finite Element Study by Beam Theory

    PubMed Central

    Bosbach, Wolfram A.

    2015-01-01

    Background The finite element method has complimented research in the field of network mechanics in the past years in numerous studies about various materials. Numerical predictions and the planning efficiency of experimental procedures are two of the motivational aspects for these numerical studies. The widespread availability of high performance computing facilities has been the enabler for the simulation of sufficiently large systems. Objectives and Motivation In the present study, finite element models were built for sintered, metallic fibre networks and validated by previously published experimental stiffness measurements. The validated models were the basis for predictions about so far unknown properties. Materials and Methods The finite element models were built by transferring previously published skeletons of fibre networks into finite element models. Beam theory was applied as simplification method. Results and Conclusions The obtained material stiffness isn’t a constant but rather a function of variables such as sample size and boundary conditions. Beam theory offers an efficient finite element method for the simulated fibre networks. The experimental results can be approximated by the simulated systems. Two worthwhile aspects for future work will be the influence of size and shape and the mechanical interaction with matrix materials. PMID:26569603

  3. Weight Gain Prevention: Identifying Theory-Based Targets for Health Behavior Change in Young Adults

    PubMed Central

    Strong, Kathryn A.; Parks, Serena L.; Anderson, Eileen; Winett, Richard; Davy, Brenda M.

    2008-01-01

    Young adults attending college are more vulnerable to weight gain than the general population. We sought to identify health behavior change targets related to weight management in college students. Based on the social cognitive theory model for health behavior change, we investigated the health-related lifestyle behaviors and physiological characteristics of this population. Forty-three college students (18.3±0.1 years) completed a series of quantitative assessments (body weight and composition, cardiorespiratory fitness, diet and activity habits) and structured qualitative assessments (structured interview or focus group). Participants were predominantly normal-weight (mean BMI=22.2±0.4 kg/m2) and fit (VO2max = 50.5±1.5 ml/kg/min). However, healthy eating and physical activity were not considered high priorities, despite having ample free time, high exercise self-efficacy, positive outcome expectations for exercise, and a desire to exercise more. Participants reported that regularly engaging in exercise was difficult. This may have been due to poor planning/time management, satisfaction with body image, lack of accountability and feelings of laziness. Dietary patterns generally met recommendations but were low in fruits, vegetables and whole grains. Social support for exercise and healthy dietary habits were important factors associated with health behaviors. Students reported a decline in exercise and dietary habits relative to high school, which may contribute to college weight gain. Our results suggest that this population may not have adequate self-regulatory skills, such as planning and self-monitoring, to maintain healthy behaviors in the college environment. Dietitians working with young adults attending college may use these findings to guide the behavioral therapy component of their weight management medical nutrition therapy goals and outcomes. PMID:18926139

  4. FY2014 FES (Fusion Energy Sciences) Theory & Simulation Performance Target, Final Report

    SciTech Connect

    Fu, Guoyong; Budny, Robert; Gorelenkov, Nikolai; Poli, Francesca; Chen, Yang; McClenaghan, Joseph; Lin, Zhihong; Spong, Don; Bass, Eric; Waltz, Ron

    2014-10-14

    We report here the work done for the FY14 OFES Theory Performance Target as given below: "Understanding alpha particle confinement in ITER, the world's first burning plasma experiment, is a key priority for the fusion program. In FY 2014, determine linear instability trends and thresholds of energetic particle-driven shear Alfven eigenmodes in ITER for a range of parameters and profiles using a set of complementary simulation models (gyrokinetic, hybrid, and gyrofluid). Carry out initial nonlinear simulations to assess the effects of the unstable modes on energetic particle transport". In the past year (FY14), a systematic study of the alpha-driven Alfven modes in ITER has been carried out jointly by researchers from six institutions involving seven codes including the transport simulation code TRANSP (R. Budny and F. Poli, PPPL), three gyrokinetic codes: GEM (Y. Chen, Univ. of Colorado), GTC (J. McClenaghan, Z. Lin, UCI), and GYRO (E. Bass, R. Waltz, UCSD/GA), the hybrid code M3D-K (G.Y. Fu, PPPL), the gyro-fluid code TAEFL (D. Spong, ORNL), and the linear kinetic stability code NOVA-K (N. Gorelenkov, PPPL). A range of ITER parameters and profiles are specified by TRANSP simulation of a hybrid scenario case and a steady-state scenario case. Based on the specified ITER equilibria linear stability calculations are done to determine the stability boundary of alpha-driven high-n TAEs using the five initial value codes (GEM, GTC, GYRO, M3D-K, and TAEFL) and the kinetic stability code (NOVA-K). Both the effects of alpha particles and beam ions have been considered. Finally, the effects of the unstable modes on energetic particle transport have been explored using GEM and M3D-K.

  5. Methods of studying the composition of the low-energy ion beams and the surface of deuterated-metal targets

    NASA Astrophysics Data System (ADS)

    Kuznetsov, S. I.; Dudkin, G. N.; Nechaev, B. A.; Bystritsky, I. D.

    2016-06-01

    To study the reactions between the light nuclei (dd, pd, d3He, d4He) with ultralow collision energies, there is a need to obtain the high-precision experimental results on the purity of the target surface saturated with the hydrogen isotopes (protium, deuterium) and on the number and composition of the accelerated particles falling on the target. To solve this problem, a method has been developed and tested for operational testing the quality of the vacuum system and the cleaning of the metal target surface saturated with deuterium. The paper also presents the measurement results for the true flow of the accelerated ions and neutrals of hydrogen (deuterium), using a multigrid electrostatic energy analyzer. The values of the ion and neutral components of the accelerated particle flow were received for the Hall ion source. The values of the secondary electron emission coefficients were determined for a number of the metal targets (Cu, Ti, Ta, Zr) in the range of the accelerated ion energies of 3-12 keV.

  6. Microjet formation and hard x-ray production from a liquid metal target irradiated by intense femtosecond laser pulses

    SciTech Connect

    Lar'kin, A. Uryupina, D.; Ivanov, K.; Savel'ev, A.; Bonnet, T.; Gobet, F.; Hannachi, F.; Tarisien, M.; Versteegen, M.; Spohr, K.; Breil, J.; Chimier, B.; Dorchies, F.; Fourment, C.; Leguay, P.-M.; Tikhonchuk, V. T.

    2014-09-15

    By using a liquid metal as a target one may significantly enhance the yield of hard x-rays with a sequence of two intense femtosecond laser pulses. The influence of the time delay between the two pulses is studied experimentally and interpreted with numerical simulations. It was suggested that the first arbitrary weak pulse produces microjets from the target surface, while the second intense pulse provides an efficient electron heating and acceleration along the jet surface. These energetic electrons are the source of x-ray emission while striking the target surface. The microjet formation is explained based on the results given by both optical diagnostics and hydrodynamic modeling by a collision of shocks originated from two distinct zones of laser energy deposition.

  7. Mechanical properties of lightweight metals from first principles orbital-free density functional theory

    NASA Astrophysics Data System (ADS)

    Shin, Ilgyou

    Accurate quantum mechanics theory and a fast linear-scaling algorithm that OFDFT adopts can create a great synergy to understand underlying atomic-scale physics of material properties and to provide accurate predictions of mesoscale properties for novel materials. We employ OFDFT simulations to study mechanical properties of lightweight metals: FCC Al, HCP Mg, and BCC Mg-Li alloys. The accuracy of OFDFT is mainly governed by two approximations: an electron kinetic energy density functional (KEDF) and a local electron-ion pseudopotential (LPS). We propose and validate a new KEDF for semiconductors and a new LPS for Mg-Li alloys. First, we investigate dislocation structures in Al. OFDFT-optimized dislocation structures are consistent with an experimental estimation. We then calculate the Peierls stress (sigmap) of Al dislocations. We discover two possible screw dislocation structures (dissociated and undissociated), whose sigmaps differ by two orders of magnitude. This result may resolve the decades-long mystery in FCC metals regarding the two orders of magnitude discrepancy in sigmap measurements. Next, we investigate plastic properties of various slip systems in Mg. We propose that strong anisotropies in stacking fault energy surfaces, cross-slip of screw dislocations to basal planes, and the compact nature of edge dislocations on non-basal planes are responsible for Mg's limited ductility. We then explicitly calculate the sigma p of Mg dislocations on the basal and prismatic slip planes. OFDFT-calculated sigma ps are in excellent agreement with experiments. We predict a basal edge dislocation can move 59 times more readily than a prismatic one, which gives rise to the characteristically large anisotropy in Mg's plasticity. Next, we study plasticity of novel BCC Mg-Li alloys as potential lightweight metals. We propose alloys with 31-50 at.% Li can maximize potential strength while increasing ductility compared to Mg, with their sigmaps predicted to be ~0.3 GPa

  8. Proceedings of Soil Decon `93: Technology targeting radionuclides and heavy metals

    SciTech Connect

    Not Available

    1993-09-01

    The principal objective for convening this workshop was to exchange ideas and discuss with scientists and engineers methods for removing radionuclides and/or toxic metals from soils. Over the years there have been numerous symposia, conferences, and workshops directed at soil remediation. However, this may be the first where the scope was narrowed to the removal of radionuclides and toxic metals from soils. The intent was to focus on the separation processes controlling the removal of the radionuclide and/or metal from soil. Its purpose was not intended to be a soil washing/leaching workshop, but rather to identify a variety or combination of processes (chemical, physical, and biological) that can be used in concert with the applicable engineering approaches to decontaminate soils of radionuclides and toxic metals. Abstracts and visual aids used by the speakers of the workshop are presented in this document.

  9. Density functional theory study of CO2 capture with transition metal oxides and hydroxides

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Duan, Yuhua; Johnson, Karl

    2012-02-01

    We have used density functional theory (DFT) employing several different exchange-correlation functionals (PW91, PBE, PBEsol, TPSS, and revTPSS) coupled with lattice dynamics calculations to compute the thermodynamics of CO2 absorption/desorption reactions for selected transition metal oxides, (TMO), and hydroxides, TM(OH)2, where TM = Mn, Ni, Zn, and Cd. The van't Hoff plots, which describe the reaction equilibrium as a function of the partial pressures of CO2 and H2O as well as temperature, were computed from DFT total energies, complemented by the free energy contribution of solids and gases from lattice dynamics and statistical mechanics, respectively. We find that the PBEsol functional calculations are generally in better agreement with experimental phase equilibrium data compared with the other functionals we tested. In contrast, the formation enthalpies of the compounds are better computed with the TPSS and revTPSS functionals. The PBEsol functional gives better equilibrium properties due to a partial cancellation of errors in the enthalpies of formation. We have identified all CO2 capture reactions that lie on the Gibbs free energy convex hull as a function of temperature and the partial pressures of CO2 and H2O for all TMO and TM(OH)2 systems studied here.

  10. Theory of molecule metal nano-particle interaction: Quantum description of plasmonic lasing

    SciTech Connect

    Zhang, Yuan May, Volkhard

    2015-06-14

    The recent quantum description of a few molecules interacting with plasmon excitations of a spherical metal nano-particle (MNP) as presented in the work of Zhang and May [Phys. Rev. B 89, 245441 (2014)] is extended to systems with up to 100 molecules. We demonstrate the possibility of multiple plasmon excitation and describe their conversion into far-field photons. The calculation of the steady-state photon emission spectrum results in an emission line-narrowing with an increasing number of molecules coupled to the MNP. This is considered as an essential criterion for the action of the molecule-MNP system as a nano-laser. To have exact results for systems with up to 20 molecules, we proceed as recently described by Richter et al. [Phys. Rev. B 91, 035306 (2015)] and study a highly symmetric system. It assumes an equatorial and regular position of identical molecules in such a way that their coupling is dominated by that to a single MNP dipole-plasmon excitation. Changing from the exact computation of the system’s complete density matrix to an approximate theory based on the reduced plasmon density matrix, systems with more than 100 molecules can be described. Finally, nonlinear rate equations are proposed which reproduce the mean number of excited plasmons in their dependence of the number of molecules and of the used pump rate. The second order intensity correlation function of emitted photons is related to the respective plasmon correlation function which approaches unity when the system starts lasing.

  11. Electrolyte decomposition on Li-metal surfaces from first-principles theory

    NASA Astrophysics Data System (ADS)

    Ebadi, Mahsa; Brandell, Daniel; Araujo, C. Moyses

    2016-11-01

    An important feature in Li batteries is the formation of a solid electrolyte interphase (SEI) on the surface of the anode. This film can have a profound effect on the stability and the performance of the device. In this work, we have employed density functional theory combined with implicit solvation models to study the inner layer of SEI formation from the reduction of common organic carbonate electrolyte solvents (ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate) on a Li metal anode surface. Their stability and electronic structure on the Li surface have been investigated. It is found that the CO producing route is energetically more favorable for ethylene and propylene carbonate decomposition. For the two linear solvents, dimethyl and diethyl carbonates, no significant differences are observed between the two considered reduction pathways. Bader charge analyses indicate that 2 e- reductions take place in the decomposition of all studied solvents. The density of states calculations demonstrate correlations between the degrees of hybridization between the oxygen of adsorbed solvents and the upper Li atoms on the surface with the trend of the solvent adsorption energies.

  12. Theory of molecule metal nano-particle interaction: Quantum description of plasmonic lasing.

    PubMed

    Zhang, Yuan; May, Volkhard

    2015-06-14

    The recent quantum description of a few molecules interacting with plasmon excitations of a spherical metal nano-particle (MNP) as presented in the work of Zhang and May [Phys. Rev. B 89, 245441 (2014)] is extended to systems with up to 100 molecules. We demonstrate the possibility of multiple plasmon excitation and describe their conversion into far-field photons. The calculation of the steady-state photon emission spectrum results in an emission line-narrowing with an increasing number of molecules coupled to the MNP. This is considered as an essential criterion for the action of the molecule-MNP system as a nano-laser. To have exact results for systems with up to 20 molecules, we proceed as recently described by Richter et al. [Phys. Rev. B 91, 035306 (2015)] and study a highly symmetric system. It assumes an equatorial and regular position of identical molecules in such a way that their coupling is dominated by that to a single MNP dipole-plasmon excitation. Changing from the exact computation of the system's complete density matrix to an approximate theory based on the reduced plasmon density matrix, systems with more than 100 molecules can be described. Finally, nonlinear rate equations are proposed which reproduce the mean number of excited plasmons in their dependence of the number of molecules and of the used pump rate. The second order intensity correlation function of emitted photons is related to the respective plasmon correlation function which approaches unity when the system starts lasing.

  13. Theory-guided design of nanoscale multi-metallic catalysts for fuel cells

    SciTech Connect

    Balbuena, Perla B; Seminario, Jorge M

    2007-04-30

    Research goals This project aims to address the following aspects of the oxygen reduction reaction on multimetallic nanocatalysts: 1. Elucidate physical and chemical aspects of electron and proton transfer 2. Incorporate local and nonlocal field effects to the analysis 3. Investigate the performance of bimetallic and multimetallic nanocatalytic ensembles a. Explore combinations of Pt with other non-precious metals b. Explore theoretically the performance of active catalytic sites/substrate/proton-carrier systems towards maximizing oxygen reduction currents. c. Explore compatibility catalyst/substrate/ionic carrier. 4. Investigate nanocatalyst stability under the reaction conditions, effects of pH and overall composition; surface segregation phenomena in nanoclusters. 5. Carry out theory-guided experiments involving electron transfer as proof of concept. Specific objectives for the previous year: Determine trends for catalytic activity towards the oxygen reduction reaction and stability against dissolution of Pt-based alloy nanocatalysts exposed to acid medium. Reactivity and stability trends are sought as a function of surface composition and atomic distribution in the first 2-3 surface layers. Investigate possible mechanisms for metal dissolution. Developing and testing new computational approaches to characterize the catalytic interface. Significant achievements and results for the previous year: Catalytic activity: Variations in atomic distribution (mixed vs. ordered structures) analyzed in small clusters and extended surfaces of PtxPdy at fixed overall composition revealed polarization effects caused by specific electronic density distributions determining trends in reactivity. We studied other bimetallic and trimetallic systems to characterize the ability of various alloy elements for modifying Pt reactivity. We found an interesting parallelism between metalloenzymes and bimetallic nanocatalysts for the oxygen reduction reaction. Along the same lines, we are

  14. Modeling of remelting processes of metal targets using pulses of continuous laser with pre-impulses

    NASA Astrophysics Data System (ADS)

    Jach, Karol; Marczak, Jan; Świerczyński, Robert; Strzelec, Marek; Ostrowski, Roman; Sarzyński, Antoni; Skrzeczanowski, Wojciech; Rycyk, Antoni; CzyŻ, Krzysztof

    2016-12-01

    The study presents preliminary results of theoretical analyses concerning interaction of quasi-cw laser radiation with an aluminium target. The range of laser power the authors were interested in was from 1 to 10 kW, and target thicknesses from 0.1 to 1 cm. It was also assumed that a laser beam diameter on the target (Al) was around 0.5 cm. A mathematicalphysical model of the phenomenon was based on the equation of conservation of energy (spatially one-dimensional model - (z,t)) taking into account: radiation absorption and transport inside the target, heat conduction, reflection of part of radiation from the target's surface, and heat losses in the processes of melting and evaporation. Coefficients of light absorption and reflection from the target's surface were described with semi-empirical expressions, which took into account their dependence on the temperature and density. Initially, a case of target static during heating was considered. Subsequently, the problem of enhancement of radiation interaction with the target (decrease of reflection coefficient) by the use of short (< 20 ns), high power pre-impulse was analyzed. The last case needed expansion of a set of equations with the continuity equation and the equation of motion, to take into account evaporation of target's surface under influence of the pre-impulse. It was shown that thermal effect of the pre-impulse is practically not influencing final depths of target remelting. On the other hand, damage (matting) of the target's surface by the pre-impulse, causing the decrease of reflection coefficient can have a substantial influence on the remelting depth.

  15. Polymer-based metal nano-coated disposable target for matrix-assisted and matrix-free laser desorption/ionization mass spectrometry.

    PubMed

    Bugovsky, Stefan; Winkler, Wolfgang; Balika, Werner; Koranda, Manfred; Allmaier, Günter

    2016-07-15

    The ideal MALDI/LDI mass spectrometry sample target for an axial TOF instrument possesses a variety of properties. Primarily, it should be chemically inert to the sample, i.e. analyte, matrix and solvents, highly planar across the whole target, without any previous chemical contact and provide a uniform surface to facilitate reproducible measurements without artifacts from previous sample or matrix compounds. This can be hard to achieve with a metal target, which has to be extensively cleaned every time after use. Any cleaning step may leave residues behind, may change the surface properties due to the type of cleaning method used or even cause microscopic scratches over time hence altering matrix crystallization behavior. Alternatively, use of disposable targets avoids these problems. As each possesses the same surface they therefore have the potential to replace the conventional full metal targets so commonly employed. Furthermore, low cost single-use targets with high planarity promise an easier compliance with GLP guidelines as they alleviate the problem of low reproducibility due to inconsistent sample/matrix crystallization and changes to the target surface properties. In our tests, polymeric metal nano-coated targets were compared to a stainless steel reference. The polymeric metal nano-coated targets exhibited all the performance characteristics for a MALDI MS sample support, and even surpassed the - in our lab commonly used - reference in some aspects like limit of detection. The target exhibits all necessary features such as electrical conductivity, vacuum, laser and solvent compatibility.

  16. Actinide chelation: biodistribution and in vivo complex stability of the targeted metal ions.

    PubMed

    Kullgren, Birgitta; Jarvis, Erin E; An, Dahlia D; Abergel, Rebecca J

    2013-01-01

    Because of the continuing use of nuclear fuel sources and heightened threats of nuclear weapon use, the amount of produced and released radionuclides is increasing daily, as is the risk of larger human exposure to fission product actinides. A rodent model was used to follow the in vivo distribution of representative actinides, administered as free metal ions or complexed with chelating agents including diethylenetriamine pentaacetic acid (DTPA) and the hydroxypyridinonate ligands 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO). Different metabolic pathways for the different metal ions were evidenced, resulting in intricate ligand- and metal-dependent decorporation mechanisms. While the three studied chelators are known for their unrivaled actinide decorporation efficiency, the corresponding metal complexes may undergo in vivo decomposition and release metal ions in various biological pools. This study sets the basis to further explore the metabolism and in vivo coordination properties of internalized actinides for the future development of viable therapeutic chelating agents.

  17. Localization of metal targets by time reversal of electromagnetic waves . 3D-numerical and experimental study

    NASA Astrophysics Data System (ADS)

    Benhamouche, Mehdi; Bernard, Laurent; Serhir, Mohammed; Pichon, Lionel; Lesselier, Dominique

    2013-11-01

    This paper proposes a criterion for locating obstacles by time reversal (TR) of electromagnetic (EM) waves based on the analysis of the density of EM energy map in time domain. Contrarily to a monochromatic study of the TR, the wide-band approach requires to determine the instant of the wave focus. This enables us to locate the focal spots that are indicative of the positions. The criterion proposed is compared to the inverse of the minimum entropy criterion as used in the literature [X. Xu, E.L. Miller, C.M. Rappaport, IEEE Trans. Geosci. Remote Sens. 41, 1804 (2003)]. An application for the localization of 3D metal targets is proposed using finite integration technique (FIT) as computational tool at the modeling stage. An experimental validation is presented for canonical three-dimensional configurations with two kinds of metal objects. Contribution to the Topical Issue "Numelec 2012", Edited by Adel Razek.

  18. A multi-element screening method to identify metal targets for blood biomonitoring in green sea turtles (Chelonia mydas).

    PubMed

    Villa, C A; Finlayson, S; Limpus, C; Gaus, C

    2015-04-15

    Biomonitoring of blood is commonly used to identify and quantify occupational or environmental exposure to chemical contaminants. Increasingly, this technique has been applied to wildlife contaminant monitoring, including for green turtles, allowing for the non-lethal evaluation of chemical exposure in their nearshore environment. The sources, composition, bioavailability and toxicity of metals in the marine environment are, however, often unknown and influenced by numerous biotic and abiotic factors. These factors can vary considerably across time and space making the selection of the most informative elements for biomonitoring challenging. This study aimed to validate an ICP-MS multi-element screening method for green turtle blood in order to identify and facilitate prioritisation of target metals for subsequent fully quantitative analysis. Multi-element screening provided semiquantitative results for 70 elements, 28 of which were also determined through fully quantitative analysis. Of the 28 comparable elements, 23 of the semiquantitative results had an accuracy between 67% and 112% relative to the fully quantified values. In lieu of any available turtle certified reference materials (CRMs), we evaluated the use of human blood CRMs as a matrix surrogate for quality control, and compared two commonly used sample preparation methods for matrix related effects. The results demonstrate that human blood provides an appropriate matrix for use as a quality control material in the fully quantitative analysis of metals in turtle blood. An example for the application of this screening method is provided by comparing screening results from blood of green turtles foraging in an urban and rural region in Queensland, Australia. Potential targets for future metal biomonitoring in these regions were identified by this approach.

  19. Target depth dependence of damage rate in metals by 150 MeV proton irradiation

    NASA Astrophysics Data System (ADS)

    Yoshiie, T.; Ishi, Y.; Kuriyama, Y.; Mori, Y.; Sato, K.; Uesugi, T.; Xu, Q.

    2015-01-01

    A series of irradiation experiments with 150 MeV protons was performed. The relationship between target depth (or shield thickness) and displacement damage during proton irradiation was obtained by in situ electrical resistance measurements at 20 K. Positron annihilation lifetime measurements were also performed at room temperature after irradiation, as a function of the target thickness. The displacement damage was found to be high close to the beam incident surface area, and decreased with increasing target depth. The experimental results were compared with damage production calculated with an advanced Monte Carlo particle transport code system (PHITS).

  20. A HIGH FIELD PULSED SOLENOID MAGNET FOR LIQUID METAL TARGET STUDIES.

    SciTech Connect

    KIRK,H.G.IAROCCI,M.SCADUTO,J.WEGGEL,R.J.MULHOLLAND,G.MCDONALD,K.T.

    2003-05-12

    The target system for a muon collider/neutrino factory requires the conjunction of an intense proton beam, a high-Z liquid target and a high-field solenoid magnet. We describe here the design parameters for a pulsed solenoid, including the magnet cryogenic system and power supply, that can generate transient fields of greater than 10T with a flat-tops on the order of 1 second. It is envisioned to locate this device at the Brookhaven AGS for proof-of-principle testing of a liquid-jet target system with pulses of le13 protons.

  1. Crystal structure of the pressure-induced metallic phase of SiH4 from ab initio theory.

    PubMed

    Kim, D Y; Scheicher, R H; Lebègue, S; Prasongkit, J; Arnaud, B; Alouani, M; Ahuja, R

    2008-10-28

    Metallization of pure solid hydrogen is of great interest, not least because it could lead to high-temperature superconductivity, but it continues to be an elusive goal because of great experimental challenges. Hydrogen-rich materials, in particular, CH(4), SiH(4), and GeH(4), provide an opportunity to study related phenomena at experimentally achievable pressures, and they too are expected to be high-temperature superconductors. Recently, the emergence of a metallic phase has been observed in silane for pressures just above 60 GPa. However, some uncertainty exists about the crystal structure of the discovered metallic phase. Here, we show by way of elimination, that a single structure that possesses all of the required characteristics of the experimentally observed metallic phase of silane from a pool of plausible candidates can be identified. Our density functional theory and GW calculations show that a structure with space group P4/nbm is metallic at pressures >60 GPa. Based on phonon calculations, we furthermore demonstrate that the P4/nbm structure is dynamically stable at >43 GPa and becomes the ground state at 97 GPa when zero-point energy contributions are considered. These findings could lead the way for further theoretical analysis of metallic phases of hydrogen-rich materials and stimulate experimental studies.

  2. Classification of processes for the atomic layer deposition of metals based on mechanistic information from density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Elliott, S. D.; Dey, G.; Maimaiti, Y.

    2017-02-01

    Reaction cycles for the atomic layer deposition (ALD) of metals are presented, based on the incomplete data that exist about their chemical mechanisms, particularly from density functional theory (DFT) calculations. ALD requires self-limiting adsorption of each precursor, which results from exhaustion of adsorbates from previous ALD pulses and possibly from inactivation of the substrate through adsorption itself. Where the latter reaction does not take place, an "abbreviated cycle" still gives self-limiting ALD, but at a much reduced rate of deposition. Here, for example, ALD growth rates are estimated for abbreviated cycles in H2-based ALD of metals. A wide variety of other processes for the ALD of metals are also outlined and then classified according to which a reagent supplies electrons for reduction of the metal. Detailed results on computing the mechanism of copper ALD by transmetallation are summarized and shown to be consistent with experimental growth rates. Potential routes to the ALD of other transition metals by using complexes of non-innocent diazadienyl ligands as metal sources are also evaluated using DFT.

  3. Electronic Structure of Semiconducting and Metallic Tubes in TiO2/Carbon Nanotube Heterojunctions: Density Functional Theory Calculations.

    PubMed

    Long, Run

    2013-04-18

    The electronic structure of the TiO2(110) surface interfaced with both a semiconducting and metallic carbon nanotube (CNT) was investigated by density functional theory. Our simulations rationalized visible light photocatalytic activity of CNT/TiO2 hybrid materials higher than that under ultraviolent irradiation and showed that the photoactivity of a semiconducting CNT decorating TiO2 is better than that of the metallic CNT/TiO2 system due to efficient charge separation across the interface. This suggests that semiconducting CNT/TiO2 could be a potential photovoltaic material. In contrast, strong interaction between a metallic CNT and TiO2 leads to large charge transfer. Such charge transfer reduces the built-in potential, in turn resulting in inefficient charge separation. Functionalizing the metallic CNT with a small platinum cluster can increase the built-in potential and drive charge separation. These observations indicate that the CNT/TiO2 interface can be a potential photovoltaic material by a metal cluster decorating a CNT despite a real tube being composed of the mixture of metallic and semiconducting CNTs.

  4. The electrostatic interaction of an external charged system with a metal surface: a simplified density functional theory approach

    NASA Astrophysics Data System (ADS)

    Scivetti, Iván; Persson, Mats

    2013-09-01

    As a first step to meet the challenge to calculate the electronic structure and total energy of charged states of atoms and molecules adsorbed on ultrathin insulating films supported by a metallic substrate using density functional theory (DFT), we have developed a simplified new DFT scheme that only describes the electrostatic interaction of an external charged system with a metal surface. This purely electrostatic interaction is obtained from the assumption that the electron densities of the two fragments (charged system and metal surface) are non-overlapping and by neglecting non-local exchange-correlation effects such as the van der Waals interactions between the two fragments. In addition, the response of the metal surface to the electrostatic potential from the charged system is treated to linear order, whereas the charged system is treated fully within DFT. In particular, we consider the classical perfect conductor model for the metal response, although our formalism is not limited to this approximation. To test the computational implementation of this new scheme, we have considered the case of a Na+ cation interacting with a perfect conductor. The application of this new methodology to realistic problems involving charged systems adsorbed on insulating films supported by a metal surface are deferred to a separate following publication.

  5. Classification of processes for the atomic layer deposition of metals based on mechanistic information from density functional theory calculations.

    PubMed

    Elliott, S D; Dey, G; Maimaiti, Y

    2017-02-07

    Reaction cycles for the atomic layer deposition (ALD) of metals are presented, based on the incomplete data that exist about their chemical mechanisms, particularly from density functional theory (DFT) calculations. ALD requires self-limiting adsorption of each precursor, which results from exhaustion of adsorbates from previous ALD pulses and possibly from inactivation of the substrate through adsorption itself. Where the latter reaction does not take place, an "abbreviated cycle" still gives self-limiting ALD, but at a much reduced rate of deposition. Here, for example, ALD growth rates are estimated for abbreviated cycles in H2-based ALD of metals. A wide variety of other processes for the ALD of metals are also outlined and then classified according to which a reagent supplies electrons for reduction of the metal. Detailed results on computing the mechanism of copper ALD by transmetallation are summarized and shown to be consistent with experimental growth rates. Potential routes to the ALD of other transition metals by using complexes of non-innocent diazadienyl ligands as metal sources are also evaluated using DFT.

  6. Physics of laser fusion. Vol. I. Theory of the coronal plasma in laser-fusion targets

    SciTech Connect

    Max, C.E.

    1981-12-01

    This monograph deals with the physics of the coronal region in laser fusion targets. The corona consists of hot plasma which has been evaporated from the initially solid target during laser heating. It is in the corona that the laser light is absorbed by the target, and the resulting thermal energy is conducted toward cold high-density regions, where ablation occurs. The topics to be discussed are theoretical mechanisms for laser light absorption and reflection, hot-electron production, and the physics of heat conduction in laser-produced plasmas. An accompanying monograph by H. Ahlstrom (Vol.II) reviews the facilities, diagnostics, and data from recent laser fusion experiments.

  7. Interaction Of CO2 Laser Nanosecond Pulse Train With The Metallic Targets In Optical Breakdown Regime

    NASA Astrophysics Data System (ADS)

    Apollonov, V. V.; Firsov, K. N.; Konov, V. I.; Nikitin, P. I.; Prokhorov, A. M.; Silenok, A. S.; Sorochenko, V. R.

    1986-11-01

    In the present paper the electric field and currents in the air-breakdown plasma, produced by the train of nanosecond pulses of TEA-002 - regenerative amplifier near the un-charged targets are studied. The breakdown thresholds and the efficiency of plasma-target heat transmission are also measured. The results of numerical calculations made for increasing of the pulse train contrast with respect to the background in a regenerative amplifier are advanced.

  8. Inside HOLMES experiment: 163Ho metallic target production for the micro-calorimeter absorber

    NASA Astrophysics Data System (ADS)

    Pizzigoni, G.; Alpert, B.; Balata, M.; Bennett, D.; Biasotti, M.; Boragno, C.; Brofferio, C.; De Gerone, M.; Dressler, R.; Faverazani, M.; Ferri, E.; Folwer, J.; Gatti, F.; Giachero, A.; Heinitz, S.; Hilton, G.; Köster, U.; Lusignoli, M.; Maino, M.; Mates, J.; Nisi, S.; Nizzolo, R.; Nucciotti, A.; Pessina, G.; Puiu, A.; Ragazzi, S.; Reintsema, C.; Ribeiro Gomes, M.; Shmidt, D.; Schumann, D.; Sisti, M.; Swetz, D.; Terranova, F.; Ullom, J.; Day, P. K.

    2016-07-01

    The main goal in the HOLMES experiment is the neutrino mass measurement using an array of 1000 micro-calorimeters with standard metallic absorber. A good isotope for such measurement is the 163Ho, those isotopes embedded in the metallic absorber will be 1011-1013. Since 163Ho is not available in nature, a dedicated process must be set up to produce the amount needed for this neutrino mass experiment. The process with the highest born-up cross-section is the neutron irradiation of Er2O3 enriched in 162Er: 162Er(n,γ)163Er →163Ho+νe, where the decay is an EC with half-life of about 75 min and the (n,γ) is about 20 barns for thermal neutron. After the neutron irradiation in the oxide powder there are several radioactive isotopes which are potentially disturbing because of the background that they cause below 5 keV. The chemical separation of holmium from the irradiation enriched Er2O3 powder is therefore mandatory and will be performed by means of ion exchange chromatography. On the end of those processes the oxide powder enriched in 162Er will have the 163Ho isotope number required. The holmium chemical state influences the end point of the EC spectrum, in order to avoid such effect it is necessary to embed in the absorber only the metallic isotope. Reduction and distillation technique allowed us to obtain a pure metallic holmium, starting from natural oxide holmium. This technique will be applied on the irradiated oxide powder to obtain the metallic 163Ho, ready to be embedded in the micro-calorimeter absorber.

  9. Hypoxia-inducible factor prolyl hydroxylases as targets for neuroprotection by "antioxidant" metal chelators: From ferroptosis to stroke.

    PubMed

    Speer, Rachel E; Karuppagounder, Saravanan S; Basso, Manuela; Sleiman, Sama F; Kumar, Amit; Brand, David; Smirnova, Natalya; Gazaryan, Irina; Khim, Soah J; Ratan, Rajiv R

    2013-09-01

    Neurologic conditions including stroke, Alzheimer disease, Parkinson disease, and Huntington disease are leading causes of death and long-term disability in the United States, and efforts to develop novel therapeutics for these conditions have historically had poor success in translating from bench to bedside. Hypoxia-inducible factor (HIF)-1α mediates a broad, evolutionarily conserved, endogenous adaptive program to hypoxia, and manipulation of components of the HIF pathway is neuroprotective in a number of human neurological diseases and experimental models. In this review, we discuss molecular components of one aspect of hypoxic adaptation in detail and provide perspective on which targets within this pathway seem to be ripest for preventing and repairing neurodegeneration. Further, we highlight the role of HIF prolyl hydroxylases as emerging targets for the salutary effects of metal chelators on ferroptosis in vitro as well in animal models of neurological diseases.

  10. Note: study of extreme ultraviolet and soft x-ray emission of metal targets produced by laser-plasma-interaction.

    PubMed

    Mantouvalou, I; Jung, R; Tuemmler, J; Legall, H; Bidu, T; Stiel, H; Malzer, W; Kanngiesser, B; Sandner, W

    2011-06-01

    Different metal targets were investigated as possible source material for tailored laser-produced plasma-sources. In the wavelength range from 1 to 20 nm, x-ray spectra were collected with a calibrated spectrometer with a resolution of λ/Δλ = 150 at 1 nm up to λ/Δλ = 1100 at 15 nm. Intense line emission features of highly ionized species as well as continuum-like spectra from unresolved transitions are presented. With this knowledge, the optimal target material can be identified for the envisioned application of the source in x-ray spectrometry on the high energy side of the spectra at about 1 keV. This energy is aimed for because 1 keV-radiation is ideally suited for L-shell x-ray spectroscopy with nm-depth resolution.

  11. Hypoxia inducible factor prolyl hydroxylases as targets for neuroprotection by “antioxidant” metal chelators: from ferroptosis to stroke

    PubMed Central

    Speer, Rachel E.; Karuppagounder, Saravanan S.; Basso, Manuela; Sleiman, Sama; Kumar, Amit; Brand, David; Smirnova, Natalya; Gazaryan, Irina; Khim, Soah J.; Ratan, Rajiv R.

    2015-01-01

    Neurologic conditions including stroke, Alzheimer’s disease, Parkinson’s disease and Huntington’s disease are leading causes of death and long-term disability in the United States, and efforts to develop novel therapeutics for these conditions have historically had poor success in translating from bench to bedside. Hypoxia Inducible Factor-1alpha (HIF-1α) mediates a broad, evolutionarily conserved, endogenous adaptive program to hypoxia, and manipulation of components of the HIF pathway are neuroprotective in a number of human neurological diseases and experimental models. In this review, we discuss molecular components of one aspect of hypoxic adpatation in detail, and provide perspective on which targets within this pathway appear to be ripest for preventing and repairing neurodegeneration. Further, we highlight the role of HIF prolyl hydroxylases as emerging targets for the salutary effects of metal chelators on ferroptosis in vitro as well in animal models of neurological diseases. PMID:23376032

  12. The Qualification of Target Materials Using the Integral Theory of Impact

    DTIC Science & Technology

    1976-12-01

    corresponds to V* and is shown to be a function of depth of penetration. The work performed to date and reported upcn here consists of two parts : -4. (1...kinetic energy of a nondeforming pene- trator is absorbed by the target in three different forms * i (Eq. (16)). Part of the energy, given by KDRAG... tensometer , which is capable of applying up to a 2-ton compressive load, a tungsten carbide ball was Yressed into several target materials and the elastic

  13. Enantioselectivity of (321) chiral noble metal surfaces: A density functional theory study of lactate adsorption

    SciTech Connect

    Franke, J.-H.; Kosov, D. S.

    2013-12-14

    The adsorption of the chiral molecule lactate on the intrinsically chiral noble metal surfaces Pt(321), Au(321), and Ag(321) is studied by density functional theory calculations. We use the oPBE-vdW functional which includes van der Waals forces on an ab initio level. It is shown that the molecule binds via its carboxyl and the hydroxyl oxygen atoms to the surface. The binding energy is larger on Pt(321) and Ag(321) than on Au(321). An analysis of the contributions to the binding energy of the different molecular functional groups reveals that the deprotonated carboxyl group contributes most to the binding energy, with a much smaller contribution of the hydroxyl group. The Pt(321) surface shows considerable enantioselectivity of 0.06 eV. On Au(321) and Ag(321) it is much smaller if not vanishing. The chiral selectivity of the Pt(321) surface can be explained by two factors. First, it derives from the difference in van der Waals attraction of L- and D-lactate to the surface that we trace to differences in the binding energy of the methyl group. Second, the multi-point binding pattern for lactate on the Pt(321) surface is sterically more sensitive to surface chirality and also leads to large binding energy contributions of the hydroxyl group. We also calculate the charge transfer to the molecule and the work function to gauge changes in electronic structure of the adsorbed molecule. The work function is lowered by 0.8 eV on Pt(321) with much smaller changes on Au(321) and Ag(321)

  14. A Density Functional Theory Analysis of Trends in Glycerol Decomposition on Close-Packed Transition Metal Surfaces

    SciTech Connect

    Liu, Bin; Greeley, Jeffrey P.

    2013-05-07

    We describe an accelerated density functional theory (DFT)-based computational strategy to determine trends in the decomposition of glycerol via elementary dehydrogenation, C–C, and C–O bond scission reactions on close-packed transition metal surfaces. Beginning with periodic DFT calculations on Pt(111), the thermochemistry of glycerol dehydrogenation on Pd(111), Rh(111), Cu(111) and Ni(111) is determined using a parameter-free, bond order-based scaling relationship. By combining the results with Brønsted–Evans–Polanyi (BEP) relationships to estimate elementary reaction barriers, free energy diagrams are developed on the respective metal surfaces, and trends concerning the relative selectivity and activity for C–C and C–O bond scission in glycerol on the various metals are obtained. The results are consistent with available theoretical and experimental literature and demonstrate that scaling relationships are capable of providing powerful insights into the catalytic chemistry of complex biomolecules.

  15. Perturbation theory of structure in classical liquid mixtures: Application to metallic systems near phase separation. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Henderson, R. L.

    1974-01-01

    The partial structure factors of classical simple liquid mixtures near phase separation are dicussed. The theory is developed for particles interacting through pair potentials, and is thus appropriate both to insulating fluids, and also to metallic systems if these may be described by an effective ion-ion pair interaction. The motivation arose from consideration of metallic liquid mixtures, in which resistive anomalies have been observed near phase separation. A mean field theory correction appropriate to 3 pair potential for the effects of correlated motions in the reference fluid is studied. The work is cast in terms of functions which are closely related to the direct correlation functions of Ornstein and Zernike. The results are qualitatively in accord with physical expectations. Quantitative agreement with experiment seems to turn on the selection of the hard core reference potential in terms of the metallic effective pair potential. It is suggested that the present effective pair potentials are perhaps not properly used to calculate the metallic structure factors at long wavelength.

  16. Thin-film preparation by back-surface irradiation pulsed laser deposition using metal powder targets

    NASA Astrophysics Data System (ADS)

    Kawasaki, Hiroharu; Ohshima, Tamiko; Yagyu, Yoshihito; Ihara, Takeshi; Yamauchi, Makiko; Suda, Yoshiaki

    2017-01-01

    Several kinds of functional thin films were deposited using a new thin-film preparation method named the back-surface irradiation pulsed laser deposition (BIPLD) method. In this BIPLD method, powder targets were used as the film source placed on a transparent target holder, and then a visible-wavelength pulsed laser was irradiated from the holder side to the substrate. Using this new method, titanium oxide and boron nitride thin films were deposited on the silicon substrate. Surface scanning electron microscopy (SEM) images suggest that all of the thin films were deposited on the substrate with some large droplets irrespective of the kind of target used. The deposition rate of the films prepared by using this method was calculated from film thickness and deposition time to be much lower than that of the films prepared by conventional PLD. X-ray diffraction (XRD) measurement results suggest that rutile and anatase TiO2 crystal peaks were formed for the films prepared using the TiO2 rutile powder target. Crystal peaks of hexagonal boron nitride were observed for the films prepared using the boron nitride powder target. The crystallinity of the prepared films was changed by annealing after deposition.

  17. Theoretical investigation of the thermal hydraulic behaviour of a slab-type liquid metal target

    SciTech Connect

    Dury, T.V.; Smith, B.L.

    1996-06-01

    The thermal hydraulics codes CFDS-FLOW3D and ASTEC have been used to simulate a slabtype design of ESS spallation target. This design is single-skinned, and of tapering form (in the beam direction), with rounded sides in a cross-section through a plane normal to the beam. The coolant fluid used is mercury, under forced circulation, with an inlet temperature of 180{degrees}C. The goal of these computer studies was to understand the behaviour of the coolant flow, and hence to arrive at a design which optimises the heat extraction for a given beam power - in the sense of: (1) minimising the peak local fluid temperature within the target, (2) maintaining an acceptable temperature level and distribution over and through the target outer wall, (3) keeping the overall fluid pressure loss through the complete target to a minimum, (4) staying within the physical limits of overall size required, particularly in the region of primary spallation. Two- and three-dimensional models have been used, with different arrangements and design of internal baffles, and different coolant flow distributions at the target inlet. Nominal total inlet mass flow was 245 kg/s, and a heat deposition profile used which was based on the proton beam energy distribution. This gave a nominal total heat load of 3.23 MW - of which 8.2kW were deposited in the window steel.

  18. Shock Ignition in Non-Cryogenic Metal-Gas Targets on the National Ignition Facility

    NASA Astrophysics Data System (ADS)

    Perkins, L. John; Cerjan, C.; Smalyuk, V.; Bailey, D.; Comley, A.; Garbett, W.; McKenty, P.; Cheng, B.

    2011-10-01

    Shock ignition offers the possibility of volumetric ignition and burn in single-shell, room-temperature gas targets on the National Ignition Facility. We are investigating whether the high fusion energy gains potentially available with shock ignition in cryogenic DT targets on NIF (L.J.Perkins et al, PRL 103 (2009)) can be traded for modest gains and yields in such platforms. If so, being non-cryogenic with simple single-shell construction and medium-pressure gas fill, they should easier to field and diagnose. The targets are characterized by a thick, graded-density Be-Au ablator-pusher shell with low in-flight-aspect-ratios. Because the high-Z Au shell reflects Bremsstrahlung, such targets are capable of volumetric ignition at temperatures of around 4 keV with low shell velocities around 1.5e7cm/s. Gas targets are inherently low gain (<=10) so they are probably not IFE relevant. The ultimate performance will be determined by degree and control of high-Z mix in the gas. Simulations indicate that we can potentially trade fusion yield for good ignition fall-line behavior by tuning gas pressure and shock launch time. This work performed under the auspices of U.S. DOE by LLNL under Contract DE-AC52-07NA27344.

  19. Metal concentrations in selected brands of canned fish in Nigeria: estimation of dietary intakes and target hazard quotients.

    PubMed

    Iwegbue, Chukwujindu M A

    2015-03-01

    The concentrations of metals (Cd, Pb, Ni, Cr, Cu, Co, Fe, Mn, and Zn) were determined in selected brands of canned mackerel, sardine, and tuna in Nigeria with a view to providing information on the dietary intakes of metals and lifelong health hazards associated with the consumption of these products. The concentrations of metals were determined by using atomic absorption spectrometry after acid digestion. The mean concentrations of metals in canned mackerel, sardine, and tuna were found as 0.04-0.58, 0.06-0.44, 0.32-0.83 μg/g for Cd; 0.05-2.82, 0.70-2.98, 0.23-2.56 μg/g for Pb, 1.33-11.33, <0.20-17.53, nd-34.2 μg/g for Ni, 0.49-3.79, 0.22-1.89, 0.66-14.39 μg/g for Cr, 0.33-0.92, 0.03-1.51, <0.08-1.31 μg/g for Cu, 0.11-2.17, nd-0.75, 0.14-0.50 μg/g for Co, 6.45-26.90, 6.06-53.54, 3.06-95.78 μg/g for Fe, 2.30-3.84, 0.95-21.78, 1.65-2.33 μg/g for Mn, 1.15-7.19, 3.60-17.88, 1.21-5.35 μg/g for Zn, respectively. The mean concentrations of Cd, Pb, and Fe in some of these brands of canned fish were above their permissible limits while other metals occurred at levels below their permissible limits. The estimated daily intakes of metals from consumption of 20.8 g fish per day by a 60 kg body weight adult were below the provisional tolerable daily intakes for Cd, Pb, Ni, Cr, and Cu and recommended daily intakes for Co, Fe, Mn, and Zn. The estimated target hazard quotients of the examined metals were less than 1 in the majority of the samples indicating no long-term health hazard at the present circumstance.

  20. Recent developments in human biomonitoring: non-invasive assessment of target tissue dose and effects of pneumotoxic metals

    PubMed Central

    Mutti, A.; Corradi, M.

    2006-01-01

    Summary Tobacco smoke and polluted environments substantially increase the lung burden of pneumotoxic chemicals, particularly pneumotoxic metallic elements. To achieve a better understanding of the early events between exposure to inhaled toxicants and the onset of adverse effects on the lung, the characterization of dose at the target organ would be extremely useful. Exhaled breath condensate (EBC), obtained by cooling exhaled air under conditions of spontaneous breathing, is a novel technique that could provide a non-invasive assessment of pulmonary pathobiology. Considering that EBC is water practically free of interfering solutes, it represents an ideal biological matrix for elemental characterization. Published data show that several toxic metals and trace elements are detectable in EBC, raising the possibility of using this medium to quantify the lung tissue dose of pneumotoxic substances. This novel approach may represent a significant advance over the analysis of alternative media (blood, serum, urine, hair), which are not as reliable (owing to interfering substances in the complex matrix) and reflect systemic rather than lung (target tissue) levels of both toxic metals and essential trace elements. Data obtained among workers occupationally exposed to either hard metals or chromium (VI) and in smokers with or without chronic obstructive pulmonary disease (COPD) are reviewed to show that – together with biomarkers of exposure – EBC also allows the simultaneous quantification of biomarkers of effect directly sampled from the epithelial lining fluid, thus providing novel insights on both kinetic and dynamic aspects of metal toxicology. Riassunto «Recenti sviluppi nel biomonitoraggio umano: valutazione non invasiva della dose a livello dell’organo bersaglio e degli effetti pneumotossici». L’esposizione cronica a fumo di tabacco ed ad altri inquinati ambientali determina un accumulo polmonare di sostanze pneumotossiche, soprattutto metalli. Allo scopo

  1. Charge transfer between sensing and targeted metal nanoparticles in indirect nanoplasmonic sensors

    NASA Astrophysics Data System (ADS)

    Zhdanov, Vladimir P.; Langhammer, Christoph

    2017-03-01

    In indirect nanoplasmonic sensors, the plasmonic metal nanoparticles are adjacent to the material of interest, and the material-related changes of their optical properties are used to probe that material. If the latter itself represents another metal in the form of nanoparticles, its deposition is accompanied by charge transfer to or from the plasmonic nanoparticles in order to equalize the Fermi levels. We estimate the value of the transferred charge and show on the two examples, nanoparticle sintering and hydride formation, that the charge transfer has negligible influence on the probed processes, because the effect of charge transfer is less important than that of nanoparticle surface energy. This further corroborates the non-invasive nature of nanoplasmonic sensors.

  2. Assessment of the lifetime of the beam window of MEGAPIE target liquid metal container

    NASA Astrophysics Data System (ADS)

    Dai, Y.; Henry, J.; Auger, T.; Vogt, J.-B.; Almazouzi, A.; Glasbrenner, H.; Groeschel, F.

    2006-09-01

    The lifetime of the beam window of the T91 liquid Pb-Bi container in the MEGAPIE target is discussed based on the present knowledge of lead bismuth eutectic (LBE) corrosion, embrittlement and radiation effects in relevant conditions. In the MEGAPIE target, since the high hydrogen production will likely reduce the oxygen content to a low level, LBE corrosion may reduce the wall thickness up to 2%. In addition, the corrosion induced grain boundary dissolution will promote LBE embrittlement on the T91 steel in the beam window. The DBTT data and fracture toughness values of T91 specimens tested in contact with LBE suggest a lower bound of the lifetime of the T91 beam window to be limited to a dose of 6 dpa, corresponding to 2.4 Ah proton charge to be received by the target in about 20 weeks in the normal operation condition.

  3. Metal vapor target for precise studies of ion-atom collisions

    SciTech Connect

    Chen, W. Vorobyev, G.; Herfurth, F.; Hillenbrand, P.-M.; Spillmann, U.; Guo, D.; Trotsenko, S.; Gumberidze, A.; Stöhlker, Th.

    2014-05-15

    Although different ion-atom collisions have been studied in various contexts, precise values of cross-sections for many atomic processes were seldom obtained. One of the main uncertainties originates from the value of target densities. In this paper, we describe a unique method to measure a target density precisely with a combination of physical vapor deposition and inductively coupled plasma optical emission spectrometry. This method is preliminarily applied to a charge transfer cross-section measurement in collisions between highly charged ions and magnesium vapor. The final relative uncertainty of the target density is less than 2.5%. This enables the precise studies of atomic processes in ion-atom collisions, even though in the trial test the deduction of precise capture cross-sections was limited by other systematic errors.

  4. Viscosity contribution to the impurity resistivity of metals by means of the current-density functional theory

    NASA Astrophysics Data System (ADS)

    Nazarov, Vladimir U.; Vignale, Giovanni

    2008-03-01

    Within the time-dependent density functional theory formalism we relate the impurity resistivity ρ of a metal to the friction coefficient Q of the metal for the same impurity moving with the infinitesimally small velocity, i.e., ρ=niQ / ne^2 ,1), where ni and ne are the concentrations of the randomly distributed impurities and the valence electrons, respectively. While Eq.(1) occurs trivial within the single-particle theory with the scattering at the statically screened impurities, its general validity within the many-body theory with the dynamical exchange and correlation included presents a progress. We utilize results [1,2] on Q of the electron liquid to put the electron-electron scattering contribution into the terms of the viscosity coefficients [3]. Calculations of the residual resistivity of aluminum as a function of the atomic number of the impurity are performed, improving the agreement with experiment compared to the single- particle theory [4]. [1].V. U. Nazarov, J. M. Pitarke, C. S. Kim, and Y. Takada, Phys. Rev. B 71, 121106(R) (2005). [2].V. U. Nazarov, J. M. Pitarke, Y. Takada, G. Vignale, and Y.-C. Chang, Phys. Rev. B 76, 205103 (2007). [3].G. Vignale, C. A. Ullrich, and S. Conti, Phys. Rev. Lett. 79, 4878 (1997). [4].M. J. Puska and R. M. Nieminen, Phys. Rev. B 27, 6121 (1983).

  5. Targeting high value metals in lithium-ion battery recycling via shredding and size-based separation.

    PubMed

    Wang, Xue; Gaustad, Gabrielle; Babbitt, Callie W

    2016-05-01

    Development of lithium-ion battery recycling systems is a current focus of much research; however, significant research remains to optimize the process. One key area not studied is the utilization of mechanical pre-recycling steps to improve overall yield. This work proposes a pre-recycling process, including mechanical shredding and size-based sorting steps, with the goal of potential future scale-up to the industrial level. This pre-recycling process aims to achieve material segregation with a focus on the metallic portion and provide clear targets for subsequent recycling processes. The results show that contained metallic materials can be segregated into different size fractions at different levels. For example, for lithium cobalt oxide batteries, cobalt content has been improved from 35% by weight in the metallic portion before this pre-recycling process to 82% in the ultrafine (<0.5mm) fraction and to 68% in the fine (0.5-1mm) fraction, and been excluded in the larger pieces (>6mm). However, size fractions across multiple battery chemistries showed significant variability in material concentration. This finding indicates that sorting by cathode before pre-treatment could reduce the uncertainty of input materials and therefore improve the purity of output streams. Thus, battery labeling systems may be an important step towards implementation of any pre-recycling process.

  6. Applying Theory of Mind Concepts When Designing Interventions Targeting Social Cognition among Youth Offenders

    ERIC Educational Resources Information Center

    Noel, Kristine K.; Westby, Carol

    2014-01-01

    This study employed a multiple baseline, across-participants, single-subject design to investigate the feasibility of an individual, narrative-based, social problem-solving intervention on the social problem-solving, narrative, and theory of mind (ToM) abilities of 3 incarcerated adolescent youth offenders identified as having emotional…

  7. Target organs of the Manila clam Ruditapes philippinarum for studying metal accumulation and biomarkers in pollution monitoring: laboratory and in-situ transplantation experiments.

    PubMed

    Won, Eun-Ji; Kim, Kyung-Tae; Choi, Jin-Young; Kim, Eun-Soo; Ra, Kongtae

    2016-08-01

    To characterize the target organs of the Manila clam Ruditapes philippinarum for use in environmental study, the accumulation of trace metals and three biomarkers was measured in different organs. Exposure with Cu and Pb carried out under laboratory conditions revealed a linear uptake of metals throughout the experimental period in each tissue. In particular, significant increase was observed in gills and mantle. The increase of intracellular reactive oxygen species showed the great potential of gills as a target tissue for both Cu and Pb exposure. The highest activity of glutathione S-transferase and their relative increase in activity were also observed in gills. Metallothionein-like protein levels, however, increased greatly in the digestive gland and mantle during Cu and Pb exposure, respectively, although all tissues, except the foot, showed significant changes after 24 h of metal exposure. In the field study, the highest concentration of metals was recorded in the gills and mantle, accounting for over 50 % of the total accumulated metal in all sites. Additionally, Cu and Pb increased significantly in these two organs, respectively. However, the order of accumulation rate in laboratory exposure was not concomitant with those of the lab-based study, suggesting that different routes of metal uptake and exposure duration induce distinct partitioning of metals and regulating system in R. philippinarum. These series of exposure studies demonstrated that gills, mantle, and digestive gland in R. philippinarum are potential target tissues in environmental monitoring study using metal concentrations and biomarkers.

  8. Design strategies to improve the sensitivity of photoactive metal carbonyl complexes (photoCORMs) to visible light and their potential as CO-donors to biological targets.

    PubMed

    Chakraborty, Indranil; Carrington, Samantha J; Mascharak, Pradip K

    2014-08-19

    The recent surprising discovery of the beneficial effects of carbon monoxide (CO) in mammalian physiology has drawn attention toward site-specific delivery of CO to biological targets. To avoid difficulties in handling of this noxious gas in hospital settings, researchers have focused their attention on metal carbonyl complexes as CO-releasing molecules (CORMs). Because further control of such CO delivery through light-triggering can be achieved with photoactive metal carbonyl complexes (photoCORMs), we and other groups have attempted to isolate such complexes in the past few years. Typical metal carbonyl complexes release CO when exposed to UV light, a fact that often deters their use in biological systems. From the very beginning, our effort therefore was directed toward identifying design principles that could lead to photoCORMs that release CO upon illumination with low-power (5-15 mW/cm(2)) visible and near-IR light. In our work, we have utilized Mn(I), Re(I), and Ru(II) centers (all d(6) ground state configuration) to ensure overall stability of the carbonyl complexes. We also hypothesized that transfer of electron density from the electron-rich metal centers to π* MOs of the ligand frame via strong metal-to-ligand charge transfer (MLCT) transitions in the visible/near-IR region would weaken metal-CO back-bonding and promote rapid CO photorelease. This expectation has been realized in a series of carbonyl complexes derived from a variety of designed ligands and smart choice of ligand/coligand combinations. Several principles have emerged from our systematic approach to the design of principal ligands and the choice of auxiliary ligands (in addition to the number of CO) in synthesizing these photoCORMs. In each case, density functional theory (DFT) and time-dependent DFT (TDDFT) study afforded insight into the dependence of the CO photorelease from a particular photoCORM on the wavelength of light. Results of these theoretical studies indicate that extended

  9. Structural-hydraulic test of the liquid metal EURISOL target mock-up

    NASA Astrophysics Data System (ADS)

    Milenković, Rade Ž.; Dementjevs, Sergejs; Samec, Karel; Platacis, Ernests; Zik, Anatolij; Flerov, Aleksej; Manfrin, Enzo; Thomsen, Knud

    2009-08-01

    Structural-hydraulic tests of the European Isotope Separation On-Line (EURISOL) neutron converter target mock-up, named MErcury Target EXperiment 1 (METEX 1), have been conducted by Paul Scherrer Institut (PSI, Switzerland) in cooperation with Institute of Physics of the University of Latvia (IPUL, Latvia). PSI proceeded with extensive thermal-hydraulic and structural computational studies, followed by the target mock-up tests carried out on the mercury loop at IPUL. One of the main goals of the METEX 1 test is to investigate the hydraulic and structural behaviour of the EURISOL target mock-up for various inlet flow conditions (i.e. mass flow rates) and, in particular, for nominal operating flow rate and pressure in the system. The experimental results were analysed by advanced time-frequency methods such as Short-Time Fourier Transform in order to check the vibration characteristics of the mock-up and the resonance risk. The experimental results (obtained in METEX 1), which include inlet flow rate, pressure of the cover gas, total pressure loss, structural acceleration, sound and strain data, were jointly analysed together with numerical data obtained from Computational Fluid Dynamics (CFD).

  10. A Theory for the RF Surface Field for Various Metals at the Destructive Breakdown Limit

    SciTech Connect

    Wilson, Perry B.; /SLAC

    2007-03-06

    By destructive breakdown we mean a breakdown event that results in surface melting over a macroscopic area in a high E-field region of an accelerator structure. A plasma forms over the molten area, bombarding the surface with an intense ion current ({approx} 10{sup 8} A/cm{sup 2}), equivalent to a pressure of about a thousand Atmospheres. This pressure in turn causes molten copper to migrate away from the iris tip, resulting in measurable changes in the iris shape. The breakdown process can be roughly divided into four stages: (1) the formation of ''plasma spots'' at field emission sites, each spot leaving a crater-like footprint; (2) crater clustering, and the formation of areas with hundreds of overlapping craters; (3) surface melting in the region of a crater cluster; (4) the process after surface melting that leads to destructive breakdown. The physics underlying each of these stages is developed, and a comparison is made between the theory and experimental evidence whenever possible. The key to preventing breakdown lies in stage (3). A single plasma spot emits a current of several amperes, a portion of which returns to impact the surrounding area with a power density on the order 10{sup 7} Watt/cm{sup 2}. This power density is not quite adequate to melt the surrounding surface on a time scale short compared to the rf pulse length. In a crater field, however, the impact areas from multiple plasma spots overlap to provide sufficient power density for surface melting over an area on the order of 0.1 mm{sup 2} or more. The key to preventing breakdown is to choose an iris tip material that requires the highest power density (proportional to the square of the rf surface field) for surface melting, taking into account the penetration depth of the impacting electrons. The rf surface field required for surface melting (relative to copper) has been calculated for a large number elementary metals, plus stainless-steel and carbon.

  11. Effects study on the thermal stresses in a LEU metal foil annular target.

    PubMed

    Govindarajan, Srisharan G; Solbrekken, Gary L

    2015-09-01

    The effects of fission gas pressure, uranium swelling and thermal contact conductance on the thermal-mechanical behavior of an annular target containing a low-enriched uranium foil (LEU) encapsulated in a nickel foil have been presented in this paper. The draw-plug assembly method is simulated to obtain the residual stresses, which are applied to the irradiation model as initial inputs, and the integrated assembly-irradiation process is simulated as an axisymmetric problem using the commercial finite element code Abaqus FEA. Parametric studies were performed on the LEU heat generation rate and the results indicate satisfactory irradiation performance of the annular target. The temperature and stress margins have been provided along with a discussion of the results.

  12. Channels of energy redistribution in short-pulse laser interactions with metal targets

    NASA Astrophysics Data System (ADS)

    Zhigilei, Leonid V.; Ivanov, Dmitriy S.

    2005-07-01

    The kinetics and channels of laser energy redistribution in a target irradiated by a short, 1 ps, laser pulse is investigated in computer simulations performed with a model that combines molecular dynamics (MD) simulations with a continuum description of the laser excitation and relaxation of the conduction band electrons, based on the two-temperature model (TTM). The energy transferred from the excited electrons to the lattice splits into several parts, namely the energy of the thermal motion of the atoms, the energy of collective atomic motions associated with the relaxation of laser-induced stresses, the energy carried away from the surface region of the target by a stress wave, the energy of quasi-static anisotropic stresses, and, at laser fluences above the melting threshold, the energy transferred to the latent heat of melting and then released upon recrystallization. The presence of the non-thermal channels of energy redistribution (stress wave and quasi-static stresses), not accounted for in the conventional TTM model, can have important implications for interpretation of experimental results on the kinetics of thermal and mechanical relaxation of a target irradiated by a short laser pulse as well as on the characteristics of laser-induced phase transformations. The fraction of the non-thermal energy in the total laser energy partitioning increases with increasing laser fluence.

  13. R&D-needs and opportunities to broaden the data base on materials and technology for liquid metal spallation targets

    SciTech Connect

    Bauer, G.S.

    1996-06-01

    Liquid metals have so far only been used to a very limited extent as spallation targets, notably at the ISOLDE-facility at CERN (Pb and La) to produce radioactive isotopes. Virtually no systematic studies have been carried out so far. The available data base is by no means sufficient to answer conclusively very important questions such as predicting reliably the service time of medium-to-high power target systems or determining precisely what technological measures are required and appropriate to maintain an optimum coolant quality, to mitigate the effects of pressure waves in short pulse sources and others. During the workshop several areas have been identified, where there exists an urgent need for improved knowledge and reliable data, and opportunities have been presented to acquire such knowledge and to generate such data. Opportunities to do such research and pertinent know-how, although scarce, are spread over institutions in several countries, and efforts to use these opportunities often require substantial resources both in man power and money. The workshop participants therefore unanimously supported the view that a coordinated and internationally concerted effort should be undertaken to make the best possible use of existing opportunities and available resources in order to develop the knowledge and technology necessary for the deployment and safe operation of target systems suitable for pulsed spallation neutron sources in the multi-megawatt range of beam power.

  14. General atomistic approach for modeling metal-semiconductor interfaces using density functional theory and nonequilibrium Green's function

    NASA Astrophysics Data System (ADS)

    Stradi, Daniele; Martinez, Umberto; Blom, Anders; Brandbyge, Mads; Stokbro, Kurt

    2016-04-01

    Metal-semiconductor contacts are a pillar of modern semiconductor technology. Historically, their microscopic understanding has been hampered by the inability of traditional analytical and numerical methods to fully capture the complex physics governing their operating principles. Here we introduce an atomistic approach based on density functional theory and nonequilibrium Green's function, which includes all the relevant ingredients required to model realistic metal-semiconductor interfaces and allows for a direct comparison between theory and experiments via I -Vbias curve simulations. We apply this method to characterize an Ag/Si interface relevant for photovoltaic applications and study the rectifying-to-Ohmic transition as a function of the semiconductor doping. We also demonstrate that the standard "activation energy" method for the analysis of I -Vbias data might be inaccurate for nonideal interfaces as it neglects electron tunneling, and that finite-size atomistic models have problems in describing these interfaces in the presence of doping due to a poor representation of space-charge effects. Conversely, the present method deals effectively with both issues, thus representing a valid alternative to conventional procedures for the accurate characterization of metal-semiconductor interfaces.

  15. Theory of Monte Carlo simulations of the magnetic circular dichroism spectra of alkali metal/rare gas systems

    NASA Astrophysics Data System (ADS)

    Kenney, John W.; Boatz, Jerry A.; Terrill Vosbein, Heidi A.

    The history of magnetic circular dichroism (MCD) spectroscopy in the study of alkali metal/rare gas (M/Rg) cryogenic systems is reviewed in the context of developing a better understanding of alkali metal/hydrogen systems of current interest to the U.S. Air Force as enhanced-performance cryogenic rocket propellants. A new theory for simulating the MCD spectra of M/Rg systems is presented together with a careful discussion of the theory's implicit and explicit approximations and their implications. This theory uses a classical Monte Carlo (MC) simulation scheme to model the perturbing effects of the Rg environment on the 2S → 2P MCD-active transition of the M atom. The theory sets up the MC-MCD simulation as a 6 × 6 matrix eigenvalue/eigenvector problem in the 2P manifold in which are included the effects of M-Rg interactions, metal atom spin-orbit coupling in the 2P manifold, magnetic Zeeman perturbations of the 2S and 2P manifolds, Boltzmann temperature factors, and electric dipole transition moment integrals for left circularly polarized (LCP) and right circularly polarized (RCP) light. The theory may be applied to any type of trapping site of the host M in the guest Rg matrix; a single atom substitutional metal atom trapping site (one host Rg atom is replaced by one guest M atom) is modeled in this study for M = Na and Rg = Ar. Two temperature factors are used in these simulations; a lattice temperature to model the mobility of the Rg lattice and a magnetic temperature to model Boltzmann factors in the 2S ground manifold. The 6 × 6 eigenvalue/eigenvector problem is solved for a number of randomly generated and suitably averaged Rg configurations to yield the simulated MC-MCD spectrum for the single substitutional Na/Ar system. The MC-MCD simulations of Na/Ar give the characteristic triplet MCD spectrum with the correct Boltzmann temperature dependence. The simulated MC-MCD spectrum correctly inverts when the direction of the applied magnetic field is

  16. Nonlinear absorption of surface plasmons and emission of electrons from metallic targets

    SciTech Connect

    Singh, D. B.; Kumar, Gagan; Tripathi, V. K.

    2007-10-15

    A large-amplitude surface plasma wave (SPW) over a metal-vacuum interface Ohmically heats the electrons and undergoes nonlinear absorption. The attenuation rate increases with the local SPW amplitude. The enhanced electron temperature leads to stronger thermionic emission of electrons. At typical Nd:glass laser intensity I{sub L}=7 GW/cm{sup 2}, if one takes the amplitude of the SPW to be {approx_equal}6 times the amplitude of the laser, one obtains the thermionic electron emission current density J=200 A/cm{sup 2}. However, the emission current density decreases with propagation distance at a much faster rate than the SPW amplitude and electron temperature.

  17. Fusion of Imperfect Information in the Unified Framework of Random Sets Theory: Application to Target Identification

    DTIC Science & Technology

    2007-11-01

    another. For instance, Smets [9] and Voorbraak [10] developed a transformation between evidence and probability theories. Klir and Parviz [11] give...319 2. We can also recall the transformation of Klir and Parviz [11], which preserves the imperfection measure. For a probability distribution function...i∑ j=1 π(θσ(j)) (82) Considering this, Klir and Parviz proposed the following transformation: π(θσ(i)) = P (θσ(i)) H(P ) P (θσ(1))H(P ) (83) P (θσ(i

  18. Size effects and charge transport in metals: Quantum theory of the resistivity of nanometric metallic structures arising from electron scattering by grain boundaries and by rough surfaces

    NASA Astrophysics Data System (ADS)

    Munoz, Raul C.; Arenas, Claudio

    2017-03-01

    We discuss recent progress regarding size effects and their incidence upon the coefficients describing charge transport (resistivity, magnetoresistance, and Hall effect) induced by electron scattering from disordered grain boundaries and from rough surfaces on metallic nanostructures; we review recent measurements of the magneto transport coefficients that elucidate the electron scattering mechanisms at work. We review as well theoretical developments regarding quantum transport theories that allow calculating the increase in resistivity induced by electron-rough surface scattering (in the absence of grain boundaries) from first principles—from the parameters that describe the surface roughness that can be measured with a Scanning Tunnelling Microscope (STM). We evaluate the predicting power of the quantum version of the Fuchs-Sondheimer theory and of the model proposed by Calecki, abandoning the method of parameter fitting used for decades, but comparing instead theoretical predictions with resistivity measured in thin films where surface roughness has also been measured with a STM, and where electron-grain boundary scattering can be neglected. We also review the theory of Mayadas and Shatzkes (MS) [Phys. Rev. B 1, 1382 (1970)] used for decades, and discuss its severe conceptual difficulties that arise out of the fact that: (i) MS employed plane waves to describe the electronic states within the metal sample having periodic grain boundaries, rather than the Bloch states known since the thirties to be the solutions of the Schrödinger equation describing electrons propagating through a Krönig-Penney [Proc. R. Soc. London Ser. A 130, 499 (1931)] periodic potential; (ii) MS ignored the fact that the wave functions describing electrons propagating through a 1-D disordered potential are expected to decay exponentially with increasing distance, a fact known since the work of Anderson [Phys. Rev. 109, 1492 (1958)] in 1958 for which he was awarded the Nobel Prize in

  19. Why iron? A spin-polarized conceptual density functional theory study on metal-binding specificity of porphyrin.

    PubMed

    Feng, Xin-Tian; Yu, Jian-Guo; Liu, Ruo-Zhuang; Lei, Ming; Fang, Wei-Hai; De Proft, Frank; Liu, Shubin

    2010-06-03

    Heme is a key cofactor of hemoproteins in which porphyrin is often found to be preferentially metalated by the iron cation. In our previous work [Feng, X. T.; Yu, J. G.; Lei, M.; Fang, W. H.; Liu, S. B. J. Phys. Chem. B 2009, 113, 13381], conceptual density functional theory (CDFT) descriptors have been applied to understand the metal-binding specificity of porphyrin. We found that the iron-porphyrin complex significantly differs in many aspects from porphyrin complexes with other metal cations except Ru, for which similar behaviors for the reactivity descriptors were discovered. In this study, we employ the spin-polarized version of CDFT to investigate the reactivity for a series of (pyridine)(n)-M(ll)-porphyrin complexes-where M = Mg, Ca, Cr, Mn, Co, Ni, Cu, Zn, Ru, and Cd, and n = 0, 1, and 2-to further appreciate the metal-binding specificity of porphyrin. Both global and local descriptors were examined within this framework. We found that, within the spin resolution, not only chemical reactivity descriptors from CDFT of the iron complex are markedly different from that of other metal complexes, but we also discovered substantial differences in reactivity descriptors between Fe and Ru complexes. These results confirm that spin properties play a highly important role in physiological functions of hemoproteins. Quantitative reactivity relationships have been revealed between global and local spin-polarized reactivity descriptors. These results contribute to our better understanding of the metal binding specificity and reactivity for heme-containing enzymes and other metalloproteins alike.

  20. An Estimation Theory Approach to Detection and Ranging of Obscured Targets in 3-D LADAR Data

    DTIC Science & Technology

    2006-03-01

    set consists of 100 laser pulse returns. The first set was collected as a control set using the target shown in figure 2.2. The second set was...containing 2 surfaces. 36 0 2 4 6 8 10 12 14 16 18 0 500 1000 1500 2000 2500 3000 3500 Pixel (99,107) Control # of P ho to ns Sample # Figure 4.4...show the first pulse return of control data from a pixel corresponding to the front surface and back surface respectively. 37 0 2 4 6 8 10

  1. Control of Structure in Conventional Friction Stir Welds Through a Kinematic Theory of Metal Flow

    DTIC Science & Technology

    2009-02-01

    suggested a “chaotic-dynamic mixing” in the material [2]. Later tracer studies, using steel shot [3], aluminum shims [4], copper foil [5], bi-metallic...35812 Keywords: friction stir welding, AA2219, material flow Abstract In friction stir welding ( FSW ), a rotating pin is translated along a...welding, by a shoulder on the pin. In conventional FSW , the weld metal rests on an “anvil”, which supports the heavy “plunge” load on the tool. In

  2. Comments on the possibility of cavitation in liquid metal targets for pulsed spallation neutron sources

    SciTech Connect

    Carpenter J.M.

    1996-06-01

    When short pulses of protons strike the volume of a liquid target, the rapid heating produces a pressurized region which relaxes as the pressure wave propagates outward. Skala and Bauer have modeled the effects of the pressure wave impinging on the container walls of a liquid mercury target under ESS conditions. They find that high pressures and high wall stresses result if the medium is uniform, nearly incompressible liquid. The pressure and the stresses are much reduced if the liquid contains bubbles of helium, due to their high compressibility. However, according to the calculation, the pressure still reaches an atmosphere or so at the surface, which reflects the compressive wave as a rarefaction wave of the same magnitude. Even such modest underpressures can lead to the growth of bubbles (cavitation) at or near the surface, which can collapse violently and erode the container surface. It is necessary to avoid this. Leighton provides a wide ranging discussion of pressure waves in bubbly media, which may provide insights into the nature and control of cavitation phenomena. The paper surveys some of the relevant information from that source.

  3. Large-signal model of the bilayer graphene field-effect transistor targeting radio-frequency applications: Theory versus experiment

    SciTech Connect

    Pasadas, Francisco Jiménez, David

    2015-12-28

    Bilayer graphene is a promising material for radio-frequency transistors because its energy gap might result in a better current saturation than the monolayer graphene. Because the great deal of interest in this technology, especially for flexible radio-frequency applications, gaining control of it requires the formulation of appropriate models for the drain current, charge, and capacitance. In this work, we have developed them for a dual-gated bilayer graphene field-effect transistor. A drift-diffusion mechanism for the carrier transport has been considered coupled with an appropriate field-effect model taking into account the electronic properties of the bilayer graphene. Extrinsic resistances have been included considering the formation of a Schottky barrier at the metal-bilayer graphene interface. The proposed model has been benchmarked against experimental prototype transistors, discussing the main figures of merit targeting radio-frequency applications.

  4. Overcoming target-mediated quinolone resistance in topoisomerase IV by introducing metal-ion-independent drug-enzyme interactions.

    PubMed

    Aldred, Katie J; Schwanz, Heidi A; Li, Gangqin; McPherson, Sylvia A; Turnbough, Charles L; Kerns, Robert J; Osheroff, Neil

    2013-12-20

    Quinolones, which target gyrase and topoisomerase IV, are the most widely prescribed antibacterials worldwide. Unfortunately, their use is threatened by the increasing prevalence of target-mediated drug resistance. Greater than 90% of mutations that confer quinolone resistance act by disrupting enzyme-drug interactions coordinated by a critical water-metal ion bridge. Quinazolinediones are quinolone-like drugs but lack the skeletal features necessary to support the bridge interaction. These compounds are of clinical interest, however, because they retain activity against the most common quinolone resistance mutations. We utilized a chemical biology approach to determine how quinazolinediones overcome quinolone resistance in Bacillus anthracis topoisomerase IV. Quinazolinediones that retain activity against quinolone-resistant topoisomerase IV do so primarily by establishing novel interactions through the C7 substituent, rather than the drug skeleton. Because some quinolones are highly active against human topoisomerase IIα, we also determined how clinically relevant quinolones discriminate between the bacterial and human enzymes. Clinically relevant quinolones display poor activity against topoisomerase IIα because the human enzyme cannot support drug interactions mediated by the water-metal ion bridge. However, the inclusion of substituents that allow quinazolinediones to overcome topoisomerase IV-mediated quinolone resistance can cause cross-reactivity against topoisomerase IIα. Therefore, a major challenge in designing drugs that overcome quinolone resistance lies in the ability to identify substituents that mediate strong interactions with the bacterial, but not the human, enzymes. On the basis of our understanding of quinolone-enzyme interactions, we have identified three compounds that display high activity against quinolone-resistant B. anthracis topoisomerase IV but low activity against human topoisomerase IIα.

  5. Theory of the electron spin resonance in the heavy fermion metal β-YbAlB4.

    PubMed

    Ramires, Aline; Coleman, Piers

    2014-03-21

    The heavy fermion metal β-YbAlB4 exhibits a bulk room temperature conduction electron spin resonance (ESR) signal which evolves into an Ising-anisotropic f-electron signal exhibiting hyperfine features at low temperatures. We develop a theory for this phenomenon based on the development of resonant scattering off a periodic array of Kondo centers. We show that the hyperfine structure arises from the scattering off the Yb atoms with nonzero nuclear spin, while the constancy of the ESR intensity is a consequence of the presence of crystal electric field excitations of the order of the hybridization strength.

  6. On the limitation of density functional theory (DFT) for the treatment of the anharmonicity in FCC metals

    NASA Astrophysics Data System (ADS)

    Seifitokaldani, Ali; Gheribi, Aïmen E.; Dollé, Mickael

    2016-12-01

    It has been already shown that the density functional theory (DFT) combined with the quasi-harmonic approximation (QHA) overestimates the specific heat capacity (and in general the thermal properties) of fcc metals. DFT + QHA seemingly shows a large anharmonic contribution to the heat capacity. However, in this article we show that this anharmonicity has no physical origin and it is a consequence of the deviation of the QHA from the Maxwell relations. We show that one can simply avoid this overestimation by enforcing the QHA method to obey the Maxwell relations throughout the thermodynamically self-consistent (TSC) method, instead of considering non-real local anharmonic effects.

  7. Laser heating of a cavity versus a plane surface for metal targets utilizing photothermal deflection measurements

    NASA Astrophysics Data System (ADS)

    Jeong, S. H.; Greif, R.; Russo, R. E.

    1996-08-01

    The effects of a cylindrical cavity in a metal surface on the energy coupling of a laser beam with the solid were investigated by using a photothermal deflection technique. The photothermal deflection of a probe beam over the cavity was measured while the bottom of the cavity was heated with a Nd-YAG laser with a wavelength of 1064 nm. Cavities in three different materials and with two different aspect ratios were used for the experiment. Temperature distributions in the solid and the surrounding air were computed numerically and used to calculate photothermal deflections for cavity heating and for plane surface heating. Reflection of the heating laser beam inside the cavity increased the photothermal deflection amplitude significantly with larger increases for materials with larger thermal diffusivity. The computed photothermal deflections agreed more closely with the experimental results when reflection of the heating laser beam inside the cavity was included in the numerical model. The overall energy coupling between a heating laser and a solid is enhanced by a cavity.

  8. Folate-targeted single-wall metal-organic nanotubes used as multifunctional drug carriers

    NASA Astrophysics Data System (ADS)

    Yang, Linyan; Liu, Min; Huang, Kebin; Ai, Xia; Li, Cun; Ma, Jifei; Jin, Tianming; Liu, Xin

    2017-01-01

    Doxorubicin (DOX) is a member of the anthracycline class of chemotherapeutic agents that are used for the treatment of many common human cancers. A self-assembled functionalized metal-organic nanotubes, SWMONTs could be loaded with the anticancer drug DOX. Via the modification of SWMONTs, DOX/SWMONTs-SiO2, DOX/SWMONTs-SiO2-NH2, DOX/SWMONTs-SiO2-NH2-FA samples could be obtained. The SEM characterization of the samples indicated that the particle size of DOX/SWMONTs-SiO2NH2 samples were smaller than 200 nm. Drug-release experiments implied that DOX from the DOX/SWMONTs-SiO2-NH2-FA samples could be released faster at acidic tumor tissue than at normal body fluid (pH7.4). DOX has strong cytotoxicity, and at 20 μg/mL dosage of DOX large amount of apoptotic cells could be seen. Cellular uptaking experiments were used to study the apoptotic mechanism, while for DOX/SWMONTs-SiO2-NH2-FA samples, the strong drug fluorescence was found in the cytoplasm rather than in the nucleus.

  9. X-ray and gamma ray emission from petawatt laser-driven nanostructured metal targets

    NASA Astrophysics Data System (ADS)

    Hill, Matthew; Allan, Peter; Brown, Colin; Hoarty, David; Hobbs, Lauren; James, Steven; Bargsten, Clayton; Hollinger, Reed; Rocca, Jorge; Park, Jaebum; Chen, Hui; London, Richard; Shepherd, Ronnie; Tommasini, Riccardo; Vinko, Sam; Wark, Justin; Marjoribanks, Robin; Neely, David; Spindloe, Chris

    2016-10-01

    Nano-wire arrays of nickel and gold have been fired at the Orion laser facility using high contrast 1 ω and 2 ω short pulse beams (0.7 ps pulse length, >1020 W cm-2 intensity). Time-resolved and time-integrated K-shell and M-shell emission have been characterized and compared to those of flat foils, investigating the capability of these metamaterial coatings to enhance laser-target coupling and X-ray emission. Bremsstrahlung emission of gamma rays and associated pair production via the Bethe-Heitler process have also been investigated by use of 1 mm-thick gold substrates attached to the gold nanowires. We present our latest experimental data and outline some potential future applications.

  10. Electronic and optical properties of a metal-organic framework with ab initio many-body perturbation theory

    NASA Astrophysics Data System (ADS)

    Berland, Kristian; Lee, Kyuho; Sharifzadeh, Sahar; Neaton, Jeffrey B.

    2015-03-01

    With their unprecedented surface area, and their structural and chemical tunability, metal-organic frameworks (MOFs) are being thoroughly explored for applications related to gas storage. Less studied are their electronic, excited-state, and optical properties. Here we explored such properties of Mg-MOF-74 using a combination of density functional theory (DFT) and many-body perturbation theory (MBPT) within the GW approximation and the Bethe-Salpeter equation (BSE) approach. The near-gap electronic conduction states were found to fall into two distinct categories: molecular-like and 1d-dispersive. Further, using the BSE approach, we predict a strongly anisotropic absorption spectrum, which we link to the nature of its strongly-bound excitons. Our calculations are found to be in good agreement with experimental absorption spectra, validating our theoretical approach. This work is supported by Chalmers Area of Advance: Materials, Vetenskapsradet, DOE, and computational resources provided by NERSC.

  11. Theory of a continuous stripe melting transition in a two-dimensional metal: a possible application to cuprate superconductors.

    PubMed

    Mross, David F; Senthil, T

    2012-06-29

    We construct a theory of continuous stripe melting quantum phase transitions in two-dimensional metals and the associated Fermi surface reconstruction. Such phase transitions are strongly coupled but yet theoretically tractable in situations where the stripe ordering is destroyed by proliferating doubled dislocations of the charge stripe order. The resulting non-Landau quantum critical point has strong stripe fluctuations which we show decouple dynamically from the Fermi surface even though static stripe ordering reconstructs the Fermi surface. We discuss connections to various stripe phenomena in the cuprates. We point out several puzzling aspects of old experimental results [G. Aeppli et al., Science 278, 1432 (1997)] on singular stripe fluctuations in the cuprates, and provide a possible explanation within our theory. These results may thus have been the first observation of non-Landau quantum criticality in an experiment.

  12. The Metallicity Distribution and Hot Jupiter Rate of the Kepler Field: Hectochelle High-resolution Spectroscopy for 776 Kepler Target Stars

    NASA Astrophysics Data System (ADS)

    Guo, Xueying; Johnson, John A.; Mann, Andrew W.; Kraus, Adam L.; Curtis, Jason L.; Latham, David W.

    2017-03-01

    The occurrence rate of hot Jupiters from the Kepler transit survey is roughly half that of radial velocity surveys targeting solar neighborhood stars. One hypothesis to explain this difference is that the two surveys target stars with different stellar metallicity distributions. To test this hypothesis, we measure the metallicity distribution of the Kepler targets using the Hectochelle multi-fiber, high-resolution spectrograph. Limiting our spectroscopic analysis to 610 dwarf stars in our sample with {log}g > 3.5, we measure a metallicity distribution characterized by a mean of {[{{M}}/{{H}}]}{mean}=-0.045+/- 0.009, in agreement with previous studies of the Kepler field target stars. In comparison, the metallicity distribution of the California Planet Search radial velocity sample has a mean of {[{{M}}/{{H}}]}{CPS,{mean}}=-0.005+/- 0.006, and the samples come from different parent populations according to a Kolmogorov–Smirnov test. We refit the exponential relation between the fraction of stars hosting a close-in giant planet and the host star metallicity using a sample of dwarf stars from the California Planet Search with updated metallicities. The best-fit relation tells us that the difference in metallicity between the two samples is insufficient to explain the discrepant hot Jupiter occurrence rates; the metallicity difference would need to be ≃0.2–0.3 dex for perfect agreement. We also show that (sub)giant contamination in the Kepler sample cannot reconcile the two occurrence calculations. We conclude that other factors, such as binary contamination and imperfect stellar properties, must also be at play.

  13. The metallicity distribution and hot Jupiter rate of the Kepler field: Hectochelle High-resolution spectroscopy for 776 Kepler target stars

    NASA Astrophysics Data System (ADS)

    Guo, Xueying; Johnson, John A.; Mann, Andrew W.; Kraus, Adam L.; Curtis, Jason L.; Latham, David W.

    2017-01-01

    The occurrence rate of hot Jupiters from the Kepler transit survey is roughly half that of radial velocity surveys targeting solar neighborhood stars. One hypothesis to explain this difference is that the two surveys target stars with different stellar metallicity distributions. To test this hypothesis, we measure the metallicity distribution of the Kepler targets using the Hectochelle multi-fiber, high-resolution spectrograph. Limiting our spectroscopic analysis to 610 dwarf stars in our sample with log(g) > 3.5, we measure a metallicity distribution characterized by a mean of [M/H]_{mean} = -0.045 +/- 0.009, in agreement with previous studies of the Kepler field target stars. In comparison, the metallicity distribution of the California Planet Search radial velocity sample has a mean of [M/H]_{CPS, mean} = -0.005 +\\- 0.006, and the samples come from different parent populations according to a Kolmogorov-Smirnov test. We refit the exponential relation between the fraction of stars hosting a close-in giant planet and the host star metallicity using a sample of dwarf stars from the California Planet Search with updated metallicities. The best-fit relation tells us that the difference in metallicity between the two samples is insufficient to explain the discrepant Hot Jupiter occurrence rates; the metallicity difference would need to be 0.2-0.3 dex for perfect agreement. We also show that (sub)giant contamination in the Kepler sample cannot reconcile the two occurrence calculations. We conclude that other factors, such as binary contamination and imperfect stellar properties, must also be at play.

  14. Targeting Parents for Childhood Weight Management: Development of a Theory-Driven and User-Centered Healthy Eating App

    PubMed Central

    Lahiri, Sudakshina; Brown, Katherine Elizabeth

    2015-01-01

    Background The proliferation of health promotion apps along with mobile phones' array of features supporting health behavior change offers a new and innovative approach to childhood weight management. However, despite the critical role parents play in children’s weight related behaviors, few industry-led apps aimed at childhood weight management target parents. Furthermore, industry-led apps have been shown to lack a basis in behavior change theory and evidence. Equally important remains the issue of how to maximize users’ engagement with mobile health (mHealth) interventions where there is growing consensus that inputs from the commercial app industry and the target population should be an integral part of the development process. Objective The aim of this study is to systematically design and develop a theory and evidence-driven, user-centered healthy eating app targeting parents for childhood weight management, and clearly document this for the research and app development community. Methods The Behavior Change Wheel (BCW) framework, a theoretically-based approach for intervention development, along with a user-centered design (UCD) philosophy and collaboration with the commercial app industry, guided the development process. Current evidence, along with a series of 9 focus groups (total of 46 participants) comprised of family weight management case workers, parents with overweight and healthy weight children aged 5-11 years, and consultation with experts, provided data to inform the app development. Thematic analysis of focus groups helped to extract information related to relevant theoretical, user-centered, and technological components to underpin the design and development of the app. Results Inputs from parents and experts working in the area of childhood weight management helped to identify the main target behavior: to help parents provide appropriate food portion sizes for their children. To achieve this target behavior, the behavioral diagnosis

  15. Interactions of calmodulin with metal ions and with its target proteins revealed by conformation-sensitive monoclonal antibodies.

    PubMed

    Wolf, T; Solomon, B; Ivnitski, D; Rishpon, J; Fleminger, G

    1998-01-01

    Two monoclonal antibodies (mAbs) raised against bovine calmodulin (CaM), CAM1 and CAM4, enable one to monitor conformational changes that occur in the molecule. The interaction of CAM1 with CaM depends on the Ca2+ occupancy of its Ca(2+)-binding sites. CAM4, in contrast, interacts with CaM in a Ca(2+)-independent manner, interacting with both holoCaM and EGTA-treated CaM to a similar extent. Their interaction with various CaMs, CaM tryptic fragments and chemically modified CaM, as well as molecular graphics, led to identification of the CAM1 and CAM4 epitopes on the C- and N-terminal lobes of CAM respectively. The two mAbs were used as macromolecular probes to detect conformational changes occurring in the CaM molecule upon binding of metal ions and target proteins and peptides. MAb CAM1 successfully detected changes associated with Al3+ binding even in the presence of Ca2+, indicating that Al3+ and Ca2+ ions may bind to the protein simultaneously, leading to a new conformation of the molecule. MAbs CAM1 and CAM4 were used to follow the interactions of CaM with its target peptides and proteins. Complexes with melittin, mastoparan, calcineurin and phosphodiesterase showed different immunological properties on an immuno-enzyme electrode, indicating unique structural properties for each complex.

  16. THEY MIGHT BE GIANTS: LUMINOSITY CLASS, PLANET OCCURRENCE, AND PLANET-METALLICITY RELATION OF THE COOLEST KEPLER TARGET STARS

    SciTech Connect

    Mann, Andrew W.; Hilton, Eric J.; Gaidos, Eric; Lepine, Sebastien

    2012-07-01

    We estimate the stellar parameters of late K- and early M-type Kepler target stars. We obtain medium-resolution visible spectra of 382 stars with K{sub P} - J > 2 ({approx_equal}K5 and later spectral type). We determine luminosity class by comparing the strength of gravity-sensitive indices (CaH, K I, Ca II, and Na I) to their strength in a sample of stars of known luminosity class. We find that giants constitute 96% {+-} 1% of the bright (K{sub P} < 14) Kepler target stars, and 7% {+-} 3% of dim (K{sub P} > 14) stars, significantly higher than fractions based on the stellar parameters quoted in the Kepler Input Catalog (KIC). The KIC effective temperatures are systematically (110{sup +15}{sub -35} K) higher than temperatures we determine from fitting our spectra to PHOENIX stellar models. Through Monte Carlo simulations of the Kepler exoplanet candidate population, we find a planet occurrence of 0.36 {+-} 0.08 when giant stars are properly removed, somewhat higher than when a KIC log g > 4 criterion is used (0.27 {+-} 0.05). Last, we show that there is no significant difference in g - r color (a probe of metallicity) between late-type Kepler stars with transiting Earth-to-Neptune-size exoplanet candidates and dwarf stars with no detected transits. We show that a previous claimed offset between these two populations is most likely an artifact of including a large number of misidentified giants.

  17. A simplified density functional theory method for investigating charged adsorbates on an ultrathin, insulating film supported by a metal substrate.

    PubMed

    Scivetti, Ivan; Persson, Mats

    2014-04-02

    A simplified density functional theory (DFT) method for investigating charged adsorbates on an ultrathin, insulating film supported by a metal substrate is developed and presented. This new method is based on a previous DFT development that uses a perfect conductor (PC) model to approximate the electrostatic response of the metal substrate, while the film and the adsorbate are both treated fully within DFT (Scivetti and Persson 2013 J. Phys.: Condens. Matter 25 355006). The missing interactions between the metal substrate and the insulating film in the PC approximation are modelled by a simple force field (FF). The parameters of the PC model and the force field are obtained from DFT calculations of the film and the substrate, here shown explicitly for a NaCl bilayer supported by a Cu(100) surface. In order to obtain some of these parameters and the polarizability of the force field, we have to include an external, uniformly charged plane in the DFT calculations, which has required the development of a periodic DFT formalism to include such a charged plane in the presence of a metal substrate. This extension and implementation should be of more general interest and applicable to other challenging problems, for instance, in electrochemistry. As illustrated for the gold atom on the NaCl bilayer supported by a Cu(100) surface, our new DFT-PC-FF method allows us to handle different charge states of adsorbates in a controlled and accurate manner with a considerable reduction of the computational time. In addition, it is now possible to calculate vertical transition and reorganization energies for the charging and discharging of adsorbates that cannot be obtained by current DFT methodologies that include the metal substrate. We find that the computed vertical transition energy for charging of the gold adatom is in good agreement with experiments.

  18. Signal enhancement in electrospray laser desorption/ionization mass spectrometry by using a black oxide-coated metal target and a relatively low laser fluence.

    PubMed

    Kononikhin, Alexey; Huang, Min-Zong; Popov, Igor; Kostyukevich, Yury; Kukaev, Evgeny; Boldyrev, Alexey; Spasskiy, Alexander; Leypunskiy, Ilya; Shiea, Jentaie; Nikolaev, Eugene

    2013-01-01

    The electrospray Laser desorption/ionization (ELDI) method is actively used for direct sample analysis and ambient mass spectrometry imaging. The optimizing of Laser desorption conditions is essential for this technology. In this work, we propose using a metal target with a black oxide (Fe3O4) coating to increase the signal in ELDI-MS for peptides and small proteins. The experiments were performed on an LTQ-FT mass spectrometer equipped with a home-made ELDI ion source. A cutter blade with black oxide coating was used as a target. A nitrogen laser was used with the following parameters: 337 nm, pulse duration 4ns, repetition rate 10 Hz, fluence to approximately 700 Jm(-2). More than a five times signal increase was observed for a substance P peptide when a coated and a non-coated metal target were compared. No ion signal was observed for proteins if the same fluence and the standard stainless steel target were used. With the assistance of the Fe3O4 coated metal target and a relatively low laser fluence < or =700 Jm(-2)), proteins such as insulin, ubiquitin and myoglobin were successfully ionized. It was demonstrated that the Fe3O4-coated metal target can be used efficiently to assist laser desorption and thus significantly increase the analyte signal in ELDI-MS. A relatively low laser fluence (< or = 700 Jm(-2)) was enough to desorb peptides and proteins (up to 17 kDal with the assistance of the Fe3O4-coated metal target under ambient conditions.

  19. Thermochromism of metal-doped VO{sub 2} films deposited by dual-target sputtering

    SciTech Connect

    Jin, P.; Tazawa, M.; Yoshimura, K.; Miki, T.; Igarashi, K.; Tanemura, S.

    1994-12-31

    There are several kinds of chromogenic materials such as photochromic material, electrochromic material and thermochromic material, of which the thermochromic one is known for its optical properties (transmittance and reflectance) being able to change reversibly upon temperature. Among the chromogenic materials feasible to smart window coatings, thermochromic (TC) one has recently received increasing attention, since a window with TC coating enables automatic control of the energy throughputs of the solar radiation as well as the environmental radiation in response to the ambient temperature. Here, thermochromic VO{sub 2} films were prepared by reactive magnetron sputtering under various conditions of substrate temperature, total sputter pressure and oxygen flow ratio and characterized by XRD, RBS, AFM and spectrophotometry. Films with VO{sub 2} single phase were formed from a fairly low substrate temperature of 300 C by precisely controlling the oxygen flow ratio. The use of vanadium nucleated substrates significantly improved the crystallinity of VO{sub 2}. Tungsten doped V{sub 1{minus}x}W{sub x}O{sub 2} films with x = 0--0.26 were formed by dual-target sputtering and the thermochromism of films was evaluated. The tungsten doping linearly decreased {tau}{sub c} by 24 C/at.%W with a reduction in the hysteresis loop width.

  20. Design of mid-infrared ultra-wideband metallic absorber based on circuit theory

    NASA Astrophysics Data System (ADS)

    Arik, Kamalodin; Abdollahramezani, Sajjad; Farajollahi, Saeed; Khavasi, Amin; Rejaei, Behzad

    2016-12-01

    An ultra-broadband absorber of light is proposed by using periodic array of ultra-thin metallic ribbons on top of a lossless quarter-wavelength dielectric spacer placed on a metallic reflector. We propose a fully analytical circuit model for the structure, and then the absorber is duly designed based on the impedance matching concept. As a result, normalized bandwidth of 99.5% is realized by the proposed absorbing structure in mid-infrared regime. Performing a numerical optimization algorithm, we could also reach to normalized bandwidth of 103%.

  1. Heat transfer to a heavy liquid metal in curved geometry: Code validation and CFD simulation for the MEGAPIE lower target

    NASA Astrophysics Data System (ADS)

    Dury, Trevor V.

    2006-06-01

    The ESS and SINQ Heat Emitting Temperature Sensing Surface (HETSS) mercury experiments have been used to validate the Computational Fluid Dynamics (CFD) code CFX-4 employed in designing the lower region of the international liquid metal cooled MEGAPIE target, to be installed at SINQ, PSI, in 2006. Conclusions were drawn on the best turbulence models and degrees of mesh refinement to apply, and a new CFD model of the MEGAPIE geometry was made, based on the CATIA CAD design of the exact geometry constructed. This model contained the fill and drain tubes as well as the bypass feed duct, with the differences in relative vertical length due to thermal expansion being considered between these tubes and the window. Results of the mercury experiments showed that CFD calculations can be trusted to give peak target window temperature under normal operational conditions to within about ±10%. The target nozzle actually constructed varied from the theoretical design model used for CFD due to the need to apply more generous separation distances between the nozzle and the window. In addition, the bypass duct contraction approaching the nozzle exit was less sharp compared with earlier designs. Both of these changes modified the bypass jet penetration and coverage of the heated window zone. Peak external window temperature with a 1.4 mA proton beam and steady-state operation is now predicted to be 375 °C, with internal temperature 354.0 °C (about 32 °C above earlier predictions). Increasing bypass flow from 2.5 to 3.0 kg/s lowers these peak temperatures by about 12 °C. Stress analysis still needs to be made, based on these thermal data.

  2. Study of underwater laser propulsion using different target materials.

    PubMed

    Qiang, Hao; Chen, Jun; Han, Bing; Shen, Zhong-Hua; Lu, Jian; Ni, Xiao-Wu

    2014-07-14

    In order to investigate the influence of target materials, including aluminum (Al), titanium (Ti) and copper (Cu), on underwater laser propulsion, the analytical formula of the target momentum IT is deduced from the enhanced coupling theory of laser propulsion in atmosphere with transparent overlay metal target. The high-speed photography method and numerical simulation are employed to verify the IT model. It is shown that the enhanced coupling theory, which was developed originally for laser propulsion in atmosphere, is also applicable to underwater laser propulsion with metal targets.

  3. Quantum particle interacting with a metallic particle: Spectra from quantum Langevin theory

    NASA Astrophysics Data System (ADS)

    Loh, W. M. Edmund; Ooi, C. H. Raymond

    2017-01-01

    The effect of a nearby metallic particle on the quantum optical properties of a quantum particle in the four-level double Raman configuration is studied using the quantum Langevin approach. We obtain analytical expressions for the correlated quantum fields of Stokes and anti-Stokes photons emitted from the system and perform analysis on how the interparticle distance, the direction of observation or detection, the strengths of controllable laser fields, the presence of surface plasmon resonance, and the number density of the quantum particle affect the quantum spectra of the Stokes and anti-Stokes fields. We explore the physics behind the quantum-particle-metallic-nanoparticle interaction within the dipole approximation, that is, when the interparticle distance is much larger than the sizes of the particles. Our results show the dependence of the spectra on the interparticle distance in the form of oscillatory behavior with damping as the interparticle distance increases. At weaker laser fields the enhancement of quantum fields which manifests itself in the form of a Fano dip in the central peak of the spectra becomes significant. Also, the quantum-particle-metallic-nanoparticle coupling, which is affected by the size of the metallic nanoparticle and the number density of the quantum particle, changes the angular dependence of the spectra by breaking the angular rotational symmetry. In the presence of surface plasmon resonance the oscillatory dependence of the spectra on the interparticle distance and angles of observation becomes even stronger due to the plasmonic enhancement effect.

  4. Adsorption of a metalorganic complex at a metal surface: A density functional theory study vs. model description

    SciTech Connect

    Kostyrko, T. Ślusarski, T.

    2015-01-21

    A modification of the electronic and magnetic structure of a metalorganic complex by chemisorption at a metallic surface is addressed. The density functional theory (DFT) is applied to investigate a simplified form of a copper-dioxolene complex in a free state and connected to Au(111) surface with alkanethiol linkers. A systematic study of the dependence of the system electronic structure on the linker length is performed. It is found that the electronic structure of the complex is well preserved during the adsorption process. The magnetic moment of the Cu-dioxolene functional group is shown to be strictly correlated with the amount of the charge residing at the complex. On the basis of the DFT results, a model Hamiltonian of the adsorbed metalorganic system is proposed. The model is an extension of the Sandorfy's model of the alkanes and includes explicitly Coulomb interaction between electrons both within the alkane's backbone and the end group. We show that the latter feature is necessary to understand the evolution of the system's properties with the length of the linkers. The advantage of this approach is that it not only reproduces the main results of our DFT analysis but also provides a simple common basis to analyse a wide class of metal complexes bound to metal surfaces with alkanethiol linkers.

  5. Use the superconducting proximity effect to investigate alkali metal films and the comparison between the experiment and theory

    NASA Astrophysics Data System (ADS)

    Zhang, Manjiang

    Bilayers of Pb and the alkali metals Cs, Rb, K and Na were quench condensed on the quartz plate. The transition temperature measurement provides information about interface barriers between the Pb and the alkali metals. Such a barrier, which is not due to impurities or oxidation, is particularly large in Pb/Cs sandwiches. The thin K film is forced into an insulating state by being covered with sub-monolayers of Pb. The SPE is used to investigate the electronic change in the alkali film. The K film behaves as if its electrons are unable to carry a current in the x-y-plane but can easily move in the z-direction. This shows on the length scale of the K film thickness, the electronic properties of the film do not change noticeably during the metal-insulator transition. The superconducting proximity effect is investigated for SN-double layers in the thin film limit. In this regime, the normalized initial slope Ssn = (ds=Ts )|dTc=ddn| is independent of the thickness of the superconductor, the mean free path of the films and the transparency of the interface if it is not too small. The transition temperature Tc is compared with a numerical calculation developed in our group. The deviation between the experiment and theory decreases from the normal metal to the superconductor with a relative high transition temperature. The deviation factor decreases from 2.5 for Cu, Ag, Au, Mg to 1.5 for Cd, Zn, Al and finally no disagreement for In and Sn. A weak perpendicular magnetic field is applied on the super- and normal conductor double layers. The difference of the transition temperature dTc measured with and without magnetic field increases with increasing the normal metal thickness. A quantitative explanation is given based on the increased dephasing of the electrons in the magnetic field. Numerical calculation of the transition temperature based on the strong coupling theory is also given and compared with the experimental results.

  6. Magneto-Rayleigh-Taylor Instability: Theory and simulation in planar and cylindrical pulsed power targets

    NASA Astrophysics Data System (ADS)

    Weis, Matthew R.

    Cylindrical liner implosions in the Magnetized Liner Inertial Fusion (MagLIF) concept are susceptible to the magneto-Rayleigh-Taylor instability (MRT). The danger of MRT enters in two phases, (1) during the main implosion, the outer surface of the liner is MRT unstable, and (2) during the short time period when the liner decelerates onto hot fuel, the inner surface becomes unstable. Growth of MRT on the outer surface may also feedthrough, which may seed the inner surface leading to high MRT growth in the second phase. If MRT growth becomes large enough, confinement of the fuel is lost. To characterize MRT we solve the linearized, ideal MHD equations in both planar and cylindrical geometries, including the presence of an axial magnetic field and the effects of sausage and kink modes (present in cylindrical coordinates only). In general, the total instability growth rates in cylindrical geometry are found to be larger than those in planar geometry. MRT and feedthrough is shown to be suppressed by strong magnetic field line bending (tension). However, for the same amount of field line bending, feedthrough is the most stabilized. Application of the planar and the cylindrical model to results from the Z-machine at Sandia National Laboratories is presented. Analytic MRT growth rates for a typical magnetized MagLIF-like implosion show the kink mode to be the fastest growing early and very late in the liner implosion (during deceleration). 1D HYDRA MHD simulations are used to generate realistic, evolving profiles (in density, pressure, and magnetic field) during the implosion from which instantaneous growth rates can be computed exactly, using either the planar or cylindrical analytic formulae developed in this thesis. Sophisticated 2D HYDRA MHD simulations were also performed to compare with the analytic theory and experimental results. In 2D, highly compressed axial magnetic fields can reduce the growth of perturbations at the fuel/liner interface during the implosion

  7. An automated flow system incorporating in-line acid dissolution of bismuth metal from a cyclotron irradiated target assembly for use in the isolation of astatine-211.

    PubMed

    O'Hara, Matthew J; Krzysko, Anthony J; Niver, Cynthia M; Morrison, Samuel S; Owsley, Stanley L; Hamlin, Donald K; Dorman, Eric F; Scott Wilbur, D

    2017-04-01

    Astatine-211 ((211)At) is a promising cyclotron-produced radionuclide being investigated for use in targeted alpha therapy. The wet chemical isolation of trace quantities of (211)At, produced within several grams of Bi metal deposited onto an aluminum cyclotron target assembly, involves a multi-step procedure. Because the (211)At isolation method is labor-intensive and complex, automation of the method is being developed to facilitate routine processing at the University of Washington and to make it easier to transfer the process to other institutions. As part of that automation effort, a module useful in the initial step of the isolation procedure, dissolution of the Bi target, was designed and tested. The computer-controlled module performs in-line dissolution of Bi metal from the target assembly using an enclosed target dissolution block, routing the resulting solubilized (211)At/Bi mixture to the subsequent process step. The primary parameters involved in Bi metal solubilization (influent HNO3 concentration and flow rate) were optimized prior to evaluation of the system using replicate (211)At-bearing cyclotron irradiated targets. The results indicate that the system performs in a predictable and reproducible manner, with cumulative Bi and (211)At recoveries following a sigmoidal function.

  8. Effect of metal in M3(btc)2 and M2(dobdc) MOFs for O2/N2 separations: A combined density functional theory and experimental study

    DOE PAGES

    Parkes, Marie V.; Sava Gallis, Dorina F.; Greathouse, Jeffery A.; ...

    2015-03-02

    Computational screening of metal-organic framework (MOF) materials for selective oxygen adsorption from air could lead to new sorbents for the oxyfuel combustion process feedstock streams. A comprehensive study on the effect of MOF metal chemistry on gas binding energies in two common but structurally disparate metal-organic frameworks has been undertaken. Dispersion-corrected density functional theory methods were used to calculate the oxygen and nitrogen binding energies with each of fourteen metals, respectively, substituted into two MOF series, M2(dobdc) and M3(btc)2. The accuracy of DFT methods was validated by comparing trends in binding energy with experimental gas sorption measurements. A periodic trendmore » in oxygen binding energies was found, with greater oxygen binding energies for early transition-metal-substituted MOFs compared to late transition metal MOFs; this was independent of MOF structural type. The larger binding energies were associated with oxygen binding in a side-on configuration to the metal, with concomitant lengthening of the O-O bond. In contrast, nitrogen binding energies were similar across the transition metal series, regardless of both MOF structural type and metal identity. Altogether, these findings suggest that early transition metal MOFs are best suited to separating oxygen from nitrogen, and that the MOF structural type is less important than the metal identity.« less

  9. Improving Theory of Mind in Schizophrenia by Targeting Cognition and Metacognition with Computerized Cognitive Remediation: A Multiple Case Study.

    PubMed

    Thibaudeau, Élisabeth; Cellard, Caroline; Reeder, Clare; Wykes, Til; Ivers, Hans; Maziade, Michel; Lavoie, Marie-Audrey; Pothier, William; Achim, Amélie M

    2017-01-01

    Schizophrenia is associated with deficits in theory of mind (ToM) (i.e., the ability to infer the mental states of others) and cognition. Associations have often been reported between cognition and ToM, and ToM mediates the relationship between impaired cognition and impaired functioning in schizophrenia. Given that cognitive deficits could act as a limiting factor for ToM, this study investigated whether a cognitive remediation therapy (CRT) that targets nonsocial cognition and metacognition could improve ToM in schizophrenia. Four men with schizophrenia received CRT. Assessments of ToM, cognition, and metacognition were conducted at baseline and posttreatment as well as three months and 1 year later. Two patients reached a significant improvement in ToM immediately after treatment whereas at three months after treatment all four cases reached a significant improvement, which was maintained through 1 year after treatment for all three cases that remained in the study. Improvements in ToM were accompanied by significant improvements in the most severely impaired cognitive functions at baseline or by improvements in metacognition. This study establishes that a CRT program that does not explicitly target social abilities can improve ToM.

  10. Improving Theory of Mind in Schizophrenia by Targeting Cognition and Metacognition with Computerized Cognitive Remediation: A Multiple Case Study

    PubMed Central

    Cellard, Caroline; Reeder, Clare; Wykes, Til; Ivers, Hans; Maziade, Michel; Lavoie, Marie-Audrey; Pothier, William

    2017-01-01

    Schizophrenia is associated with deficits in theory of mind (ToM) (i.e., the ability to infer the mental states of others) and cognition. Associations have often been reported between cognition and ToM, and ToM mediates the relationship between impaired cognition and impaired functioning in schizophrenia. Given that cognitive deficits could act as a limiting factor for ToM, this study investigated whether a cognitive remediation therapy (CRT) that targets nonsocial cognition and metacognition could improve ToM in schizophrenia. Four men with schizophrenia received CRT. Assessments of ToM, cognition, and metacognition were conducted at baseline and posttreatment as well as three months and 1 year later. Two patients reached a significant improvement in ToM immediately after treatment whereas at three months after treatment all four cases reached a significant improvement, which was maintained through 1 year after treatment for all three cases that remained in the study. Improvements in ToM were accompanied by significant improvements in the most severely impaired cognitive functions at baseline or by improvements in metacognition. This study establishes that a CRT program that does not explicitly target social abilities can improve ToM. PMID:28246557

  11. Iron-Targeting Antitumor Activity of Gallium Compounds and Novel Insights Into Triapine®-Metal Complexes

    PubMed Central

    Antholine, William E.

    2013-01-01

    Abstract Significance: Despite advances made in the treatment of cancer, a significant number of patients succumb to this disease every year. Hence, there is a great need to develop new anticancer agents. Recent Advances: Emerging data show that malignant cells have a greater requirement for iron than normal cells do and that proteins involved in iron import, export, and storage may be altered in cancer cells. Therefore, strategies to perturb these iron-dependent steps in malignant cells hold promise for the treatment of cancer. Recent studies show that gallium compounds and metal-thiosemicarbazone complexes inhibit tumor cell growth by targeting iron homeostasis, including iron-dependent ribonucleotide reductase. Chemical similarities of gallium(III) with iron(III) enable the former to mimic the latter and interpose itself in critical iron-dependent steps in cellular proliferation. Newer gallium compounds have emerged with additional mechanisms of action. In clinical trials, the first-generation-compound gallium nitrate has exhibited activity against bladder cancer and non-Hodgkin's lymphoma, while the thiosemicarbazone Triapine® has demonstrated activity against other tumors. Critical Issues: Novel gallium compounds with greater cytotoxicity and a broader spectrum of antineoplastic activity than gallium nitrate should continue to be developed. Future Directions: The antineoplastic activity and toxicity of the existing novel gallium compounds and thiosemicarbazone-metal complexes should be tested in animal tumor models and advanced to Phase I and II clinical trials. Future research should identify biologic markers that predict tumor sensitivity to gallium compounds. This will help direct gallium-based therapy to cancer patients who are most likely to benefit from it. Antioxid. Redox Signal. 00, 000–000. PMID:22900955

  12. Solid state theory. Quantum spin Hall effect in two-dimensional transition metal dichalcogenides.

    PubMed

    Qian, Xiaofeng; Liu, Junwei; Fu, Liang; Li, Ju

    2014-12-12

    Quantum spin Hall (QSH) effect materials feature edge states that are topologically protected from backscattering. However, the small band gap in materials that have been identified as QSH insulators limits applications. We use first-principles calculations to predict a class of large-gap QSH insulators in two-dimensional transition metal dichalcogenides with 1T' structure, namely, 1T'-MX2 with M = (tungsten or molybdenum) and X = (tellurium, selenium, or sulfur). A structural distortion causes an intrinsic band inversion between chalcogenide-p and metal-d bands. Additionally, spin-orbit coupling opens a gap that is tunable by vertical electric field and strain. We propose a topological field effect transistor made of van der Waals heterostructures of 1T'-MX2 and two-dimensional dielectric layers that can be rapidly switched off by electric field through a topological phase transition instead of carrier depletion.

  13. Target-stimulated metallic HgS nanostructures on a DNA-based polyion complex membrane for highly efficient impedimetric detection of dissolved hydrogen sulfide.

    PubMed

    Zhuang, Junyang; Fu, Libing; Lai, Wenqiang; Tang, Dianping; Chen, Guonan

    2013-12-11

    Target-stimulated metallic HgS nanostructures formed on the DNA-based polyion complex (PIC) membrane were for the first time utilized as an efficient scheme for impedimetric detection of hydrogen sulfide (H2S) by coupling insoluble precipitation with sensitivity enhancement.

  14. Theory of Strength and High-Rate Plasticity in BCC Metals Laser-Driven to High Pressures

    NASA Astrophysics Data System (ADS)

    Rudd, Robert E.; Barton, N. R.; Cavallo, R. M.; Hawreliak, J. A.; Maddox, B. R.; Park, H.-S.; Prisbrey, S. T.; Remington, B. A.; Comley, A. J.; Ross, P. W.; Brickner, N.

    2012-10-01

    High-rate plastic deformation is the subject of increasing experimental activity. High energy laser platforms such as those at the National Ignition Facility and the Laboratory for Laser Energetics offer the possibility to study plasticity at extremely high rates in shock waves and, importantly, in non-shock ramp-compression waves. Here we describe the theory of high-rate deformation of metals and how high energy lasers can be, and are, used to study the mechanical strength of materials under extreme conditions. Specifically, we describe how LLNL's multiscale strength model has been used to interpret the microscopic plastic flow in laser-driven Rayleigh-Taylor strength experiments, and how molecular dynamics (MD) and plasticity theory have been used to help understand in-situ diffraction based strength experiments for tantalum. The multiscale model provides information about the dislocation flow associated with plasticity and makes predictions that are compared with the experimental in-situ radiography of the Rayleigh-Taylor growth rate. We also use multi-million atom MD simulations inform the analytic theory of 1D to 3D plastic relaxation and compare to diffraction.

  15. Stoichiometry determined exchange interactions in amorphous ternary transition metal oxides: Theory and experiment

    SciTech Connect

    Hu, Shu-jun; Yan, Shi-shen Zhang, Yun-peng; Zhao, Ming-wen; Kang, Shi-shou; Mei, Liang-mo

    2014-07-28

    Amorphous transition metal oxides exhibit exotic transport and magnetic properties, while the absence of periodic structure has long been a major obstacle for the understanding of their electronic structure and exchange interaction. In this paper, we have formulated a theoretical approach, which combines the melt-quench approach and the spin dynamic Monte-Carlo simulations, and based on it, we explored amorphous Co{sub 0.5}Zn{sub 0.5}O{sub 1−y} ternary transition metal oxides. Our theoretical results reveal that the microstructure, the magnetic properties, and the exchange interactions of Co{sub 0.5}Zn{sub 0.5}O{sub 1−y} are strongly determined by the oxygen stoichiometry. In the oxygen-deficient sample (y > 0), we have observed the long-range ferromagnetic spin ordering which is associated with the non-stoichiometric cobalt-rich region rather than metallic clusters. On the other hand, the microstructure of stoichiometric sample takes the form of continuous random networks, and no long-range ferromagnetism has been observed in it. Magnetization characterization of experimental synthesized Co{sub 0.61}Zn{sub 0.39}O{sub 1−y} films verifies the relation between the spin ordering and the oxygen stoichiometry. Furthermore, the temperature dependence of electrical transport shows a typical feature of semiconductors, in agreement with our theoretical results.

  16. Theory of Plasmonic Waves on a Chain of Metallic Nanoparticles in a Liquid Crystalline Host

    NASA Astrophysics Data System (ADS)

    Stroud, David; Pike, Nicholas

    2014-03-01

    Linearly polarized plasmonic waves can propagate along a chain of metallic particles, of sufficiently small diameter and spacing. We have calculated the dispersion relations for these plasmonic waves when the host is either a nematic or a cholesteric liquid crystal (NLC or CLC). An NLC is found to alter the dispersion relations of both transverse (T) and or longitudinal (L) waves significantly from those for an isotropic host. If the NLC director is perpendicular to the metallic chain, the doubly degenerate T branch is split into two linearly polarized branches. Similar results are obtained for a CLC with twist axis parallel to the chain, except that the T branches are elliptically polarized. When a magnetic field is applied parallel to the chain, the dispersion relations for the T branches are no longer symmetric about k = 0 and the chain may act as a one-way waveguide at certain frequencies. We present numerical examples assuming spherical metal particle with a Drude dielectric function. This work was supported by the Center for Emerging Materials at The Ohio State University, an NSF MRSEC (Grant No. DMR0820414).

  17. Three-Dimensional Characterization of Buried Metallic Targets via a Tomographic Algorithm Applied to GPR Synthetic Data

    NASA Astrophysics Data System (ADS)

    Comite, Davide; Galli, Alessandro; Catapano, Ilaria; Soldovieri, Francesco; Pettinelli, Elena

    2013-04-01

    This work is focused on the three-dimensional (3-D) imaging of buried metallic targets achievable by processing GPR (ground penetrating radar) simulation data via a tomographic inversion algorithm. The direct scattering problem has been analysed by means of a recently-developed numerical setup based on an electromagnetic time-domain CAD tool (CST Microwave Studio), which enables us to efficiently explore different GPR scenarios of interest [1]. The investigated 3D domain considers here two media, representing, e.g., an air/soil environment in which variously-shaped metallic (PEC) scatterers can be buried. The GPR system is simulated with Tx/Rx antennas placed in a bistatic configuration at the soil interface. In the implementation, the characteristics of the antennas may suitably be chosen in terms of topology, offset, radiative features, frequency ranges, etc. Arbitrary time-domain waveforms can be used as the input GPR signal (e.g., a Gaussian-like pulse having the frequency spectrum in the microwave range). The gathered signal at the output port includes the backscattered wave from the objects to be reconstructed, and the relevant data may be displayed in canonical radargram forms [1]. The GPR system sweeps along one main rectilinear direction, and the scanning process is here repeated along different close parallel lines to acquire data for a full 3-D analysis. Starting from the processing of the synthetic GPR data, a microwave tomographic approach is used to tackle the imaging, which is based on the Kirchhoff approximation to linearize the inverse scattering problem [2]. The target reconstruction is given in terms of the amplitude of the 'object function' (normalized with respect to its maximum inside the 3-D investigation domain). The data of the scattered field are collected considering a multi-frequency step process inside the fixed range of the signal spectrum, under a multi-bistatic configuration where the Tx and Rx antennas are separated by an offset

  18. Density Functional Theory of Open-Shell Systems. The 3d-Series Transition-Metal Atoms and Their Cations.

    PubMed

    Luo, Sijie; Averkiev, Boris; Yang, Ke R; Xu, Xuefei; Truhlar, Donald G

    2014-01-14

    The 3d-series transition metals (also called the fourth-period transition metals), Sc to Zn, are very important in industry and biology, but they provide unique challenges to computing the electronic structure of their compounds. In order to successfully describe the compounds by theory, one must be able to describe their components, in particular the constituent atoms and cations. In order to understand the ingredients required for successful computations with density functional theory, it is useful to examine the performance of various exchange-correlation functionals; we do this here for 4s(N)3d(N') transition-metal atoms and their cations. We analyze the results using three ways to compute the energy of the open-shell states: the direct variational method, the weighted-averaged broken symmetry (WABS) method, and a new broken-symmetry method called the reinterpreted broken symmetry (RBS) method. We find the RBS method to be comparable in accuracy with the WABS method. By examining the overall accuracy in treating 18 multiplicity-changing excitations and 10 ionization potentials with the RBS method, 10 functionals are found to have a mean-unsigned error of <5 kcal/mol, with ωB97X-D topping the list. For local density functionals, which are more practical for extended systems, the M06-L functional is the most accurate. And by combining the results with our previous studies of p-block and 4d-series elements as well as databases for alkyl bond dissociation, main-group atomization energies, and π-π noncovalent interactions, we find five functionals, namely, PW6B95, MPW1B95, M08-SO, SOGGA11-X, and MPWB1K, to be highly recommended. We also studied the performance of PW86 and C09 exchange functionals, which have drawn wide interest in recent studies due to their claimed ability to reproduce Hartree-Fock exchange at long distance. By combining them with four correlation functionals, we find the performance of the resulting functionals disappointing both for 3d

  19. Atomistic simulation study of short pulse laser interactions with a metal target under conditions of spatial confinement by a transparent overlayer

    NASA Astrophysics Data System (ADS)

    Karim, Eaman T.; Shugaev, Maxim; Wu, Chengping; Lin, Zhibin; Hainsey, Robert F.; Zhigilei, Leonid V.

    2014-05-01

    The distinct characteristics of short pulse laser interactions with a metal target under conditions of spatial confinement by a solid transparent overlayer are investigated in a series of atomistic simulations. The simulations are performed with a computational model combining classical molecular dynamics (MD) technique with a continuum description of the laser excitation, electron-phonon equilibration, and electronic heat transfer based on two-temperature model (TTM). Two methods for incorporation of the description of a transparent overlayer into the TTM-MD model are designed and parameterized for Ag-silica system. The material response to the laser energy deposition is studied for a range of laser fluences that, in the absence of the transparent overlayer, covers the regimes of melting and resolidification, photomechanical spallation, and phase explosion of the overheated surface region. In contrast to the irradiation in vacuum, the spatial confinement by the overlayer facilitates generation of sustained high-temperature and high-pressure conditions near the metal-overlayer interface, suppresses the generation of unloading tensile wave, decreases the maximum depth of melting, and prevents the spallation and explosive disintegration of the surface region of the metal target. At high laser fluences, when the laser excitation brings the surface region of the metal target to supercritical conditions, the confinement prevents the expansion and phase decomposition characteristic for the vacuum conditions leading to a gradual cooling of the hot compressed supercritical fluid down to the liquid phase and eventual solidification. The target modification in this case is limited to the generation of crystal defects and the detachment of the metal target from the overlayer.

  20. Evaluation of the immunological profile of antibody-functionalized metal-filled single-walled carbon nanocapsules for targeted radiotherapy

    PubMed Central

    Perez Ruiz de Garibay, Aritz; Spinato, Cinzia; Klippstein, Rebecca; Bourgognon, Maxime; Martincic, Markus; Pach, Elzbieta; Ballesteros, Belén; Ménard-Moyon, Cécilia; Al-Jamal, Khuloud T.; Tobias, Gerard; Bianco, Alberto

    2017-01-01

    This study investigates the immune responses induced by metal-filled single-walled carbon nanotubes (SWCNT) under in vitro, ex vivo and in vivo settings. Either empty amino-functionalized CNTs [SWCNT-NH2 (1)] or samarium chloride-filled amino-functionalized CNTs with [SmCl3@SWCNT-mAb (3)] or without [SmCl3@SWCNT-NH2 (2)] Cetuximab functionalization were tested. Conjugates were added to RAW 264.7 or PBMC cells in a range of 1 μg/ml to 100 μg/ml for 24 h. Cell viability and IL-6/TNFα production were determined by flow cytometry and ELISA. Additionally, the effect of SWCNTs on the number of T lymphocytes, B lymphocytes and monocytes within the PBMC subpopulations was evaluated by immunostaining and flow cytometry. The effect on monocyte number in living mice was assessed after tail vein injection (150 μg of each conjugate per mouse) at 1, 7 and 13 days post-injection. Overall, our study showed that all the conjugates had no significant effect on cell viability of RAW 264.7 but conjugates 1 and 3 led to a slight increase in IL-6/TNFα. All the conjugates resulted in significant reduction in monocyte/macrophage cell numbers within PBMCs in a dose-dependent manner. Interestingly, monocyte depletion was not observed in vivo, suggesting their suitability for future testing in the field of targeted radiotherapy in mice. PMID:28198410

  1. Evaluation of the immunological profile of antibody-functionalized metal-filled single-walled carbon nanocapsules for targeted radiotherapy

    NASA Astrophysics Data System (ADS)

    Perez Ruiz de Garibay, Aritz; Spinato, Cinzia; Klippstein, Rebecca; Bourgognon, Maxime; Martincic, Markus; Pach, Elzbieta; Ballesteros, Belén; Ménard-Moyon, Cécilia; Al-Jamal, Khuloud T.; Tobias, Gerard; Bianco, Alberto

    2017-02-01

    This study investigates the immune responses induced by metal-filled single-walled carbon nanotubes (SWCNT) under in vitro, ex vivo and in vivo settings. Either empty amino-functionalized CNTs [SWCNT-NH2 (1)] or samarium chloride-filled amino-functionalized CNTs with [SmCl3@SWCNT-mAb (3)] or without [SmCl3@SWCNT-NH2 (2)] Cetuximab functionalization were tested. Conjugates were added to RAW 264.7 or PBMC cells in a range of 1 μg/ml to 100 μg/ml for 24 h. Cell viability and IL-6/TNFα production were determined by flow cytometry and ELISA. Additionally, the effect of SWCNTs on the number of T lymphocytes, B lymphocytes and monocytes within the PBMC subpopulations was evaluated by immunostaining and flow cytometry. The effect on monocyte number in living mice was assessed after tail vein injection (150 μg of each conjugate per mouse) at 1, 7 and 13 days post-injection. Overall, our study showed that all the conjugates had no significant effect on cell viability of RAW 264.7 but conjugates 1 and 3 led to a slight increase in IL-6/TNFα. All the conjugates resulted in significant reduction in monocyte/macrophage cell numbers within PBMCs in a dose-dependent manner. Interestingly, monocyte depletion was not observed in vivo, suggesting their suitability for future testing in the field of targeted radiotherapy in mice.

  2. Room Temperature Growth of Al-Doped ZnO Thin Films by Reactive DC Sputtering Technique with Metallic Target

    NASA Astrophysics Data System (ADS)

    Hasuike, Noriyuki; Nishio, Koji; Kisoda, Kenji; Harima, Hiroshi

    2013-01-01

    We prepared Al-deopd ZnO (AZO) films by reactive DC sputtering method using metallic target at room temperature. All the tested AZO films (0<[Al]<8.9%) with the transmittance above 85% in visible region were successfully grown on quartz substrate. All the AZO films have wurtzite structure with no impurity phase. The AZO films with [Al]<2.9% have the preferential orientation in c-axis direction, and the orientation became indistinct as increasing in Al content. In the optical measurement, the absorption edge was shifted from 3.30 to 3.66 eV due to Burstein-Moss effect, and the electron densities were roughly estimated at 2.5×1019 to 1.5×1021 cm-3, respectively. On the other hand, the high transmittance in infrared region suggested low electron mobility. Since this gives rise to the high electric resistivity, the further improvements and optimization of the growth conditions are required for the realization of AZO based transparent conductive.

  3. Magnetic Resonance Imaging Distortion and Targeting Errors from Strong Rare Earth Metal Magnetic Dental Implant Requiring Revision.

    PubMed

    Seong-Cheol, Park; Chong Sik, Lee; Seok Min, Kim; Eu Jene, Choi; Do Hee, Lee; Jung Kyo, Lee

    2016-12-22

    Recently, the use of magnetic dental implants has been re-popularized with the introduction of strong rare earth metal, for example, neodymium, magnets. Unrecognized magnetic dental implants can cause critical magnetic resonance image distortions. We report a case involving surgical failure caused by a magnetic dental implant. A 62-year-old man underwent deep brain stimulation for medically insufficiently controlled Parkinson's disease. Stereotactic magnetic resonance imaging performed for the first deep brain stimulation showed that the overdenture was removed. However, a dental implant remained and contained a neodymium magnet, which was unrecognized at the time of imaging; the magnet caused localized non-linear distortions that were the largest around the dental magnets. In the magnetic field, the subthalamic area was distorted by a 4.6 mm right shift and counter clockwise rotation. However, distortions were visually subtle in the operation field and small for distant stereotactic markers, with approximately 1-2 mm distortions. The surgeon considered the distortion to be normal asymmetry or variation. Stereotactic marker distortion was calculated to be in the acceptable range in the surgical planning software. Targeting errors, approximately 5 mm on the right side and 2 mm on the left side, occurred postoperatively. Both leads were revised after the removal of dental magnets. Dental magnets may cause surgical failures and should be checked and removed before stereotactic surgery. Our findings should be considered when reviewing surgical precautions and making distortion-detection algorithm improvements.

  4. Magnetovolume effect and finite-temperature theory of magnetism in transition metals and alloys

    NASA Astrophysics Data System (ADS)

    Kakehashi, Y.

    1990-01-01

    A review of recent developments in the theory of magnetovolume effects based on the Liberman-Pettifor virial theorem is presented. The general expression of the electronic contribution to the thermal expansion is shown to cover a wide range of magnetovolume effects from the insulator to the weak ferromagnets. It consists of the positive term proportional to the specific heat and a term proportional to the temperature derivative of the amplitude of the local moment. By using the single-site spin fluctuation theory (SSF) the Fe-Ni as well as Fe3Pt invar alloys are shown to be understood from this viewpoint. The local environment effects and the electron correlations at finite temperatures improve the difficulties in the SSF.

  5. Magnetovolume effect and finite-temperature theory of magnetism in transition metals and alloys

    NASA Astrophysics Data System (ADS)

    Kakehashi, Y.

    1989-10-01

    A review of recent developments in the theory of magnetovolume effects based on the Liberman-Pettifor virial theorem is presented. The general expression of the electronic contribution to the thermal expansion is shown to cover a wide range of magnetovolume effects from the insulator to the weak ferromagnets. It consists of the positive term proportional to the specific heat and a term proportional to the temperature derivative of the amplitude of the local moment. By using the single-site spin fluctuation theory (SSF) the Fe-Ni as well as Fe 3Pt invar alloys are shown to be understood from this viewpoint. The local environment effects and the electron correlations at finite temperatures improve the difficulties in the SSF.

  6. Peridynamic theory for modeling three-dimensional damage growth in metallic and composite structures

    NASA Astrophysics Data System (ADS)

    Ochoa-Ricoux, Juan Pedro

    A recently introduced nonlocal peridynamic theory removes the obstacles present in classical continuum mechanics that limit the prediction of crack initiation and growth in materials. It is also applicable at different length scales. This study presents an alternative approach for the derivation of peridynamic equations of motion based on the principle of virtual work. It also presents solutions for the longitudinal vibration of a bar subjected to an initial stretch, propagation of a pre-existing crack in a plate subjected to velocity boundary conditions, and crack initiation and growth in a plate with a circular cutout. Furthermore, damage growth in composites involves complex and progressive failure modes. Current computational tools are incapable of predicting failure in composite materials mainly due to their mathematical structure. However, the peridynamic theory removes these obstacles by taking into account non-local interactions between material points. Hence, an application of the peridynamic theory to predict how damage propagates in fiber reinforced composite materials subjected to mechanical and thermal loading conditions is presented. Finally, an analysis approach based on a merger of the finite element method and the peridynamic theory is proposed. Its validity is established through qualitative and quantitative comparisons against the test results for a stiffened composite curved panel with a central slot under combined internal pressure and axial tension. The predicted initial and final failure loads, as well as the final failure modes, are in close agreement with the experimental observations. This proposed approach demonstrates the capability of the PD approach to assess the durability of complex composite structures.

  7. Theory and applications of surface energy transfer for 2-20 nm diameter metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Riskowski, Ryan A.

    The development and experimental validation of a mathematical model for nanoparticle-based surface energy transfer (SET) between gold nanoparticles and fluorescent dye labels, has enabled biophysical studies of nucleic acid structure and function previously inaccessible by other methods. The main advantages of SET for optical distance measurements are that it can operate over longer distances than other similar methods, such as Forster Resonance Energy Transfer (FRET), thus enabling measurements across biological structures much larger than otherwise possible. This work discusses the fundamental theory for the SET interaction and expansion of SET theory to account for multiple interacting dye labels and demonstrated on DNA and RNA in order to allow 3D triangulation of labeled structures. SET theory has also been expanded to core shell structures which represent a new class of designer SET platforms with dramatically increased spectral windows; allowing for a multitude of dye labels to be used simultaneously over a broad range of wavelengths. Additionally, these designer nanostructures can incorporate the material properties of the core. So that , for example Ni Au, can provide a SET measurement platform coupled with a magnetic moment for sample purification and manipulation. These efforts to develop and establish optical SET methods lays a foundation of a powerful methodology for biophysical characterization, and allows researchers to study biological structures previously too large or complex to be easily studied, such as the unknown tertiary structures of large RNA elements.

  8. A solid-state density functional theory investigation of the effect of metal substitution (Metal = Mn, Cd, Co) on the terahertz spectra of isomorphous molecular metal 5-(4-pyridyl)tetrazolato complexes

    NASA Astrophysics Data System (ADS)

    Pellizzeri, Steven; Witko, Ewelina M.; Korter, Timothy M.; Zubieta, Jon

    2013-09-01

    The crystal structure and experimental terahertz spectroscopy of an isomorphous series [Mn(C6H4N5)2(H2O)4]ṡ2H2O (Mn-4PT), [Co(C6H4N5)2(H2O)4]ṡ2H2O (Co-4PT), and [Cd(C6H4N5)2(H2O)4]ṡ2H2O (Cd-4PT) were compared using solid-state density functional theory (DFT) simulations. The effect of the central metal atom was investigated to determine the influence on the low energy lattice and molecular vibrations exhibited in the region from 10 to 100 cm-1, known as the terahertz (THz) region. Using solid-state DFT the normal modes of these THz vibrations were determined and it was shown that the mass and size of the metal center has a large effect in this region. Each complex exhibited common vibrational modes involving whole ligand motion around the central metal atom. These vibrations were found to shift to lower frequencies with a drastic mass increase; however, this trend is reversed with the smaller mass change between the manganese and cobalt due to the stronger cobalt-nitrogen bond compared to the manganese-nitrogen bond.

  9. Effect of scanning speed on continuous wave laser scribing of metal thin films: theory and experiment

    NASA Astrophysics Data System (ADS)

    Shahbazi, AmirHossein; Koohian, Ata; Madanipour, Khosro

    2017-01-01

    In this paper continuous wave laser scribing of the metal thin films have been investigated theoretically and experimentally. A formulation is presented based on parameters like beam power, spot size, scanning speed and fluence thresholds. The role of speed on the transient temperature and tracks width is studied numerically. By using two frameworks of pulsed laser ablation of thin films and laser printing on paper, the relation between ablation width and scanning speed has been derived. Furthermore, various speeds of the focused 450 nm continuous laser diode with an elliptical beam spot applied to a 290 nm copper thin film coated on glass, experimentally. The beam power was 150 mW after spatial filtering. By fitting the theoretical formulation to the experimental data, the threshold fluence and energy were obtained to be 13.2 J mm-2 and 414~μ J respectively. An anticipated theoretical parameter named equilibrium~border was verified experimentally. It shows that in the scribing of the 290 nm copper thin film, at a distance where the intensity reaches about 1/e of its maximum value, the absorbed fluence on the surface is equal to zero. Therefore the application of continuous laser in metal thin film ablation has different mechanism from pulsed laser drilling and beam scanning in printers.

  10. Physical Theory of Voltage Fade in Lithium- and Manganese-Rich Transition Metal Oxides

    SciTech Connect

    Rinaldo, Steven G.; Gallagher, Kevin G.; Long, Brandon R.; Croy, Jason R.; Bettge, Martin; Abraham, Daniel P.; Bareno, Javier; Dees, Dennis W.

    2015-03-04

    Lithium- and manganese-rich (LMR) transition metal oxide cathodes are of interest for lithium-ion battery applications due to their increased energy density and decreased cost. However, the advantages in energy density and cost are offset, in part, due to the phenomena of voltage fade. Specifically, the voltage profiles (voltage as a function of capacity) of LMR cathodes transform from a high energy configuration to a lower energy configuration as they are repeatedly charged (Li removed) and discharged (Li inserted). Here, we propose a physical model of voltage fade that accounts for the emergence of a low voltage Li phase due to the introduction of transition metal ion defects within a parent Li phase. The phenomenological model was re-cast in a general form and experimental LMR charge profiles were de-convoluted to extract the evolutionary behavior of various components of LMR capacitance profiles. Evolution of the voltage fade component was found to follow a universal growth curve with a maximal voltage fade capacity of ≈ 20% of the initial total capacity.

  11. Physical Theory of Voltage Fade in Lithium- and Manganese-Rich Transition Metal Oxides

    DOE PAGES

    Rinaldo, Steven G.; Gallagher, Kevin G.; Long, Brandon R.; ...

    2015-03-04

    Lithium- and manganese-rich (LMR) transition metal oxide cathodes are of interest for lithium-ion battery applications due to their increased energy density and decreased cost. However, the advantages in energy density and cost are offset, in part, due to the phenomena of voltage fade. Specifically, the voltage profiles (voltage as a function of capacity) of LMR cathodes transform from a high energy configuration to a lower energy configuration as they are repeatedly charged (Li removed) and discharged (Li inserted). Here, we propose a physical model of voltage fade that accounts for the emergence of a low voltage Li phase due tomore » the introduction of transition metal ion defects within a parent Li phase. The phenomenological model was re-cast in a general form and experimental LMR charge profiles were de-convoluted to extract the evolutionary behavior of various components of LMR capacitance profiles. Evolution of the voltage fade component was found to follow a universal growth curve with a maximal voltage fade capacity of ≈ 20% of the initial total capacity.« less

  12. Paired box gene 2 is associated with estrogen receptor α in ovarian serous tumors: Potential theory basis for targeted therapy.

    PubMed

    Wang, Min; Ma, Haifen

    2016-08-01

    It has been suggested that Paired box gene (PAX)2 is activated by estradiol via estrogen receptor (ER)α in breast and endometrial cancer. The expression of PAX2 was restricted to ovarian serous tumors and only one case was positive in borderline mucinous tumor in our previous study. In the present study, immunohistochemistry was performed to assess the expression of ERα in 58 cases of ovarian serous tumors, including 30 serous cystadenomas, 16 borderline serous cystadenomas, 12 serous carcinomas and 67 cases of ovarian mucinous tumors, including 29 mucinous cystadenoma, 23 borderline mucinous cystadenoma and 15 mucinous carcinoma, which were the same specimens with detection of PAX2 expression. The results demonstrated that ERα was expressed in 10% (3/30) of serous cystadenomas, 62.5% (10/16) borderline serous cystadenomas and 66.7% (8/12) serous carcinomas. The expression of ERα in borderline serous cystadenomas and serous carcinomas were significantly higher compared with that in serous cystadenomas (P<0.01). ERα was detected in 3.4% (1/29) mucinous cystadenoma, 26.1% (6/23) borderline mucinous cystadenoma and only 6.7% (1/15) mucinous carcinoma. Furthermore, a scatter plot of the expression of PAX2 and ERα revealed a linear correlation between them in ovarian serous tumors (P<0.0001). With few positive results, no correlation was determined in ovarian mucinous tumors. It was demonstrated that PAX2 is associated with ERα in ovarian serous tumors, and this may become a potential theory basis for targeted therapy for ovarian serous tumors. Further research is required to determine how PAX2 and ERα work together, and the role of targeted therapy in ovarian serous tumors.

  13. Luminescent properties of metal-organic framework MOF-5: relativistic time-dependent density functional theory investigations.

    PubMed

    Ji, Min; Lan, Xin; Han, Zhenping; Hao, Ce; Qiu, Jieshan

    2012-11-19

    The electronically excited state and luminescence property of metal-organic framework MOF-5 were investigated using relativistic density functional theory (DFT) and time-dependent DFT (TDDFT). The geometry, IR spectra, and UV-vis spectra of MOF-5 in the ground state were calculated using relativistic DFT, leading to good agreement between the experimental and theoretical results. The frontier molecular orbitals and electronic configuration indicated that the luminescence mechanism in MOF-5 follows ligand-to-ligand charge transfer (LLCT), namely, π* → π, rather than emission with the ZnO quantum dot (QD) proposed by Bordiga et al. The geometry and IR spectra of MOF-5 in the electronically excited state have been calculated using the relativistic TDDFT and compared with those for the ground state. The comparison reveals that the Zn4O13 QD is rigid, whereas the ligands BDC(2-) are nonrigid. In addition, the calculated emission band of MOF-5 is in good agreement with the experimental result and is similar to that of the ligand H2BDC. The combined results confirmed that the luminescence mechanism for MOF-5 should be LLCT with little mixing of the ligand-to-metal charge transfer. The reason for the MOF-5 luminescence is explained by the excellent coplanarity between the six-membered ring consisting of zinc, oxygen, carbon, and the benzene ring.

  14. A self-consistent plasticity theory for modeling the thermo-mechanical properties of irradiated FCC metallic polycrystals

    NASA Astrophysics Data System (ADS)

    Xiao, Xiazi; Song, Dingkun; Xue, Jianming; Chu, Haijian; Duan, Huiling

    2015-05-01

    A self-consistent theoretical framework is developed to model the thermo-mechanical behaviors of irradiated face-centered cubic (FCC) polycrystalline metals at low to intermediate homologous temperatures. In this model, both irradiation and temperature effects are considered at the grain level with the assist of a tensorial plasticity crystal model, and the elastic-visocoplastic self-consistent method is applied for the scale transition from individual grains to macroscopic polycrystals. The proposed theory is applied to analyze the mechanical behaviors of irradiated FCC copper. It is found that: (1) the numerical results match well with experimental data, which includes the comparison of results for single crystals under the load in different directions, and for polycrystals with the influences of irradiation and temperature. Therefore, the feasibility and accuracy of the present model are well demonstrated. (2) The main irradiation effects including irradiation hardening, post-yield softening, strain-hardening coefficient (SHC) dropping and the non-zero stress offset are all captured by the proposed model. (3) The increase of temperature results in the decrease of yield strength and SHC. The former is attributed to the weakened dislocation-defect interaction, while the latter is due to the temperature-strengthened dynamic recovery of dislocations through the thermally activated mechanism. The present model may provide a theoretical guide to predict the thermo-mechanical behaviors of irradiated FCC metals for the selection of structural materials in nuclear equipment.

  15. Analysis of amorphous indium-gallium-zinc-oxide thin-film transistor contact metal using Pilling-Bedworth theory and a variable capacitance diode model

    NASA Astrophysics Data System (ADS)

    Kiani, Ahmed; Hasko, David G.; Milne, William I.; Flewitt, Andrew J.

    2013-04-01

    It is widely reported that threshold voltage and on-state current of amorphous indium-gallium-zinc-oxide bottom-gate thin-film transistors are strongly influenced by the choice of source/drain contact metal. Electrical characterisation of thin-film transistors indicates that the electrical properties depend on the type and thickness of the metal(s) used. Electron transport mechanisms and possibilities for control of the defect state density are discussed. Pilling-Bedworth theory for metal oxidation explains the interaction between contact metal and amorphous indium-gallium-zinc-oxide, which leads to significant trap formation. Charge trapping within these states leads to variable capacitance diode-like behavior and is shown to explain the thin-film transistor operation.

  16. Theory of light scattering in subwavelength metallic slot antenna array fabricated on subwavelength thin film

    NASA Astrophysics Data System (ADS)

    Choi, S. B.; Park, D. J.

    2015-10-01

    We demonstrate an analytic model that describes the near-field electromagnetic field profile near a subwavelength-sized metallic slot antenna fabricated on a thin dielectric substrate having a subwavelength thickness reaching λ/1000 in the terahertz frequency region. We found two-dimensional light diffraction induced by the two-dimensional nature of the slot antenna, and back-reflected waves interfered with each other in a complicated manner, resulting in a coupling of the Fourierdecomposed field amplitudes between the diffraction orders along the x and the y directions. We applied these findings to our model by modifying a previously developed model [D. J. Park et al., J. Korean Phys. Soc. 65, 1390 (2014)], and we monitor the effect on far-field transmission. This coupling effect was found to contribute to removal of physically-meaningless spikes or divergences in the transmission spectra, especially for relatively thick substrates.

  17. Nonequilibrium theory of a hot-electron bolometer with normal metal-insulator-superconductor tunnel junction

    SciTech Connect

    Golubev, Dmitri; Kuzmin, Leonid

    2001-06-01

    The operation of the hot-electron bolometer with normal metal-insulator-superconductor (NIS) tunnel junction as a temperature sensor is analyzed theoretically. The responsivity and the noise equivalent power (NEP) of the bolometer are obtained numerically for typical experimental parameters. Relatively simple approximate analytical expressions for these values are derived. The time constant of the device is also found. We demonstrate that the effect of the electron cooling by the NIS junction, which serves as a thermometer, can improve the sensitivity. This effect is also useful in the presence of the finite background power load. We discuss the effect of the correlation of the shot noise and the heat flow noise in the NIS junction. {copyright} 2001 American Institute of Physics.

  18. Microstructure-based description of the deformation of metals: Theory and application

    NASA Astrophysics Data System (ADS)

    Helm, Dirk; Butz, Alexander; Raabe, Dierk; Gumbsch, Peter

    2011-04-01

    Aiming for an integrated approach to computational materials engineering in an industrial context poses big challenges in the development of suitable materials descriptions for the different steps along the processing chain. The first key component is to correctly describe the microstructural changes during the thermal and mechanical processing of the base material into a semi-finished product. Explicit representations of the microstructure are most suitable there. The final processing steps and particularly component assessment then has to describe the entire component which requires homogenized continuum mechanical representations. A key challenge is the step in between, the determination of the (macroscopic) materials descriptions from microscopic structures. This article describes methods to include microstructure into descriptions of the deformation of metal, and demonstrates the central steps of the simulation along the processing chain of an automotive component manufactured from a dual phase steel.

  19. Theory of edge-state optical absorption in two-dimensional transition metal dichalcogenide flakes

    NASA Astrophysics Data System (ADS)

    Trushin, Maxim; Kelleher, Edmund J. R.; Hasan, Tawfique

    2016-10-01

    We develop an analytical model to describe sub-band-gap optical absorption in two-dimensional semiconducting transition metal dichalcogenide (s-TMD) nanoflakes. The material system represents an array of few-layer molybdenum disulfide crystals, randomly orientated in a polymer matrix. We propose that optical absorption involves direct transitions between electronic edge states and bulk bands, depends strongly on the carrier population, and is saturable with sufficient fluence. For excitation energies above half the band gap, the excess energy is absorbed by the edge-state electrons, elevating their effective temperature. Our analytical expressions for the linear and nonlinear absorption could prove useful tools in the design of practical photonic devices based on s-TMDs.

  20. Observations vs theory: from metallicity correlations of exoplanets and debris discs to HL Tau

    NASA Astrophysics Data System (ADS)

    Nayakshin, Sergei V.

    2015-12-01

    Boley et al (2010) and Nayakshin (2010) proposed Tidal Downsizing (TD), a new hypothesis for forming all types of planets. Gas fragments born by gravitational disc instability at ~ 100 AU migrate inwards rapidly, with some becoming hot Jupiters. Grain sedimentation inside the fragments makes rocky cores. These cores are future Earths and Super Earths, leaved behind when most of the migrating fragments are tidally disrupted.TD can now be tested against data in detail thanks to a numerical population synthesis model (Nayakshin and Fletcher 2015). TD scenario is fundamentally different from Core Accretion (CA), with sub-Saturn planets and debris discs born in gas fragment disruptions, and not vice versa. I therefore find robust observational differences between CA and TD despite uncertainties inherent in any population synthesis. Here I use metallicity correlations of all sorts to test the model. In TD, the only population that correlates with metallicity (Z) of the host strongly is that of moderately massive gas giants interior to a few AU from the host. Super-Earths and debris discs correlate in mass but not in numbers with Z; very massive gas giants, brown dwarfs and directly imaged gas giants are neutral to Z. Fragment self-destruction by core feedback explains simultaneously the core mass function roll-over at ~20 Earth masses, the rapid formation of suspected planets in HL Tau, and the paucity of directly imaged gas giants. Debris discs and gas giants do not correlate in TD, as observed.I argue that TD does a better job in accounting for many of the observed properties of exoplanets and planetary debris than CA. I finish with observational predictions that can distinguish TD from Core Accretion in the near future.

  1. Application of analytic hierarchy process-grey target theory systematic model in comprehensive evaluation of water environmental quality.

    PubMed

    Wu, Jun; Tian, Xiaogang; Tang, Ya; Zhao, Yujie; Hu, Yandi; Fang, Zili

    2010-07-01

    Comprehensive evaluation of the water environment for effective water quality management is complicated by a considerable number of factors and uncertainties. It is difficult to combine micro-evaluation with the macro-evaluation process. To effectively eliminate the subjective errors of the traditional analytic hierarchy process (AHP), a new modeling approach--the analytic hierarchy process and grey target theory (AHP-GTT) systematic model--is presented in this study to evaluate water quality in a certain watershed. A case study of applying the AHP-GTT systematic model to the evaluation and analysis of the water environment was conducted in the Yibin section of the Yangtze River, China. The micro-evaluation is based on defining the weights of indices of the water quality (IWQ) of each water cross-section, while the macro-evaluation is based on calculating the comprehensive indices of water environmental quality and analyzing the tendency of the water environment of each cross-section. The results indicated that the Baixi and Shuidongmen sections are seriously polluted areas, with the tendencies of becoming worse. Also, the key IWQs of these two cross-sections are 5-day biochemical oxygen demand and chemical oxygen demand of permanganate, respectively.

  2. On the theory of ps and sub-ps laser pulse interaction with metals. II. Spatial temperature distribution

    NASA Astrophysics Data System (ADS)

    Hüttner, Bernd; Rohr, Gernot C.

    1998-04-01

    The interaction of short laser pulses with metals is described in terms of a new model involving a generalised nonlocal heat flow in time. The resulting system of coupled differential equations contains additional terms that originate in the thermal inertia of the electron subsystem. They are connected to the time derivative of both the laser intensity and the coupling of the electrons to the phonons. After briefly discussing the importance of the coefficient of heat exchange and of the different contributions to its main parts, the electron-phonon coupling and the average of the squared phonon frequencies, we present snap-shot-like calculations of the spatial temperature distribution along the z-axis for Al, Au, Pb and Nb for different intensities but fixed pulse duration τL=250 fs. In addition, the electron and phonon temperatures inside a thin Au film are studied in detail. Our results are compared to those arising from a standard two temperature model (TTM) and those of the conventional theory. While the traditional theory becomes invalid in most cases at least in the ps-range the differences between our approach and the TTM become the more pronounced the smaller the coefficient of heat exchange.

  3. Energy level alignment and quantum conductance of functionalized metal-molecule junctions: Density functional theory versus GW calculations

    SciTech Connect

    Jin, Chengjun; Markussen, Troels; Thygesen, Kristian S.; Strange, Mikkel; Solomon, Gemma C.

    2013-11-14

    We study the effect of functional groups (CH{sub 3}*4, OCH{sub 3}, CH{sub 3}, Cl, CN, F*4) on the electronic transport properties of 1,4-benzenediamine molecular junctions using the non-equilibrium Green function method. Exchange and correlation effects are included at various levels of theory, namely density functional theory (DFT), energy level-corrected DFT (DFT+Σ), Hartree-Fock and the many-body GW approximation. All methods reproduce the expected trends for the energy of the frontier orbitals according to the electron donating or withdrawing character of the substituent group. However, only the GW method predicts the correct ordering of the conductance amongst the molecules. The absolute GW (DFT) conductance is within a factor of two (three) of the experimental values. Correcting the DFT orbital energies by a simple physically motivated scissors operator, Σ, can bring the DFT conductances close to experiments, but does not improve on the relative ordering. We ascribe this to a too strong pinning of the molecular energy levels to the metal Fermi level by DFT which suppresses the variation in orbital energy with functional group.

  4. Theory, design, and operation of liquid metal fast breeder reactors, including operational health physics

    SciTech Connect

    Adams, S.R.

    1985-10-01

    A comprehensive evaluation was conducted of the radiation protection practices and programs at prototype LMFBRs with long operational experience. Installations evaluated were the Fast Flux Test Facility (FFTF), Richland, Washington; Experimental Breeder Reactor II (EBR-II), Idaho Falls, Idaho; Prototype Fast Reactor (PFR) Dounreay, Scotland; Phenix, Marcoule, France; and Kompakte Natriumgekuhlte Kernreak Toranlange (KNK II), Karlsruhe, Federal Republic of Germany. The evaluation included external and internal exposure control, respiratory protection procedures, radiation surveillance practices, radioactive waste management, and engineering controls for confining radiation contamination. The theory, design, and operating experience at LMFBRs is described. Aspects of LMFBR health physics different from the LWR experience in the United States are identified. Suggestions are made for modifications to the NRC Standard Review Plan based on the differences.

  5. Performance of Density Functional Theory for Second Row (4d) Transition Metal Thermochemistry.

    PubMed

    Laury, Marie L; Wilson, Angela K

    2013-09-10

    The performances of 22 density functionals, including generalized gradient approximation (GGA), hybrid GGAs, hybrid-meta GGAs, and range-separated and double hybrid functionals, in combination with the correlation consistent basis sets and effective core potentials, have been gauged for the prediction of gas phase enthalpies of formation for the TM-4d set, which contains 30 second row transition metal-containing molecules. The enthalpies of formation determined by the 22 density functionals were compared to those generated via the relativistic pseudopotential correlation consistent Composite Approach (rp-ccCA), which has a goal of reproducing energies akin to those from CCSD(T,FC1)-DK/aug-cc-pCV∞Z-DK calculations. B3LYP/cc-pVTZ-PP optimized geometries were used in this study, though structures determined by other functionals also were examined. Of the functionals employed, the double hybrid functionals, B2GP-PLYP and mPW2-PLYP, yielded the best overall results with mean absolute deviations (MADs) from experimental enthalpies of formation of 4.25 and 5.19 kcal mol(-1), respectively. The GGA functionals BP86 and PBEPBE resulted in deviations from experiment of nearly 100 kcal mol(-1) for molecules such as molybdenum carbonyls. The ωB97X-D functional, which includes the separation of exchange energy into long-range and short-range contributions and includes a dispersion correction, resulted in an MAD of 6.52 kcal mol(-1).

  6. The absence of intraband scattering in a consistent theory of Gilbert damping in pure metallic ferromagnets

    NASA Astrophysics Data System (ADS)

    Edwards, D. M.

    2016-03-01

    Damping of magnetization dynamics in a ferromagnetic metal, arising from spin-orbit coupling, is usually characterised by the Gilbert parameter α. Recent calculations of this quantity, using a formula due to Kambersky, find that it is infinite for a perfect crystal owing to an intraband scattering term which is of third order in the spin-orbit parameter ξ. This surprising result conflicts with recent work by Costa and Muniz who study damping numerically by direct calculation of the dynamical transverse susceptibility in the presence of spin-orbit coupling. We resolve this inconsistency by following the approach of Costa and Muniz for a slightly simplified model where it is possible to calculate α analytically. We show that to second order in ξ one retrieves the Kambersky result for α, but to higher order one does not obtain any divergent intraband terms. The present work goes beyond that of Costa and Muniz by pointing out the necessity of including the effect of long-range Coulomb interaction in calculating damping for large ξ. A direct derivation of the Kambersky formula is given which shows clearly the restriction of its validity to second order in ξ so that no intraband scattering terms appear. This restriction has an important effect on the damping over a substantial range of impurity content and temperature. The experimental situation is discussed.

  7. Pressure-induced phase transitions in Pa metal from first-principles theory

    SciTech Connect

    Soederlind, P.; Eriksson, O.

    1997-11-01

    Protactinium metal is shown to undergo a phase transition to the {alpha}-U orthorhombic structure below 1 Mbar pressure. At higher pressures, the bct phase reenters in the phase diagram and at the highest pressures, an ideal hcp structure becomes stable. Hence, Pa undergoes a sequence of transitions; bct{r_arrow}{alpha}-U{r_arrow}bct{r_arrow}hcp, with the first transition taking place at 0.25 Mbar and the subsequent ones above 1 Mbar. The bct{r_arrow}{alpha}-U transition is triggered by the pressure-induced promotion of the spd valence states to 5f states. In this regard, Pa approaches uranium which at ambient conditions has one more 5f electron than Pa at similar conditions. At higher compression of Pa, the 5f band broadens and electrostatic interactions in combination with Born-Mayer repulsion become increasingly important and this drives Pa to gradually more close-packed structures. At ultrahigh pressures, the balance between electrostatic energy, Born-Mayer repulsion, and one-electron band energy stabilizes the hcp (ideal packing) structure. The electrostatic energy and Born-Mayer repulsion rule out open crystal structures under these conditions in Pa and between the close-packed structures, the hcp structure is shown to be stabilized by filling of the 5f band. {copyright} {ital 1997} {ital The American Physical Society}

  8. Theory of magnetoresistance due to lattice dislocations in face-centred cubic metals

    NASA Astrophysics Data System (ADS)

    Bian, Q.; Niewczas, M.

    2016-06-01

    A theoretical model to describe the low temperature magneto-resistivity of high purity copper single and polycrystals containing different density and distribution of dislocations has been developed. In the model, magnetoresistivity tensor is evaluated numerically using the effective medium approximation. The anisotropy of dislocation-induced relaxation time is considered by incorporating two independent energy bands with different relaxation times and the spherical and cylindrical Fermi surfaces representing open, extended and closed electron orbits. The effect of dislocation microstructure is introduced by means of two adjustable parameters corresponding to the length and direction of electron orbits in the momentum space, which permits prediction of magnetoresistance of FCC metals containing different density and distribution of dislocations. The results reveal that dislocation microstructure influences the character of the field-dependent magnetoresistivity. In the orientation of the open orbits, the quadratic variation in magnetoresistivity changes to quasi-linear as the density of dislocations increases. In the closed orbit orientation, dislocations delay the onset of magnetoresistivity saturation. The results indicate that in the open orbit orientations of the crystals, the anisotropic relaxation time due to small-angle dislocation scattering induces the upward deviation from Kohler's rule. In the closed orbit orientations Kohler's rule holds, independent of the density of dislocations. The results obtained with the model show good agreement with the experimental measurements of transverse magnetoresistivity in deformed single and polycrystal samples of copper at 2 K.

  9. Pressure-induced phase transitions in Pa metal from first-principles theory

    NASA Astrophysics Data System (ADS)

    Söderlind, Per; Eriksson, Olle

    1997-11-01

    Protactinium metal is shown to undergo a phase transition to the α-U orthorhombic structure below 1 Mbar pressure. At higher pressures, the bct phase reenters in the phase diagram and at the highest pressures, an ideal hcp structure becomes stable. Hence, Pa undergoes a sequence of transitions; bct-->α-U-->bct-->hcp, with the first transition taking place at 0.25 Mbar and the subsequent ones above 1 Mbar. The bct-->α-U transition is triggered by the pressure-induced promotion of the spd valence states to 5f states. In this regard, Pa approaches uranium which at ambient conditions has one more 5f electron than Pa at similar conditions. At higher compression of Pa, the 5f band broadens and electrostatic interactions in combination with Born-Mayer repulsion become increasingly important and this drives Pa to gradually more close-packed structures. At ultrahigh pressures, the balance between electrostatic energy, Born-Mayer repulsion, and one-electron band energy stabilizes the hcp (ideal packing) structure. The electrostatic energy and Born-Mayer repulsion rule out open crystal structures under these conditions in Pa and between the close-packed structures, the hcp structure is shown to be stabilized by filling of the 5f band.

  10. Initial observations of cavitation-induced erosion of liquid metal spallation target vessels at the Spallation Neutron Source

    SciTech Connect

    McClintock, David A; Riemer, Bernie; Ferguson, Phillip D; Carroll, Adam J; Dayton, Michael J

    2012-01-01

    During operation of the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory the mechanical properties of the AISI 316L target module are altered by high-energy neutron and proton radiation. The interior surfaces of the target vessel are also damaged by cavitation-induced erosion, which results from repetitive rapid heating of the liquid mercury by high-energy proton beam pulses. Until recently no observations of cavitation-induced erosion were possible for conditions prototypical to the SNS. Post irradiation examination (PIE) of the first and second operational SNS targets was performed to gain insight into the radiation-induced changes in mechanical properties of the 316L target material and the extent of cavitation-induced erosion to the target vessel inner surfaces. Observations of cavitation-induced erosion of the first and second operational SNS target modules are presented here, including images of the target vessel interiors and specimens removed from the target beam-entrance regions.

  11. Predicting density functional theory total energies and enthalpies of formation of metal-nonmetal compounds by linear regression

    NASA Astrophysics Data System (ADS)

    Deml, Ann M.; O'Hayre, Ryan; Wolverton, Chris; Stevanović, Vladan

    2016-02-01

    The availability of quantitatively accurate total energies (Etot) of atoms, molecules, and solids, enabled by the development of density functional theory (DFT), has transformed solid state physics, quantum chemistry, and materials science by allowing direct calculations of measureable quantities, such as enthalpies of formation (Δ Hf ). Still, the ability to compute Etot and Δ Hf values does not, necessarily, provide insights into the physical mechanisms behind their magnitudes or chemical trends. Here, we examine a large set of calculated Etot and Δ Hf values obtained from the DFT+U -based fitted elemental-phase reference energies (FERE) approach [V. Stevanović, S. Lany, X. Zhang, and A. Zunger, Phys. Rev. B 85, 115104 (2012), 10.1103/PhysRevB.85.115104] to probe relationships between the Etot/Δ Hf of metal-nonmetal compounds in their ground-state crystal structures and properties describing the compound compositions and their elemental constituents. From a stepwise linear regression, we develop a linear model for Etot, and consequently Δ Hf , that reproduces calculated FERE values with a mean absolute error of ˜80 meV/atom. The most significant contributions to the model include calculated total energies of the constituent elements in their reference phases (e.g., metallic iron or gas phase O2), atomic ionization energies and electron affinities, Pauling electronegativity differences, and atomic electric polarizabilities. These contributions are discussed in the context of their connection to the underlying physics. We also demonstrate that our Etot/Δ Hf model can be directly extended to predict the Etot and Δ Hf of compounds outside the set used to develop the model.

  12. Predicting Bond Dissociation Energies of Transition-Metal Compounds by Multiconfiguration Pair-Density Functional Theory and Second-Order Perturbation Theory Based on Correlated Participating Orbitals and Separated Pairs.

    PubMed

    Bao, Junwei Lucas; Odoh, Samuel O; Gagliardi, Laura; Truhlar, Donald G

    2017-02-14

    We study the performance of multiconfiguration pair-density functional theory (MC-PDFT) and multireference perturbation theory for the computation of the bond dissociation energies in 12 transition-metal-containing diatomic molecules and three small transition-metal-containing polyatomic molecules and in two transition-metal dimers. The first step is a multiconfiguration self-consistent-field calculation, for which two choices must be made: (i) the active space and (ii) its partition into subspaces, if the generalized active space formulation is used. In the present work, the active space is chosen systematically by using three correlated-participating-orbitals (CPO) schemes, and the partition is chosen by using the separated-pair (SP) approximation. Our calculations show that MC-PDFT generally has similar accuracy to CASPT2, and the active-space dependence of MC-PDFT is not very great for transition-metal-ligand bond dissociation energies. We also find that the SP approximation works very well, and in particular SP with the fully translated BLYP functional SP-ftBLYP is more accurate than CASPT2. SP greatly reduces the number of configuration state functions relative to CASSCF. For the cases of FeO and NiO with extended-CPO active space, for which complete active space calculations are unaffordable, SP calculations are not only affordable but also of satisfactory accuracy. All of the MC-PDFT results are significantly better than the corresponding results with broken-symmetry spin-unrestricted Kohn-Sham density functional theory. Finally we test a perturbation theory method based on the SP reference and find that it performs slightly worse than CASPT2 calculations, and for most cases of the nominal-CPO active space, the approximate SP perturbation theory calculations are less accurate than the much less expensive SP-PDFT calculations.

  13. Adsorption and ring-opening of lactide on the chiral metal surface Pt(321)S studied by density functional theory

    NASA Astrophysics Data System (ADS)

    Franke, J.-H.; Kosov, D. S.

    2015-01-01

    We study the adsorption and ring-opening of lactide on the naturally chiral metal surface Pt(321)S. Lactide is a precursor for polylactic acid ring-opening polymerization, and Pt is a well known catalyst surface. We study, here, the energetics of the ring-opening of lactide on a surface that has a high density of kink atoms. These sites are expected to be present on a realistic Pt surface and show enhanced catalytic activity. The use of a naturally chiral surface also enables us to study potential chiral selectivity effects of the reaction at the same time. Using density functional theory with a functional that includes the van der Waals forces in a first-principles manner, we find modest adsorption energies of around 1.4 eV for the pristine molecule and different ring-opened states. The energy barrier to be overcome in the ring-opening reaction is found to be very small at 0.32 eV and 0.30 eV for LL- and its chiral partner DD-lactide, respectively. These energies are much smaller than the activation energy for a dehydrogenation reaction of 0.78 eV. Our results thus indicate that (a) ring-opening reactions of lactide on Pt(321) can be expected already at very low temperatures, and Pt might be a very effective catalyst for this reaction; (b) the ring-opening reaction rate shows noticeable enantioselectivity.

  14. Theory of electron-hole pair excitations in unimolecular processes at metal surfaces. I. X-ray edge effects

    NASA Astrophysics Data System (ADS)

    Gadzuk, J. W.; Metiu, H.

    1980-09-01

    A theory of the dynamics of molecular processes at solid surfaces must necessarily deal with those aspects of the solid which provide dissipative or irreversible reaction channels, thus giving the particular process a direction in time. While the heat-bath aspects of the solid are often considered from the phonon point of view, there is increasing speculation that the substrate electron-hole pair excitations may be a significant rate-determining factor, at least for metals. This belief is supported by various conclusions which have emerged from theoretical studies of time-dependent perturbations acting on extended Fermi systems, as physically realized in core-level spectroscopies of solids. We present here one phase of a study of surface reaction dynamics, focusing on the irreversible coupling of nuclear motion of an incident beam of atoms or molecules with the substrate electrons. For the cases in which the incident particle undergoes a substrate-induced diabatic transition in its internal electronic state, a sudden localized perturbation on the electrons is turned on. In analogy with the x-ray edge problem, an infrared divergent spectrum of electron-hole pairs is created which could give rise to irreversibility. Specific examples are considered and the ramifications on such observable quantities as sticking coefficients are detailed.

  15. Noncollinear spin-fluctuation theory of transition-metal magnetism: Role of transverse spin fluctuations in Fe

    NASA Astrophysics Data System (ADS)

    Garibay-Alonso, R.; Dorantes-Dávila, J.; Pastor, G. M.

    2015-05-01

    A local electronic theory of transition-metal magnetism at finite temperatures is presented, which takes into account longitudinal and transverse spin fluctuations on the same footing. The magnetic properties are determined in the framework of a rotational-invariant d -band model Hamiltonian by applying a four-field Hubbard-Stratonovich functional-integral method in the static approximation. The role of transverse spin excitations on the temperature-dependent magnetic properties is investigated by performing alloy averages in the single-site virtual crystal approximation. Bulk Fe is considered as the representative example for the applications. Results are given for the average magnetization M , for the spin-excitation energies, and for the transverse and longitudinal contributions to the local magnetic moments μl at atom l . The importance of noncollinear spin excitations is quantified by comparison with the corresponding collinear calculations. An important reduction of about 33% of the calculated Curie temperature TC is obtained, which now amounts to 1250 K and is thus relatively close to the experimental value. The longitudinal (transverse) components of μl are found to decrease (increase) as a function of temperature until the full rotational symmetry is reached at TC. This reflects the increasing importance of the transverse spin fluctuations. The origin of the temperature dependence of M and μl is analyzed in terms of the local spin-fluctuation energies.

  16. Assessing the density functional theory-based multireference configuration interaction (DFT/MRCI) method for transition metal complexes

    SciTech Connect

    Escudero, Daniel E-mail: thiel@kofo.mpg.de; Thiel, Walter E-mail: thiel@kofo.mpg.de

    2014-05-21

    We report an assessment of the performance of density functional theory-based multireference configuration interaction (DFT/MRCI) calculations for a set of 3d- and 4d-transition metal (TM) complexes. The DFT/MRCI results are compared to published reference data from reliable high-level multi-configurational ab initio studies. The assessment covers the relative energies of different ground-state minima of the highly correlated CrF{sub 6} complex, the singlet and triplet electronically excited states of seven typical TM complexes (MnO{sub 4}{sup −}, Cr(CO){sub 6}, [Fe(CN){sub 6}]{sup 4−}, four larger Fe and Ru complexes), and the corresponding electronic spectra (vertical excitation energies and oscillator strengths). It includes comparisons with results from different flavors of time-dependent DFT (TD-DFT) calculations using pure, hybrid, and long-range corrected functionals. The DFT/MRCI method is found to be superior to the tested TD-DFT approaches and is thus recommended for exploring the excited-state properties of TM complexes.

  17. Assessing the density functional theory-based multireference configuration interaction (DFT/MRCI) method for transition metal complexes.

    PubMed

    Escudero, Daniel; Thiel, Walter

    2014-05-21

    We report an assessment of the performance of density functional theory-based multireference configuration interaction (DFT/MRCI) calculations for a set of 3d- and 4d-transition metal (TM) complexes. The DFT/MRCI results are compared to published reference data from reliable high-level multi-configurational ab initio studies. The assessment covers the relative energies of different ground-state minima of the highly correlated CrF6 complex, the singlet and triplet electronically excited states of seven typical TM complexes (MnO4(-), Cr(CO)6, [Fe(CN)6](4-), four larger Fe and Ru complexes), and the corresponding electronic spectra (vertical excitation energies and oscillator strengths). It includes comparisons with results from different flavors of time-dependent DFT (TD-DFT) calculations using pure, hybrid, and long-range corrected functionals. The DFT/MRCI method is found to be superior to the tested TD-DFT approaches and is thus recommended for exploring the excited-state properties of TM complexes.

  18. Laser Driven Compression Equations of State and Hugoniot Pressure Measurements in Thick Solid Metallic Targets at ˜0.17-13 TW/cm2

    NASA Astrophysics Data System (ADS)

    Remo, John L.

    2010-10-01

    An electro-optic laser probe was developed to obtain parameters for high energy density equations of state (EoS), Hugoniot pressures (PH), and strain rates for high energy density laser irradiation intensity, I, experiments at ˜170 GW/cm2 (λ = 1064 nm) to ˜13 TW/cm2 (λ = 527 nm) on Al, Cu, Ti, Fe, Ni metal targets in a vacuum. At I ˜7 TW/cm2 front surface plasma pressures and temperatures reached 100's GPa and over two million K. Rear surface PH ranged from 7-120 GPa at average shock wave transit velocities 4.2-8.5 km/s, depending on target thickness and I. A surface plasma compression ˜100's GPa generated an impulsive radial expanding shock wave causing compression, rarefactions, and surface elastic and plastic deformations depending on I. A laser/fiber optic system measured rear surface shock wave emergence and particle velocity with ˜3 GHz resolution by monitoring light deflection from diamond polished rear surfaces of malleable metallic targets, analogous to an atomic force microscope. Target thickness, ˜0.5-2.9 mm, prevented front surface laser irradiation penetration, due to low radiation skin depth, from altering rear surface reflectivity (refractive index). At ˜10 TW electromagnetic plasma pulse noise generated from the target chamber overwhelmed detector signals. Pulse frequency analysis using Moebius loop antennae probed transient noise characteristics. Average shock (compression) and particle (rear surface displacement) velocity measurements determined rear surface PH and GPa) EoS that are compared with gas guns.

  19. High-k gadolinium scandate on Si obtained by high pressure sputtering from metal targets and in-situ plasma oxidation

    NASA Astrophysics Data System (ADS)

    Pampillón, M. A.; San Andrés, E.; Feijoo, P. C.; Fierro, J. L. G.

    2017-03-01

    This article studies the physical and electrical behavior of Gd2‑x Sc x O3 layers grown by high pressure sputtering from metallic Gd and Sc targets. The aim is to obtain a high permittivity dielectric for microelectronic applications. The films were obtained by the deposition of a metallic nanolaminate of Gd and Sc alternating layers, which is afterwards in-situ oxidized by plasma. The oxide films obtained were close to stoichiometry, amorphous and with minimal interfacial regrowth. By fabricating metal–insulator–semiconductor capacitors we found that a moderate temperature annealing is needed to enhance permittivity, which reaches a high value of 32 while keeping moderate leakage. Finally, the feasibility of interface scavenging in this material with Ti gate electrodes is also demonstrated.

  20. Hydrogen Abundances in Metal Grains from the Hammadah Al Hamra (HaH) 237 Metal-rich Chondrite: A Test of the Nebular-Formation Theory

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.; Guan, Y.; Leshin, L. A.

    2005-01-01

    The Bencubbin-like (CB) chondrites are metal-rich, primitive meteorites [1,2]. Some of these chondrites (HaH 237, QUE 94411) contain compositionally zoned metal grains with near-chondritic bulk compositions. Thermodynamic modeling of the zoning patterns in these grains suggests that they were formed by condensation in a region of the solar nebula with enhanced dust/gas ratios and a total pressure of 10(exp -4) bars at temperatures between 1400 - 1500 K [3]. If these predictions are correct than the metal grains would have been exposed to abundant H2 gas, which comprises the bulk of nebular systems. Since Fe-based alloys can absorb significant quantities of H, metal grains formed in the solar nebula should contain measurable abundances of H.

  1. Benchmark Calculations of Energetic Properties of Groups 4 and 6 Transition Metal Oxide Nanoclusters Including Comparison to Density Functional Theory.

    PubMed

    Fang, Zongtang; Both, Johan; Li, Shenggang; Yue, Shuwen; Aprà, Edoardo; Keçeli, Murat; Wagner, Albert F; Dixon, David A

    2016-08-09

    The heats of formation and the normalized clustering energies (NCEs) for the group 4 and group 6 transition metal oxide (TMO) trimers and tetramers have been calculated by the Feller-Peterson-Dixon (FPD) method. The heats of formation predicted by the FPD method do not differ much from those previously derived from the NCEs at the CCSD(T)/aT level except for the CrO3 nanoclusters. New and improved heats of formation for Cr3O9 and Cr4O12 were obtained using PW91 orbitals instead of Hartree-Fock (HF) orbitals. Diffuse functions are necessary to predict accurate heats of formation. The fluoride affinities (FAs) are calculated with the CCSD(T) method. The relative energies (REs) of different isomers, NCEs, electron affinities (EAs), and FAs of (MO2)n (M = Ti, Zr, Hf, n = 1-4) and (MO3)n (M = Cr, Mo, W, n = 1-3) clusters have been benchmarked with 55 exchange-correlation density functional theory (DFT) functionals including both pure and hybrid types. The absolute errors of the DFT results are mostly less than ±10 kcal/mol for the NCEs and the EAs and less than ±15 kcal/mol for the FAs. Hybrid functionals usually perform better than the pure functionals for the REs and NCEs. The performance of the two types of functionals in predicting EAs and FAs is comparable. The B1B95 and PBE1PBE functionals provide reliable energetic properties for most isomers. Long range corrected pure functionals usually give poor FAs. The standard deviation of the absolute error is always close to the mean errors, and the probability distributions of the DFT errors are often not Gaussian (normal). The breadth of the distribution of errors and the maximum probability are dependent on the energy property and the isomer.

  2. Evaluation of exchange-correlation functionals for time-dependent density functional theory calculations on metal complexes.

    PubMed

    Holland, Jason P; Green, Jennifer C

    2010-04-15

    The electronic absorption spectra of a range of copper and zinc complexes have been simulated by using time-dependent density functional theory (TD-DFT) calculations implemented in Gaussian03. In total, 41 exchange-correlation (XC) functionals including first-, second-, and third-generation (meta-generalized gradient approximation) DFT methods were compared in their ability to predict the experimental electronic absorption spectra. Both pure and hybrid DFT methods were tested and differences between restricted and unrestricted calculations were also investigated by comparison of analogous neutral zinc(II) and copper(II) complexes. TD-DFT calculated spectra were optimized with respect to the experimental electronic absorption spectra by use of a Matlab script. Direct comparison of the performance of each XC functional was achieved both qualitatively and quantitatively by comparison of optimized half-band widths, root-mean-squared errors (RMSE), energy scaling factors (epsilon(SF)), and overall quality-of-fit (Q(F)) parameters. Hybrid DFT methods were found to outperform all pure DFT functionals with B1LYP, B97-2, B97-1, X3LYP, and B98 functionals providing the highest quantitative and qualitative accuracy in both restricted and unrestricted systems. Of the functionals tested, B1LYP gave the most accurate results with both average RMSE and overall Q(F) < 3.5% and epsilon(SF) values close to unity (>0.990) for the copper complexes. The XC functional performance in spin-restricted TD-DFT calculations on the zinc complexes was found to be slightly worse. PBE1PBE, mPW1PW91 and B1LYP gave the most accurate results with typical RMSE and Q(F) values between 5.3 and 7.3%, and epsilon(SF) around 0.930. These studies illustrate the power of modern TD-DFT calculations for exploring excited state transitions of metal complexes.

  3. Size dependence of the melting temperature of metallic nanoclusters from the viewpoint of the thermodynamic theory of similarity

    NASA Astrophysics Data System (ADS)

    Samsonov, V. M.; Vasilyev, S. A.; Bembel, A. G.

    2016-08-01

    The generalized Thomson formula T m = T m (∞) (1-δ) R for the melting point of small objects T m has been analyzed from the viewpoint of the thermodynamic theory of similarity, where R is the radius of the particle and T m (∞) is the melting point of the corresponding large crystal. According to this formula, the parameter δ corresponds to the value of the radius of the T m ( R -1) particle obtained by the linear extrapolation of the dependence to the melting point of the particle equal to 0 K. It has been shown that δ = αδ0, where α is the factor of the asphericity of the particle (shape factor). In turn, the redefined characteristic length δ0 is expressed through the interphase tension σ sl at the boundary of the crystal with its own melt, the specific volume of the solid phase v s and the macroscopic value of the heat of fusion λ∞:δ0 = 2σ sl v s /λ∞. If we go from the reduced radius of the particle R/δ to the redefined reduced radius R/ r 1 or R/ d, where r 1 is the radius of the first coordination shell and d ≈ r 1 is the effective atomic diameter, then the simplex δ/ r 1 or δ/ d will play the role of the characteristic criterion of thermodynamic similarity. At a given value of α, this role will be played by the simplex Estimates of the parameters δ0 and δ0/ d have been carried out for ten metals with different lattice types. It has been shown that the values of the characteristic length δ0 are close to 1 nm and that the simplex δ0/ d is close to unity. In turn, the calculated values of the parameter δ agree on the order of magnitude with existing experimental data.

  4. Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory

    SciTech Connect

    Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan

    2015-11-09

    Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a power- ful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with con- ventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We con- sider seven low- and high-spin model complexes involving chromium, manganese and iron transition metal centers. Our results are in good agreement with experiment.

  5. Predictions of Optical Excitations in Transition-Metal Complexes with Time Dependent-Density Functional Theory:  Influence of Basis Sets.

    PubMed

    Petit, Laurence; Maldivi, Pascale; Adamo, Carlo

    2005-09-01

    The calculation of the absorption spectra of four families of transition-metal complexes (Ni(CO)4, MnO4(-), MF6 (M = Cr, Mo, W) and CpM(CO)2 (M = Rh, Ir)) has been undertaken to unravel the influence of basis sets onto excitation energies, oscillator strengths, and assignments. Three among the most common pseudopotentials, with the corresponding valence basis sets, and two all-electron basis sets have been used for the metal center description in the framework of the time dependent Density Functional Theory (TD-DFT). Our results show that this approach does not particularly depend on the basis set used on the metal atoms. Furthermore, the chosen functional PBE0 provides transitions in good agreement with experiments, and it provides an accuracy of about 0.3 eV, comparable to that of refined post-Hartree-Fock methods.

  6. Using queuing theory to analyse the government's 4-H completion time target in accident and emergency departments.

    PubMed

    Mayhew, L; Smith, D

    2008-03-01

    This paper uses a queuing model to evaluate completion times in Accident and Emergency (A&E) departments in the light of the Government target of completing and discharging 98% of patients inside 4 h. It illustrates how flows though an A&E can be accurately represented as a queuing process, how outputs can be used to visualise and interpret the 4-h Government target in a simple way and how the model can be used to assess the practical achievability of A&E targets in the future. The paper finds that A&E targets have resulted in significant improvements in completion times and thus deal with a major source of complaint by users of the National Health Service in the U.K. It suggests that whilst some of this improvement is attributable to better management, some is also due to the way some patients in A&E are designated and therefore counted through the system. It finds for example that the current target would not have been possible without some form of patient re-designation or re-labelling taking place. Further it finds that the current target is so demanding that the integrity of reported performance is open to question. Related incentives and demand management issues resulting from the target are also briefly discussed.

  7. INTERACTION OF LASER RADIATION WITH MATTER AND OTHER LASER APPLICATIONS: Changes in the emission properties of metal targets during pulse-periodic laser irradiation

    NASA Astrophysics Data System (ADS)

    Konov, Vitalii I.; Pimenov, S. M.; Prokhorov, A. M.; Chapliev, N. I.

    1988-02-01

    A scanning electron microscope was used with a pulse-periodic CO2 laser to discover the laws governing the correlation of the modified microrelief of metal surfaces, subjected to the action of multiple laser pulses, with the emission of charged particles and the luminescence of the irradiated zone. It was established that the influence of sorption and laser-induced desorption on the emission signals may be manifested differently depending on the regime of current generation in the "target-vacuum chamber" circuit.

  8. Time-domain Response of a Metal Detector to a Target Buried in Soil with Frequency-dependent Magnetic Susceptibility

    DTIC Science & Technology

    2016-07-06

    The work reported in this paper is a part of on-going studies to clarify how and to what extent soil electromagnetic properties affect the...performance of induction metal detectors widely used in humanitarian demining. This paper studies the specific case of the time-domain response of a small

  9. Au25 cluster functionalized metal-organic nanostructures for magnetically targeted photodynamic/photothermal therapy triggered by single wavelength 808 nm near-infrared light

    NASA Astrophysics Data System (ADS)

    Yang, Dan; Yang, Guixin; Gai, Shili; He, Fei; An, Guanghui; Dai, Yunlu; Lv, Ruichan; Yang, Piaoping

    2015-11-01

    Near-infrared (NIR) light-induced cancer therapy has gained considerable interest, but pure inorganic anti-cancer platforms usually suffer from degradation issues. Here, we designed metal-organic frameworks (MOFs) of Fe3O4/ZIF-8-Au25 (IZA) nanospheres through a green and economic procedure. The encapsulated Fe3O4 nanocrystals not only produce hyperthemal effects upon NIR light irradiation to effectively kill tumor cells, but also present targeting and MRI imaging capability. More importantly, the attached ultrasmall Au25(SR)18- clusters (about 2.5 nm) produce highly reactive singlet oxygen (1O2) to cause photodynamic effects through direct sensitization under NIR light irradiation. Furthermore, the Au25(SR)18- clusters also give a hand to the hyperthemal effect as photothermal fortifiers. This nanoplatform exhibits high biocompatibility and an enhanced synergistic therapeutic effect superior to any single therapy, as verified by in vitro and in vivo assay. This image-guided therapy based on a metal-organic framework may stimulate interest in developing other kinds of metal-organic materials with multifunctionality for tumor diagnosis and therapy.Near-infrared (NIR) light-induced cancer therapy has gained considerable interest, but pure inorganic anti-cancer platforms usually suffer from degradation issues. Here, we designed metal-organic frameworks (MOFs) of Fe3O4/ZIF-8-Au25 (IZA) nanospheres through a green and economic procedure. The encapsulated Fe3O4 nanocrystals not only produce hyperthemal effects upon NIR light irradiation to effectively kill tumor cells, but also present targeting and MRI imaging capability. More importantly, the attached ultrasmall Au25(SR)18- clusters (about 2.5 nm) produce highly reactive singlet oxygen (1O2) to cause photodynamic effects through direct sensitization under NIR light irradiation. Furthermore, the Au25(SR)18- clusters also give a hand to the hyperthemal effect as photothermal fortifiers. This nanoplatform exhibits high

  10. Corrosion mechanisms for metal alloy waste forms: experiment and theory Level 4 Milestone M4FT-14LA0804024 Fuel Cycle Research & Development

    SciTech Connect

    Liu, Xiang-Yang; Taylor, Christopher D.; Kim, Eunja; Goff, George Scott; Kolman, David Gary

    2014-07-31

    This document meets Level 4 Milestone: Corrosion mechanisms for metal alloy waste forms - experiment and theory. A multiphysics model is introduces that will provide the framework for the quantitative prediction of corrosion rates of metallic waste forms incorporating the fission product Tc. The model requires a knowledge of the properties of not only the metallic waste form, but also the passive oxide films that will be generated on the waste form, and the chemistry of the metal/oxide and oxide/environment interfaces. in collaboration with experimental work, the focus of this work is on obtaining these properties from fundamental atomistic models. herein we describe the overall multiphysics model, which is based on MacDonald's point-defect model for passivity. We then present the results of detailed electronic-structure calculations for the determination of the compatibility and properties of Tc when incorporated into intermetallic oxide phases. This work is relevant to the formation of multi-component oxides on metal surfaces that will incorporate Tc, and provide a kinetic barrier to corrosion (i.e. the release of Tc to the environment). Atomistic models that build upon the electronic structure calculations are then described using the modified embedded atom method to simulate metallic dissolution, and Buckingham potentials to perform classical molecular dynamics and statics simulations of the technetium (and, later, iron-technetium) oxide phases. Electrochemical methods were then applied to provide some benchmark information of the corrosion and electrochemical properties of Technetium metal. The results indicate that published information on Tc passivity is not complete and that further investigation is warranted.

  11. Target Practice: Reader Response Theory and Teachers' Interpretations of Students' SAT 10 Scores in Data-Based Professional Development

    ERIC Educational Resources Information Center

    Atkinson, Becky M.

    2012-01-01

    The study reported in this article examines how teachers read and respond to their students' Stanford Achievement Test 10 (SAT 10) scores with the goal of investigating the assumption that data-based teaching practice is more "objective" and less susceptible to divergent teacher interpretation. The study uses reader response theory to…

  12. Polarized internal target apparatus

    DOEpatents

    Holt, R.J.

    1984-10-10

    A polarized internal target apparatus with a polarized gas target of improved polarization and density (achieved by mixing target gas atoms with a small amount of alkali metal gas atoms, and passing a high intensity polarized light source into the mixture to cause the alkali metal gas atoms to become polarized which interact in spin exchange collisions with target gas atoms yielding polarized target gas atoms) is described.

  13. Polarized internal target apparatus

    DOEpatents

    Holt, Roy J.

    1986-01-01

    A polarized internal target apparatus with a polarized gas target of improved polarization and density achieved by mixing target gas atoms with a small amount of alkali metal gas atoms, and passing a high intensity polarized light source into the mixture to cause the alkali metal gas atoms to become polarized which interact in spin exchange collisions with target gas atoms yielding polarized target gas atoms.

  14. The free-radical theory of ageing--older, wiser and still alive: modelling positional effects of the primary targets of ROS reveals new support.

    PubMed

    Kirkwood, Thomas B L; Kowald, Axel

    2012-08-01

    The continuing viability of the free-radical theory of ageing has been questioned following apparently incompatible recent results. We show by modelling positional effects of the generation and primary targets of reactive oxygen species that many of the apparently negative results are likely to be misleading. We conclude that there is instead a need to look more closely at the mechanisms by which free radicals contribute to age-related dysfunction in living systems. There also needs to be deeper understanding of the dynamics of accumulation and removal of the various kinds of molecular damage, in particular mtDNA mutations. Finally, the expectation that free-radical damage on its own might cause ageing needs to be relinquished in favour of the recognition that the free-radical theory is just one of the multiple mechanisms driving the ageing process.

  15. Acoustic-wave generation in the process of CO2-TEA-laser-radiation interaction with metal targets in air

    NASA Astrophysics Data System (ADS)

    Apostol, Ileana; Teodorescu, G.; Serbanescu-Oasa, Anca; Dragulinescu, Dumitru; Chis, Ioan; Stoian, Razvan

    1995-03-01

    Laser radiation interaction with materials is a complex process in which creation of acoustic waves or stress waves is a part of it. As a function of the laser radiation energy and intensity incident on steel target surface ultrasound signals were registered and studied. Thermoelastic, ablation and breakdown mechanisms of generation of acoustic waves were analyzed.

  16. Optimizing EMI transmitter and receiver configurations to enhance detection and identification of small and deep metallic targets

    NASA Astrophysics Data System (ADS)

    Fernández, Juan Pablo; Barrowes, Benjamin; Bijamov, Alex; O'Neill, Kevin; Shamatava, Irma; Steinhurst, Daniel A.; Shubitidze, Fridon

    2012-06-01

    Current electromagnetic induction (EMI) sensors of the kind used to discriminate buried unexploded orndance (UXO) can detect targets down to a depth limited by the geometric size of the transmitter (Tx) coils, the amplitudes of the transmitting currents, and the noise floor of the receivers (Rx). The last two factors are not independent: for example, one cannot detect a deeply buried target simply by increasing the amplitude of the Tx current, since this also increases the noise and thus does not improve the SNR. The problem could in principle be overcome by increasing the size of the Tx coils and thus their moment. Current multi-transmitter instruments such as the TEMTADS sensor array can be electronically tweaked to provide a big Tx moment: they can be modified to transmit signals from two, three or more Tx coils simultaneously. We investigate the possibility of enhancing the deep-target detection capability of TEMTADS by exploring different combinations of Tx coils. We model different multi-Tx combinations within TEMTADS using a full-3D EMI solver based on the method of auxiliary sources (MAS).We determine the feasibility of honing these combinations for enhanced detection and discrimination of deep targets. We investigate how to improve the spatial resolution and focusing properties of the primary magnetic field by electronically adjusting the currents of the transmitters. We apply our findings to data taken at different UXO live sites.

  17. Dr. J. R. Huynen's main contributions in the development of polarimetric radar techniques and how the 'Radar Targets Phenomenological Concept' becomes a theory

    NASA Astrophysics Data System (ADS)

    Pottier, Eric

    1993-02-01

    Among the engineering scientists who have most decisively contributed toward forefront advances for the 'Development of POLARIMETRIC Radar Theory, Techniques and Target Phenomenology', Dr. Jean Richard HUYNEN stands out as one of the towering giants. This paper is dedicated to him, and it is a great honor for the author to present here a summary on some of the main Dr. J.R. HUYNEN's contributions in the development of Polarimetric Radar Techniques, including the 'Mueller Matrix Decomposition' approaches which this Senior Radar Polarimetrist considers as his 'life's main contribution'.

  18. Influence of alkali metal superoxides on structure, electronic, and optical properties of Be12O12 nanocage: Density functional theory study

    NASA Astrophysics Data System (ADS)

    Raoof Toosi, Ali; Shamlouei, Hamid Reza; Hesari, Asghar Mohammadi

    2016-09-01

    The effect of alkali metal superoxides M3O (M = Li, Na, K) on the electronic and optical properties of a Be12O12 nanocage was studied by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The energy gaps (Eg) of all configurations were calculated. Generally, the adsorption of alkali metal superoxides on the Be12O12 nanocage causes a decrease of Eg. Electric dipole moment μ, polarizability α, and static first hyperpolarizability β were calculated and it was shown that the adsorption of alkali metal superoxides on Be12O12 increases its polarizability. It was found that the absorption of M3O on Be12O12 nanocluster improves its nonlinear optical properties. The highest first hyperpolarizability (β ≈ 214000 a.u.) is obtained in the K3O-Be12O12 nanocluster. The TD-DFT calculations were performed to investigate the origin of the first hyperpolarizabilities and it was shown that a higher first hyperpolarizability belongs to the structure that has a lower transition energy.

  19. Quantifying Human Performance of a Dynamic Military Target Detection Task: An Application of the Theory of Signal Detection.

    DTIC Science & Technology

    1995-06-01

    applied to analyze numerous experimental tasks (Macmillan and Creelman , 1991). One of these tasks, target detection, is the subject research. In...between each associated pair of false alarm rate and hit rate z-scores is d’ for the bias level associated with the pairing (Macmillan and Creelman , 1991...unequal variance in normal distributions (Macmillan and Creelman , 1991). 61 1966). It is described in detail for the interested reader by Green and

  20. Gel versus aerogel to collect high velocity ejectas from laser shock-loaded metallic targets for postrecovery analyses

    NASA Astrophysics Data System (ADS)

    Lescoute, Emilien; De Rességuier, Thibaut; Chevalier, Jean-Marc

    2012-03-01

    Soft recovery of fast objects is an issue of considerable interest for many applications involving shock wave loading, such as ballistics, armor design, or more recently laser-driven inertial confinement fusion, where the characterization of the debris ejected from metallic shells subjected to intense laser irradiation conditions the design of the experiments. In this work, we compare the high velocity ejecta recovery efficiency of two materials: silica aerogel (density 0.03 g/cm3), which has been used as fragment collector for many years, and "varagel" (density 0.9 g/cm3), which we have tested recently in laser shock experiments. Ejected fragments have been recovered in both types of collectors. Then, samples have been analyzed by X-ray tomography at the European Synchrotron Radiation Facility (ESRF). Three-dimensional reconstructions of the fragments populations have been achieved, and quantitative comparisons between both collecting materials, used in the same conditions, have been performed.

  1. Some evidence for the base-metal potential of the Pretoria Group: stratigraphic targets, tectonic setting and REE patterns

    NASA Astrophysics Data System (ADS)

    Reczko, B. F. F.; Eriksson, P. G.; Snyman, C. P.

    1995-04-01

    The Timeball Hill and Silverton Formations of the 2.1 2.3 Ga Pretoria Group have regional lithological associations which are thought to have been favourable for the genesis of stratiform sulphide deposits. The observed association of carboniferous and pyritic black shales, tuffaceous material, stromatolitic carbonates and inferred turbidity current deposits is common in stratiform sulphide deposits of the sedimentary exhalative group. Massive sulphides in the Silverton Formation are compatible with a syngenetic brine discharge, probably related to deep fracture systems. The basal shales of the Timeball Hill Formation are significantly enriched in base-metals and Ba. Interlayered tuff beds at this stratigraphic level have PGE-contents of up to 1 g/t. The REE-geochemistry of Pretoria Group sedimentary rocks supports hydrothermal activity as an important factor in both stratigraphic units.

  2. Ionothermal synthesis and structural transformation targeted by ion exchange in metal-1,3,5-benzenetricarboxylate compounds

    NASA Astrophysics Data System (ADS)

    Xu, Qing-Qing; Liu, Bing; Xu, Ling; Jiao, Huan

    2017-03-01

    Ionothermal reactions of 1,3,5-benzenetricarboxylate acid (H3BTC) and Ni(NO3)2, Co(NO3)2 and Cu(NO3)2 gave two discrete 32-membered ring-like allomers, [M2(HBTC)2(NH2CONH2)2(H2O)4]·3H2O (M=Ni(1), Co(2)) and one layered [Cu2(BTC)Cl(H2O)4] (3). The weak interactions in 1 can be deconstructed to some degree in ion exchange by exploring the factors of divalent and trivalent metal species, metal concentration and soaking time, which are demonstrated by PXRD and N2 absorption. Cu2+ has the highest N2 adsorbance when soaking with 1, and 1 can keep structure stable when Cu2+ below 0.16 mol L-1 and the soaking time within 24d. As Cu2+ beyond 0.16 mol L-1 and the soaking time beyond 24d, the structure of compound 1 starts to transform with the crystal morphology from clear pale green to opaque blue. Ionothermal reactions of compound 1 with different Cu2+ amounts obtained Ni2+-Cu2+ hetero complexes, whose PXRD patterns are similar to that of 3 and EDS indicates Cu2+% increases with Cu2+ additions and close to 100% as Cu2+ being 1.6 mmol. It suggests that 3 is a controlled product and Cu2+ can transform discrete compound 1 into 2D compound 3.

  3. Preserving the half-metallicity at the Heusler alloy Co2MnSi(001) surface: a density functional theory study.

    PubMed

    Hashemifar, S Javad; Kratzer, Peter; Scheffler, Matthias

    2005-03-11

    We have studied the stability, the electronic, and the magnetic properties of Co2MnSi(001) thin films for 15 different terminations using density functional theory calculations. The phase diagram obtained by ab initio atomistic thermodynamics shows that in practice the MnSi, pure Mn, or pure Si terminated surfaces can be stabilized under suitable conditions. Analyzing the surface band structure, we find that the pure Mn termination, due to its strong surface-subsurface coupling, preserves the half-metallicity of the system, while surface states appear for the other terminations.

  4. Theory of laser acceleration of light-ion beams from interaction of ultrahigh-intensity lasers with layered targets.

    PubMed

    Albright, B J; Yin, L; Hegelich, B M; Bowers, Kevin J; Kwan, T J T; Fernández, J C

    2006-09-15

    Experiments at the LANL Trident facility demonstrated the production of monoenergetic ion beams from the interaction of an ultraintense laser with a target comprising a heavy ion substrate and thin layer of light ions. An analytic model is obtained that predicts how the mean energy and quality of monoenergetic ion beams and the energy of substrate ions vary with substrate material and light-ion layer composition and thickness. Dimensionless parameters controlling the dynamics are derived and the model is validated with particle-in-cell simulations and experimental data.

  5. Folate-targeted pH-responsive calcium zoledronate nanoscale metal-organic frameworks: Turning a bone antiresorptive agent into an anticancer therapeutic.

    PubMed

    Au, Kin Man; Satterlee, Andrew; Min, Yuanzeng; Tian, Xi; Kim, Young Seok; Caster, Joseph M; Zhang, Longzhen; Zhang, Tian; Huang, Leaf; Wang, Andrew Z

    2016-03-01

    Zoledronate (Zol) is a third-generation bisphosphonate that is widely used as an anti-resorptive agent for the treatment of cancer bone metastasis. While there is preclinical data indicating that bisphosphonates such as Zol have direct cytotoxic effects on cancer cells, such effect has not been firmly established in the clinical setting. This is likely due to the rapid absorption of bisphosphonates by the skeleton after intravenous (i.v.) administration. Herein, we report the reformulation of Zol using nanotechnology and evaluation of this novel nanoscale metal-organic frameworks (nMOFs) formulation of Zol as an anticancer agent. The nMOF formulation is comprised of a calcium zoledronate (CaZol) core and a polyethylene glycol (PEG) surface. To preferentially deliver CaZol nMOFs to tumors as well as facilitate cellular uptake of Zol, we incorporated folate (Fol)-targeted ligands on the nMOFs. The folate receptor (FR) is known to be overexpressed in several tumor types, including head-and-neck, prostate, and non-small cell lung cancers. We demonstrated that these targeted CaZol nMOFs possess excellent chemical and colloidal stability in physiological conditions. The release of encapsulated Zol from the nMOFs occurs in the mid-endosomes during nMOF endocytosis. In vitro toxicity studies demonstrated that Fol-targeted CaZol nMOFs are more efficient than small molecule Zol in inhibiting cell proliferation and inducing apoptosis in FR-overexpressing H460 non-small cell lung and PC3 prostate cancer cells. Our findings were further validated in vivo using mouse xenograft models of H460 and PC3. We demonstrated that Fol-targeted CaZol nMOFs are effective anticancer agents and increase the direct antitumor activity of Zol by 80-85% in vivo through inhibition of tumor neovasculature, and inhibiting cell proliferation and inducing apoptosis.

  6. Effects of Application of Social Marketing Theory and the Health Belief Model in Promoting Cervical Cancer Screening among Targeted Women in Sisaket Province, Thailand.

    PubMed

    Wichachai, Suparp; Songserm, Nopparat; Akakul, Theerawut; Kuasiri, Chanapong

    2016-01-01

    Cervical cancer is a major public health problem in Thailand, being ranked second only to breast cancer. Thai women have been reported to have a low rate of cervical cancer screening (27.7% of the 80% goal of WHO). We therefore aimed to apply the social marketing theory and health belief model in promoting cervical cancer screening in Kanthararom District, Sisaket Province. A total of 92 from 974 targeted women aged 3060 years were randomly divided into two groups. The experimental group underwent application of social marketing theory and a health belief model program promoting cervical cancer screening while the control group received normal services. Two research tools were used: (1) application of social marketing theory and health belief model program and (2) questionnaire used to evaluate perceptions of cervical cancer. Descriptive and inferential statistics including paired sample ttest and independent ttest were used to analyze the data. After the program had been used, the mean score of perception of cervical cancer of experimental group was at a higher level (x=4.09; S.D. =0.30), than in the control group (x=3.82; S.D. =0.20) with statistical significance (p<0.001). This research demonstrated an appropriate communication process in behavioral modification to prevent cervical cancer. It can be recommended that this program featuring social marketing and the health belief model be used to promote cervical cancer screening in targeted women and it can be promoted as a guideline for other health services, especially in health promotion and disease prevention.

  7. Predicting Multicomponent Adsorption Isotherms in Open-Metal Site Materials Using Force Field Calculations Based on Energy Decomposed Density Functional Theory.

    PubMed

    Heinen, Jurn; Burtch, Nicholas C; Walton, Krista S; Fonseca Guerra, Célia; Dubbeldam, David

    2016-12-12

    For the design of adsorptive-separation units, knowledge is required of the multicomponent adsorption behavior. Ideal adsorbed solution theory (IAST) breaks down for olefin adsorption in open-metal site (OMS) materials due to non-ideal donor-acceptor interactions. Using a density-function-theory-based energy decomposition scheme, we develop a physically justifiable classical force field that incorporates the missing orbital interactions using an appropriate functional form. Our first-principles derived force field shows greatly improved quantitative agreement with the inflection points, initial uptake, saturation capacity, and enthalpies of adsorption obtained from our in-house adsorption experiments. While IAST fails to make accurate predictions, our improved force field model is able to correctly predict the multicomponent behavior. Our approach is also transferable to other OMS structures, allowing the accurate study of their separation performances for olefins/paraffins and further mixtures involving complex donor-acceptor interactions.

  8. The influence of laser ablation plume at different laser incidence angle on the impulse coupling coefficient with metal target

    NASA Astrophysics Data System (ADS)

    Zhao, Xiong-Tao; Tang, Feng; Han, Bing; Ni, Xiao-Wu

    2016-12-01

    A calibrated pendulum measuring device and a dimensionless analysis method were used to measure the impulse coupling coefficient at different laser intensities with aluminum, steel, and iron targets. The experiment was performed with a pulsed laser with the wavelength of 1.06 μm and the pulse duration of 7 ns. The experimental measurements of the variation of the impulse coupling coefficient versus the laser energy density agree with the theoretical prediction, and the optimum laser energy density correlated with the maximum impulse coupling coefficient corresponding to the theoretical predictions. The impulse coupling coefficients with laser incidence angles of 0 ° and 45 ° are compared for understanding of the effects of the ablation plume on the impulse coupling effect, and the experimental result shows that the impulse coupling effect grows as the incidence angle changes from 0 ° to 45 ° . Furthermore, the transmittance of the incident laser through the ablation plume in front of the target is deduced from the impulse measurements, and the effect of the ablation plume on the impulse coupling at high laser intensity is discussed. In order to investigate the weak impulse coupling effect, which is difficult to obtain from the experiments, the impulse coupling coefficient at low laser energy density was calculated by the finite element simulation.

  9. The Effects of Sensor Performance as Modeled by Signal Detection Theory on the Performance of Reinforcement Learning in a Target Acquisition Task

    NASA Astrophysics Data System (ADS)

    Quirion, Nate

    Unmanned Aerial Systems (UASs) today are fulfilling more roles than ever before. There is a general push to have these systems feature more advanced autonomous capabilities in the near future. To achieve autonomous behavior requires some unique approaches to control and decision making. More advanced versions of these approaches are able to adapt their own behavior and examine their past experiences to increase their future mission performance. To achieve adaptive behavior and decision making capabilities this study used Reinforcement Learning algorithms. In this research the effects of sensor performance, as modeled through Signal Detection Theory (SDT), on the ability of RL algorithms to accomplish a target localization task are examined. Three levels of sensor sensitivity are simulated and compared to the results of the same system using a perfect sensor. To accomplish the target localization task, a hierarchical architecture used two distinct agents. A simulated human operator is assumed to be a perfect decision maker, and is used in the system feedback. An evaluation of the system is performed using multiple metrics, including episodic reward curves and the time taken to locate all targets. Statistical analyses are employed to detect significant differences in the comparison of steady-state behavior of different systems.

  10. Potential human health risks from toxic metals, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides via canned fish consumption: estimation of target hazard quotients.

    PubMed

    El Morsy, Fadia A M; El-Sadaawy, Manal M; Ahdy, Hoda H H; Abdel-Fattah, Laila M; El-Sikaily, Amany M; Khaled, Azza; Tayel, Fathi M T

    2013-01-01

    Canned fish (tuna and sardine) of different geographical regions were collected randomly from supermarkets and were analyzed for heavy metal contents (Hg, Cd and Pb) polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and pesticides. Canned fish samples (two brands of sardines, six brands of tuna) that were purchased from Egyptian cities between 2009 and 2010, represent four countries (Morocco, Republic of Yemen, Indonesia and Thailand). Health risks on humans via dietary intake of seafood were assessed by the target hazard quotients (THQs), potential non-carcinogenic and carcinogenic effects. The contents of trace metals in canned tuna and canned sardines were found as: 0.149-0.218 μg/g for Cd; 0.312-0.937 μg/g for Pb and 0.053-0.022 μg/g for Hg. Canned sardines fluctuated between 0.55 and 1.82, 1.08 and 1.64, 11.91 and 26.24 ng/g for total HCHs, Total cyclodienes and DDTs respectively while the corresponding concentrations in canned tuna were 0.24-1.85, 0.24-1‥85 and 6.56-49.73 ng/g, respectively. Total PCBs fluctuated between 21.75 and 55.10 for canned sardines and 8.56-208.11 ng/g for canned tuna. On the other hand the total PAHs fluctuated between 0.006-9.775 and 1.556-2.686 ng/g for tuna and sardines. From the human health point of view, there is no adverse health effect for both PAHs and heavy metals content on consumers.

  11. Chelation Motifs Affecting Metal-dependent Viral Enzymes: N′-acylhydrazone Ligands as Dual Target Inhibitors of HIV-1 Integrase and Reverse Transcriptase Ribonuclease H Domain

    PubMed Central

    Carcelli, Mauro; Rogolino, Dominga; Gatti, Anna; Pala, Nicolino; Corona, Angela; Caredda, Alessia; Tramontano, Enzo; Pannecouque, Christophe; Naesens, Lieve; Esposito, Francesca

    2017-01-01

    Human immunodeficiency virus type 1 (HIV-1) infection, still represent a serious global health emergency. The chronic toxicity derived from the current anti-retroviral therapy limits the prolonged use of several antiretroviral agents, continuously requiring the discovery of new antiviral agents with innovative strategies of action. In particular, the development of single molecules targeting two proteins (dual inhibitors) is one of the current main goals in drug discovery. In this contest, metal-chelating molecules have been extensively explored as potential inhibitors of viral metal-dependent enzymes, resulting in some important classes of antiviral agents. Inhibition of HIV Integrase (IN) is, in this sense, paradigmatic. HIV-1 IN and Reverse Transcriptase-associated Ribonuclease H (RNase H) active sites show structural homologies, with the presence of two Mg(II) cofactors, hence it seems possible to inhibit both enzymes by means of chelating ligands with analogous structural features. Here we present a series of N′-acylhydrazone ligands with groups able to chelate the Mg(II) hard Lewis acid ions in the active sites of both the enzymes, resulting in dual inhibitors with micromolar and even nanomolar activities. The most interesting identified N′-acylhydrazone analog, compound 18, shows dual RNase H-IN inhibition and it is also able to inhibit viral replication in cell-based antiviral assays in the low micromolar range. Computational modeling studies were also conducted to explore the binding attitudes of some model ligands within the active site of both the enzymes. PMID:28373864

  12. Using the theory of planned behaviour and prototype willingness model to target binge drinking in female undergraduate university students.

    PubMed

    Todd, Jemma; Mullan, Barbara

    2011-10-01

    The current study investigated whether binge drinking in female undergraduates could be reduced by the mere measurement effect (MME), and by altering binge drinker prototypes from the prototype willingness model (PWM). Whether willingness added to the theory of planned behaviour (TPB) was also explored. Female undergraduates aged 17-25 (N=122) were randomly allocated to a prototype manipulation, mere measurement, or control group, and completed two online questionnaires separated by 14-21 days. Controlling for past behaviour, MME group consumed less alcohol than the control group, and this effect was more extreme for those who previously consumed more alcohol. However, the prototype manipulation had no effect. The TPB variables were predictive of intentions and behaviour, but willingness was not. Despite limitations, the MME could be utilised to reduce binge drinking in female undergraduates. The TPB appears to model binge drinking in female undergraduates better than the PWM, implying that binge drinking can be a reasoned behaviour.

  13. Self-consistent many-electron theory of electron work functions and surface potential characteristics for selected metals

    NASA Technical Reports Server (NTRS)

    Smith, J. R.

    1969-01-01

    Electron work functions, surface potentials, and electron number density distributions and electric fields in the surface region of 26 metals were calculated from first principles within the free electron model. Calculation proceeded from an expression of the total energy as a functional of the electron number density, including exchange and correlation energies, as well as a first inhomogeneity term. The self-consistent solution was obtained via a variational procedure. Surface barriers were due principally to many-body effects; dipole barriers were small only for some alkali metals, becoming quite large for the transition metals. Surface energies were inadequately described by this model, which neglects atomistic effects. Reasonable results were obtained for electron work functions and surface potential characteristics, maximum electron densities varying by a factor of over 60.

  14. LIQUID TARGET

    DOEpatents

    Martin, M.D.; Salsig, W.W. Jr.

    1959-01-13

    A liquid handling apparatus is presented for a liquid material which is to be irradiated. The apparatus consists essentially of a reservoir for the liquid, a target element, a drain tank and a drain lock chamber. The target is in the form of a looped tube, the upper end of which is adapted to be disposed in a beam of atomic particles. The lower end of the target tube is in communication with the liquid in the reservoir and a means is provided to continuously circulate the liquid material to be irradiated through the target tube. Means to heat the reservoir tank is provided in the event that a metal is to be used as the target material. The apparatus is provided with suitable valves and shielding to provide maximum safety in operation.

  15. Supersymmetric correspondence in spectra on a graph and its line graph: From circuit theory to spoof plasmons on metallic lattices

    NASA Astrophysics Data System (ADS)

    Nakata, Yosuke; Urade, Yoshiro; Nakanishi, Toshihiro; Miyamaru, Fumiaki; Takeda, Mitsuo Wada; Kitano, Masao

    2016-04-01

    We investigate the supersymmetry (SUSY) structures for inductor-capacitor circuit networks on a simple regular graph and its line graph. We show that their eigenspectra must coincide (except, possibly, for the highest eigenfrequency) due to SUSY, which is derived from the topological nature of the circuits. To observe this spectra correspondence in the high-frequency range, we study spoof plasmons on metallic hexagonal and kagomé lattices. The band correspondence between them is predicted by a simulation. Using terahertz time-domain spectroscopy, we demonstrate the band correspondence of fabricated metallic hexagonal and kagomé lattices.

  16. The homeostatic set point of the hypothalamus-pituitary-thyroid axis – maximum curvature theory for personalized euthyroid targets

    PubMed Central

    2014-01-01

    Background Despite rendering serum free thyroxine (FT4) and thyrotropin (TSH) within the normal population ranges broadly defined as euthyroidism, many patients being treated for hyperthyroidism and hypothyroidism persistently experience subnormal well-being discordant from their pre-disease healthy euthyroid state. This suggests that intra-individual physiological optimal ranges are narrower than laboratory-quoted normal ranges and implies the existence of a homeostatic set point encoded in the hypothalamic-pituitary-thyroid (HPT) axis that is unique to every individual. Methods We have previously shown that the dose–response characteristic of the hypothalamic-pituitary (HP) unit to circulating thyroid hormone levels follows a negative exponential curve. This led to the discovery that the normal reference intervals of TSH and FT4 fall within the ‘knee’ region of this curve where the maximum curvature of the exponential HP characteristic occurs. Based on this observation, we develop the theoretical framework localizing the position of euthyroid homeostasis over the point of maximum curvature of the HP characteristic. Results The euthyroid set points of patients with primary hypothyroidism and hyperthyroidism can be readily derived from their calculated HP curve parameters using the parsimonious mathematical model above. It can be shown that every individual has a euthyroid set point that is unique and often different from other individuals. Conclusions In this treatise, we provide evidence supporting a set point-based approach in tailoring euthyroid targets. Rendering FT4 and TSH within the laboratory normal ranges can be clinically suboptimal if these hormone levels are distant from the individualized euthyroid homeostatic set point. This mathematical technique permits the euthyroid set point to be realistically computed using an algorithm readily implementable for computer-aided calculations to facilitate precise targeted dosing of patients in this modern

  17. [Colorimetric study of color reproduction in porcelain-fused-to-metal restoration. The application of Kubelka-Munk theory in porcelain mixtures].

    PubMed

    Ishikawa, S; Miyoshi, F; Ishibashi, K

    1990-06-01

    To get a more natural and harmonious color of porcelain-fused-to-metal restorations, an objective and precise systematic method from shade selection to color evaluation is needed. Thus, the absorption and scattering coefficients were determined to develop a CCM system for porcelain-fused-to-metal restorations. The Kubelka-Munk Theory was applied on the dental porcelain, opaque, dentin, and enamel. From these data, we predicted the color of the porcelain mixtures from the both coefficients. From the results of comparing the spectral curves and analyzing the color differences between measured values and predicted values of porcelain mixtures, the following was analysed; 1. In opaque, spectral curves of the predicted and measured values were exactly alike and the mean dE between two values was 0.39. 2. In dentin, the spectral curved of the predicted and measured values were exactly alike, and the mean dE was 1.13. The measured values indicated a slight increase in the level of chroma and lightness. 3. In enamel, the spectral curves were exactly alike and the mean dE was 1.16. The measured values indicated a slight decrease in the level of lightness. Therefore, it was possible to predict the color of opaque, dentin and enamel porcelain mixtures, by applying the Kubelka-Munk Theory.

  18. Classical scattering theory of waves from the view point of an eigenvalue problem and application to target identification

    SciTech Connect

    Bottcher, C.; Strayer, M.R.; Werby, M.F.

    1993-10-01

    The Helmholtz-Poincare Wave Equation (H-PWE) arises in many areas of classical wave scattering theory. In particular it can be found for the cases of acoustical scattering from submerged bounded objects and electromagnetic scattering from objects. The extended boundary integral equations (EBIE) method is derived from considering both the exterior and interior solutions of the H-PWE`s. This coupled set of expressions has the advantage of not only offering a prescription for obtaining a solution for the exterior scattering problem, but it also obviates the problem of irregular values corresponding to fictitious interior eigenvalues. Once the coupled equations are derived, they can by obtained in matrix form be expanding all relevant terms in partial wave expansions, including a biorthogonal expansion of the Green function. However some freedom of choice in the choice of the surface expansion is available since the unknown surface quantities may be expanded in a variety of ways to long as closure is obtained. Out of many possible choices, we develop an optimal method to obtain such expansions which is based on the optimum eigenfunctions related to the surface of the object. In effect, we convert part of the problem (that associated with the Fredholms integral equation of the first kind) an eigenvalue problem of a related Hermition operator. The methodology will be explained in detail and examples will be presented.

  19. A bifunctional poly(ethylene glycol) silane immobilized on metallic oxide-based nanoparticles for conjugation with cell targeting agents

    SciTech Connect

    Kohler, Nathan J.; Fryxell, Glen E.; Zhang, Miqin

    2004-06-16

    A trifluoroethylester-terminal poly (ethylene glycol) (PEG) silane was synthesized and self-assembled on iron oxide nanoparticles. The nanoparticle system thus prepared has the flexibility to conjugate with cell targeting agents having either carboxylic and amine terminal groups for a number of biomedical applications, including magnetic resonance imaging (MRI) and controlled drug delivery. The trifluoroethylester silane was synthesized by modifying a PEG diacid to form the corresponding bistrifluoroethylester (TFEE), followed by a reaction with 3-aminopropyltriethoxysilane (APS). The APS coupled with PEG chains confers the stability of PEG self-assembled monolayers (SAMs) and increases the PEG packing density on nanoparticles by establishing hydrogen bonding between the carbonyl and amine groups present within the monolayer structure. The success of the synthesis of the PEG TEFE silane was confirmed with 1H NMR and Fourier transform infrared spectroscopy (FTIR). The conjugating flexibility of the PEG TEFE was demonstrated with folic acid having carboxylic acid groups and amine terminal groups respectively and confirmed by FTIR. TEM analysis showed the dispersion of nanoparticles before and after they were coated with PEG and folic acid.

  20. The use of methods involving semi-empirical molecular orbital theory to study the structure and reactivity of transition metal complexes.

    PubMed

    Mohr, Matthias; McNamara, Jonathan P; Wang, Hong; Rajeev, Surendran A; Ge, Jun; Morgado, Claudio A; Hillier, Ian H

    2003-01-01

    The electronic structure of molecular systems containing transition metal atoms is traditionally studied using methods based on density functional theory (DFT). Although such an approach has been quite successful, the treatment of large systems, be they transition metal complexes, bioinorganic molecules or the solid state, is still extremely computationally demanding at this level, and may not be practical for many systems of interest. In this paper we describe how semi-empirical MO methods can be used to overcome these computational bottlenecks, yet still provide predictions of the necessary accuracy. We describe strategies to achieve this by focussing on: (i) obtaining appropriate parameters for transition metal atoms via a genetic algorithm, to be used within a parallelised implementation of neglect of differential diatomic overlap (NDDO) methods, and (ii) the use of multilevel treatments which involve DFT and semi-empirical methods to describe different regions of the molecule. Here we show by reference to histidine and porphyrin complexes, the importance of a correct partitioning of the organic substrate. We illustrate the potential of such a dual level approach by reporting preliminary results showing the catalytic role of the enzyme, dimethyl sulfoxide reductase.

  1. Mathematical models of radiation action on living cells: From the target theory to the modern approaches. A historical and critical review.

    PubMed

    Bodgi, Larry; Canet, Aurélien; Pujo-Menjouet, Laurent; Lesne, Annick; Victor, Jean-Marc; Foray, Nicolas

    2016-04-07

    Cell survival is conventionally defined as the capability of irradiated cells to produce colonies. It is quantified by the clonogenic assays that consist in determining the number of colonies resulting from a known number of irradiated cells. Several mathematical models were proposed to describe the survival curves, notably from the target theory. The Linear-Quadratic (LQ) model, which is to date the most frequently used model in radiobiology and radiotherapy, dominates all the other models by its robustness and simplicity. Its usefulness is particularly important because the ratio of the values of the adjustable parameters, α and β, on which it is based, predicts the occurrence of post-irradiation tissue reactions. However, the biological interpretation of these parameters is still unknown. Throughout this review, we revisit and discuss historically, mathematically and biologically, the different models of the radiation action by providing clues for resolving the enigma of the LQ model.

  2. The role of repair in the survival of mammalian cells from heavy ion irradiation - Approximation to the ideal case of target theory

    NASA Technical Reports Server (NTRS)

    Lett, J. T.; Cox, A. B.; Story, M. D.

    1989-01-01

    Experiments are discussed in which the cell-cycle dependency of the repair deficiency of the S/S variant of the L5178Y murine leukemic lymphoblast was examined by treatment with the heavy ions, Ne-20, Si-28, Ar-40, Fe-56, and Nb-93. Evidence from those studies provide support for the notion that as the linear energy transfer of the incident radiation increases the ability of the S/S cell to repair radiation damage decreases until it is eliminated around 500 keV/micron. In the region of the latter linear energy transfer value, the behavior of the S/S cell approximates the ideal case of target theory where post-irradiation metabolism does not influence cell survival.

  3. Density functional theory analysis of the interplay between Jahn-Teller instability, uniaxial magnetism, spin arrangement, metal-metal interaction, and spin-orbit coupling in Ca3CoMO6 (M = Co, Rh, Ir).

    PubMed

    Zhang, Yuemei; Kan, Erjun; Xiang, Hongjun; Villesuzanne, Antoine; Whangbo, Myung-Hwan

    2011-03-07

    In the isostructural oxides Ca(3)CoMO(6) (M = Co, Rh, Ir), the CoMO(6) chains made up of face-sharing CoO(6) trigonal prisms and MO(6) octahedra are separated by Ca atoms. We analyzed the magnetic and electronic properties of these oxides on the basis of density functional theory calculations including on-site repulsion and spin-orbit coupling, and examined the essential one-electron pictures hidden behind results of these calculations. Our analysis reveals an intimate interplay between Jahn-Teller instability, uniaxial magnetism, spin arrangement, metal-metal interaction, and spin-orbit coupling in governing the magnetic and electronic properties of these oxides. These oxides undergo a Jahn-Teller distortion, but their distortions are weak, so that their trigonal-prism Co(n+) (n = 2, 3) ions still give rise to strong easy-axis anisotropy along the chain direction. As for the d-state split pattern of these ions, the electronic and magnetic properties of Ca(3)CoMO(6) (M = Co, Rh, Ir) are consistent with d(0) < (d(2), d(-2)) < (d(1), d(-1)) but not with (d(2), d(-2)) < d(0) < (d(1), d(-1)). The trigonal-prism Co(3+) ion in Ca(3)Co(2)O(6) has the L = 2 configuration (d(0))(1)(d(2), d(-2))(3)(d(1), d(-1))(2) because of the metal-metal interaction between adjacent Co(3+) ions in each Co(2)O(6) chain, which is mediated by their z(2) orbitals, and the spin-orbit coupling of the trigonal-prism Co(3+) ion. The spins in each CoMO(6) chain of Ca(3)CoMO(6) prefer the ferromagnetic arrangement for M = Co and Rh but the antiferromagnetic arrangement for M = Ir. The octahedral M(4+) ion of Ca(3)CoMO(6) has the (1a)(1)(1e)(4) configuration for M = Rh but the (1a)(2)(1e)(3) configuration for M = Ir, which arises from the difference in the spin-orbit coupling of the M(4+) ions and the Co···M metal-metal interactions.

  4. Theory of bimolecular reactions in a solution with linear traps: Application to the problem of target search on DNA

    NASA Astrophysics Data System (ADS)

    Turkin, Alexander; van Oijen, Antoine M.; Turkin, Anatoliy A.

    2015-11-01

    One-dimensional sliding along DNA as a means to accelerate protein target search is a well-known phenomenon occurring in various biological systems. Using a biomimetic approach, we have recently demonstrated the practical use of DNA-sliding peptides to speed up bimolecular reactions more than an order of magnitude by allowing the reactants to associate not only in the solution by three-dimensional (3D) diffusion, but also on DNA via one-dimensional (1D) diffusion [A. Turkin et al., Chem. Sci. (2015), 10.1039/C5SC03063C]. Here we present a mean-field kinetic model of a bimolecular reaction in a solution with linear extended sinks (e.g., DNA) that can intermittently trap molecules present in a solution. The model consists of chemical rate equations for mean concentrations of reacting species. Our model demonstrates that addition of linear traps to the solution can significantly accelerate reactant association. We show that at optimum concentrations of linear traps the 1D reaction pathway dominates in the kinetics of the bimolecular reaction; i.e., these 1D traps function as an assembly line of the reaction product. Moreover, we show that the association reaction on linear sinks between trapped reactants exhibits a nonclassical third-order behavior. Predictions of the model agree well with our experimental observations. Our model provides a general description of bimolecular reactions that are controlled by a combined 3D+1D mechanism and can be used to quantitatively describe both naturally occurring as well as biomimetic biochemical systems that reduce the dimensionality of search.

  5. Binding selectivity of dibenzo-18-crown-6 for alkali metal cations in aqueous solution: A density functional theory study using a continuum solvation model

    PubMed Central

    2012-01-01

    Background Dibenzo-18-crown-6 (DB18C6) exhibits the binding selectivity for alkali metal cations in solution phase. In this study, we investigate the main forces that determine the binding selectivity of DB18C6 for the metal cations in aqueous solution using the density functional theory (DFT) and the conductor-like polarizable continuum model (CPCM). Results The bond dissociation free energies (BDFE) of DB18C6 complexes with alkali metal cations (M+-DB18C6, M = Li, Na, K, Rb, and Cs) in aqueous solution are calculated at the B3LYP/6-311++G(d,p)//B3LYP/6-31 + G(d) level using the CPCM. It is found that the theoretical BDFE is the largest for K+-DB18C6 and decreases as the size of the metal cation gets larger or smaller than that of K+, which agrees well with previous experimental results. Conclusion The solvation energy of M+-DB18C6 in aqueous solution plays a key role in determining the binding selectivity of DB18C6. In particular, the non-electrostatic dispersion interaction between the solute and solvent, which depends strongly on the complex structure, is largely responsible for the different solvation energies of M+-DB18C6. This study shows that the implicit solvation model like the CPCM works reasonably well in predicting the binding selectivity of DB18C6 in aqueous solution. PMID:22873431

  6. Role of sequence in salt-bridge formation for alkali metal cationized GlyArg and ArgGly investigated with IRMPD spectroscopy and theory.

    PubMed

    Prell, James S; Demireva, Maria; Oomens, Jos; Williams, Evan R

    2009-01-28

    The roles of hydrogen bonding, electrostatic interactions, sequence, gas-phase basicity, and molecular geometry in determining the structures of protonated and alkali metal-cationized glycyl-L-arginine (GlyArg) and L-arginylglycine (ArgGly) were investigated using infrared multiple photon dissociation spectroscopy in the spectral range 900-1800 cm(-1) and theory. The IRMPD spectra clearly indicate that GlyArg x M(+), M = Li, Na, and Cs, form similar salt-bridge (SB) structures that do not depend significantly on metal ion size. In striking contrast, ArgGly x Li(+) exists in a charge-solvated (CS) form, whereas ArgGly x M(+), M = K and Cs, form SB structures. SB and CS structures are similarly populated for ArgGly x Na(+). Computed energies of low-energy structures are consistent with these results deduced from the experimental spectra. By comparison to Arg x M(+), GlyArg x M(+) and ArgGly x M(+) have a greater and lesser propensity, respectively, to form SB structures. The greater propensity for GlyArg to adopt SB structures in complexes with smaller metal cations than for ArgGly is due to the ability of alkali metal-cationized GlyArg to adopt a nearly linear arrangement of formal charge sites, a structure unfavorable for ArgGly complexes due to geometric constraints induced by its different amino acid sequence. The amide carbonyl oxygen solvates charge in both the SB and CS form of both dipeptides. ArgGly is calculated to be slightly more basic than GlyArg, indicating that differences in intrinsic basicity do not play a role in the relative SB stabilization of these ions. Loss of a neutral water molecule from complexes in which SB structures are most stable indicates that CS structures are intermediates in the dissociation pathway, but these intermediates do not contribute to the measured IRMPD spectra.

  7. Partition of actinides and fission products between metal and molten salt phases: Theory, measurement, and application to IFR pyroprocess development

    SciTech Connect

    Ackerman, J.P.; Johnson, T.R.

    1993-10-01

    The chemical basis of Integral Fast Reactor fuel reprocessing (pyroprocessing) is partition of fuel, cladding, and fission product elements between molten LiCl-KCl and either a solid metal phase or a liquid cadmium phase. The partition reactions are described herein, and the thermodynamic basis for predicting distributions of actinides and fission products in the pyroprocess is discussed. The critical role of metal-phase activity coefficients, especially those of rare earth and the transuranic elements, is described. Measured separation factors, which are analogous to equilibrium constants but which involve concentrations rather than activities, are presented. The uses of thermodynamic calculations in process development are described, as are computer codes developed for calculating material flows and phase compositions in pyroprocessing.

  8. Electric field gradients of transition metal complexes from density functional theory: assessment of functionals, geometries and basis sets.

    PubMed

    Bjornsson, Ragnar; Bühl, Michael

    2010-06-14

    Electric field gradients (EFGs) were computed for the first-row transition metal nuclei in Cr(C(6)H(6))(CO)(3), MnO(3)F, Mn(CO)(5)H, MnCp(CO)(3), Co(CO)(4)H, Co(CO)(3)(NO) and VCp(CO)(4), for which experimental gas-phase data (in form of nuclear quadrupole coupling constants) are available from microwave spectroscopy. A variety of exchange-correlation functionals were assessed, among which range-separated hybrids (such as CAM-B3LYP or LC-omegaPBE) perform best, followed by global hybrids (such as B3LYP and PBE0) and gradient-corrected functionals (such as BP86). While large basis sets are required on the metal atom for converged EFGs, smaller basis sets can be employed on the ligands. In most cases, EFGs show little sensitivity toward the geometrical parameters.

  9. Theory of the magnetic and metal-insulator transitions in RNiO3 bulk and layered structures.

    PubMed

    Lau, Bayo; Millis, Andrew J

    2013-03-22

    A slave rotor--Hartree-Fock formalism is presented for studying the properties of the p-d model describing perovskite transition metal oxides, and a flexible and efficient numerical formalism is developed for its solution. The methodology is shown to yield, within a unified formulation, the significant aspects of the rare-earth nickelate phase diagram, including the paramagnetic metal state observed for the LaNiO3 and the correct ground-state magnetic order of insulating compounds. It is then used to elucidate ground state changes occurring as morphology is varied from bulk to strained and unstrained thin-film form. For ultrathin films, epitaxial strain and charge transfer to the apical out-of-plane oxygen sites are shown to have significant impact on the phase diagram.

  10. Theory of the Magnetic and Metal-Insulator Transitions in RNiO3 Bulk and Layered Structures

    NASA Astrophysics Data System (ADS)

    Lau, Bayo; Millis, Andrew J.

    2013-03-01

    A slave rotor—Hartree-Fock formalism is presented for studying the properties of the p-d model describing perovskite transition metal oxides, and a flexible and efficient numerical formalism is developed for its solution. The methodology is shown to yield, within a unified formulation, the significant aspects of the rare-earth nickelate phase diagram, including the paramagnetic metal state observed for the LaNiO3 and the correct ground-state magnetic order of insulating compounds. It is then used to elucidate ground state changes occurring as morphology is varied from bulk to strained and unstrained thin-film form. For ultrathin films, epitaxial strain and charge transfer to the apical out-of-plane oxygen sites are shown to have significant impact on the phase diagram.

  11. Theory of the magnetic and metal-insulator transitions in RNiO3 bulk and layered

    NASA Astrophysics Data System (ADS)

    Lau, Bayo; Millis, Andrew J.

    2013-03-01

    A slave rotor-Hartree Fock formalism is presented for studying the properties of the p-d model describing perovskite transition metal oxides, and a flexible and efficient numerical formalism is developed for its solution. The methodology is shown to yield, within an unified formulation, the significant aspects of the rare earth nickelate phase diagram, including the paramagnetic metal state observed for the LaNiO3 and the correct ground-state magnetic order of insulating compounds. It is then used to elucidate ground state changes occurring as morphology is varied from bulk to strained and un-strained thin-film form. For ultrathin films, epitaxial strain and charge-transfer to the apical out-of-plane oxygen sites are shown to have significant impact on the phase diagram. This effort is supported by US National Science Foundation under grant NSF-DMR-1006282

  12. Fermi surfaces, spin-mixing parameter, and colossal anisotropy of spin relaxation in transition metals from ab initio theory

    NASA Astrophysics Data System (ADS)

    Zimmermann, Bernd; Mavropoulos, Phivos; Long, Nguyen H.; Gerhorst, Christian-Roman; Blügel, Stefan; Mokrousov, Yuriy

    2016-04-01

    The Fermi surfaces and Elliott-Yafet spin-mixing parameter (EYP) of several elemental metals are studied by ab initio calculations. We focus first on the anisotropy of the EYP as a function of the direction of the spin-quantization axis [B. Zimmermann et al., Phys. Rev. Lett. 109, 236603 (2012), 10.1103/PhysRevLett.109.236603]. We analyze in detail the origin of the gigantic anisotropy in 5 d hcp metals as compared to 5 d cubic metals by band structure calculations and discuss the stability of our results against an applied magnetic field. We further present calculations of light (4 d and 3 d ) hcp crystals, where we find a huge increase of the EYP anisotropy, reaching colossal values as large as 6000 % in hcp Ti. We attribute these findings to the reduced strength of spin-orbit coupling, which promotes the anisotropic spin-flip hot loops at the Fermi surface. In order to conduct these investigations, we developed an adapted tetrahedron-based method for the precise calculation of Fermi surfaces of complicated shape and accurate Fermi-surface integrals within the full-potential relativistic Korringa-Kohn-Rostoker Green function method.

  13. A Comparison of Density Functional Theory with Ab initio Approaches for Systems Involving First Transition Row Metals

    NASA Technical Reports Server (NTRS)

    Ricca, Alessandra; Bauschlicher, Charles W.; Langhoff, Stephen R. (Technical Monitor)

    1994-01-01

    Density functional theory (DFT) is found to give a better description of the geometries and vibrational frequencies of FeL and FeL(sup +) systems than second order Moller Plesset perturbation theory (MP2). Namely, the DFT correctly predicts the shift in the CO vibrational frequency between free CO and the Sigma(sup -) state of FeCO and yields a good result for the Fe-C distance in the quartet states of FeCH4(+) 4 These are properties where the MP2 results are unsatisfactory. Thus DFT appears to be an excellent approach for optimizing the geometries and computing the zero-point energies of systems containing first transition row atoms. Because the DFT approach is biased in favor of the 3d(exp 7) occupation, whereas the more traditional approaches are biased in favor of the 3d(exp 6) occupation, differences are found in the relative ordering of states. It is shown that if the dissociation is computed to the most appropriate atomic asymptote and corrected to the ground state asymptote using the experimental separations, the DFT results are in good agreement with high levels of theory. The energetics at the DFT level are much superior to the MP2 and in most cases in good agreement with high levels of theory.

  14. Autism genes are selectively targeted by environmental pollutants including pesticides, heavy metals, bisphenol A, phthalates and many others in food, cosmetics or household products.

    PubMed

    Carter, C J; Blizard, R A

    2016-10-27

    The increasing incidence of autism suggests a major environmental influence. Epidemiology has implicated many candidates and genetics many susceptibility genes. Gene/environment interactions in autism were analysed using 206 autism susceptibility genes (ASG's) from the Autworks database to interrogate ∼1 million chemical/gene interactions in the comparative toxicogenomics database. Any bias towards ASG's was statistically determined for each chemical. Many suspect compounds identified in epidemiology, including tetrachlorodibenzodioxin, pesticides, particulate matter, benzo(a)pyrene, heavy metals, valproate, acetaminophen, SSRI's, cocaine, bisphenol A, phthalates, polyhalogenated biphenyls, flame retardants, diesel constituents, terbutaline and oxytocin, inter alia showed a significant degree of bias towards ASG's, as did relevant endogenous agents (retinoids, sex steroids, thyroxine, melatonin, folate, dopamine, serotonin). Numerous other suspected endocrine disruptors (over 100) selectively targeted ASG's including paraquat, atrazine and other pesticides not yet studied in autism and many compounds used in food, cosmetics or household products, including tretinoin, soy phytoestrogens, aspartame, titanium dioxide and sodium fluoride. Autism polymorphisms influence the sensitivity to some of these chemicals and these same genes play an important role in barrier function and control of respiratory cilia sweeping particulate matter from the airways. Pesticides, heavy metals and pollutants also disrupt barrier and/or ciliary function, which is regulated by sex steroids and by bitter/sweet taste receptors. Further epidemiological studies and neurodevelopmental and behavioural research is warranted to determine the relevance of large number of suspect candidates whose addition to the environment, household, food and cosmetics might be fuelling the autism epidemic in a gene-dependent manner.

  15. Correlated Band Structure of a Transition Metal Oxide ZnO Obtained from a Many-Body Wave Function Theory

    NASA Astrophysics Data System (ADS)

    Ochi, Masayuki; Arita, Ryotaro; Tsuneyuki, Shinji

    2017-01-01

    Obtaining accurate band structures of correlated solids has been one of the most important and challenging problems in first-principles electronic structure calculation. There have been promising recent active developments of wave function theory for condensed matter, but its application to band-structure calculation remains computationally expensive. In this Letter, we report the first application of the biorthogonal transcorrelated (BITC) method: self-consistent, free from adjustable parameters, and systematically improvable many-body wave function theory, to solid-state calculations with d electrons: wurtzite ZnO. We find that the BITC band structure better reproduces the experimental values of the gaps between the bands with different characters than several other conventional methods. This study paves the way for reliable first-principles calculations of the properties of strongly correlated materials.

  16. Optimization of the manufacturing process of a titanium aluminide metal matrix composite using a viscoplastic constitutive theory

    SciTech Connect

    Sherwood, J.A.; Quimby, H.M.

    1996-04-01

    The thermomechanical behavior of a titanium aluminide metal matrix composite reinforced with silicon carbide fibers is computationally investigated to determine an optimum manufacturing process. The investigations are completed using the Ramaswamy-Stouffer constitutive model and the finite element method. Hold times at a given temperature were used in an effort to allow the residual stresses to relax. However, the subsequent temperature changes erased the benefit of such holds. Thermomechanical cycling was determined to be the optimum method for reducing the residual stress field after cooldown from consolidation.

  17. Spin and orbital magnetism of coinage metal trimers (Cu{sub 3}, Ag{sub 3}, Au{sub 3}): A relativistic density functional theory study

    SciTech Connect

    Afshar, Mahdi; Sargolzaei, Mohsen

    2013-11-15

    We have demonstrated electronic structure and magnetic properties of Cu{sub 3}, Ag{sub 3} and Au{sub 3} trimers using a full potential local orbital method in the framework of relativistic density functional theory. We have also shown that the non-relativistic generalized gradient approximation for the exchange-correlation energy functional gives reliable magnetic properties in coinage metal trimers compared to experiment. In addition we have indicated that the spin-orbit coupling changes the structure and magnetic properties of gold trimer while the structure and magnetic properties of copper and silver trimers are marginally affected. A significant orbital moment of 0.21μ{sub B} was found for most stable geometry of the gold trimer whereas orbital magnetism is almost quenched in the copper and silver trimers.

  18. Radar Cross-Sectional Spectra of Rotating Multiple Skew-Plated Metal Fan Blades by Physical Optics/Physical Theory of Diffraction, Equivalent Currents Approximation

    NASA Astrophysics Data System (ADS)

    Bor, Sheau-Shong; Yang, Tai-Lin; Yang, Shui-Yuan

    1992-05-01

    The monostatic radar cross-sectional spectra of rotating multiple skew-plated metal fan blades are investigated. The theoretical treatment of such a slowly rotating and electrically large scatterer is based on the quasi-stationary method together with physical optics/physical theory of diffraction (PO/PTD) equivalent current techniques. Only the θθ polarization case is considered here, but the \\psi\\psi polarization case can be treated in the same way. This solution is applicable to any observation angle, and is represented by such a general form as one which enables us to treat a similar scatterer with multiple blades and with different skew angles. Three rotating skew-plated blades are taken as an example, and the agreements between the theoretical and experimental results are satisfactory.

  19. Dynamical Mean-Field Theory Plus Numerical Renormalization-Group Study of Spin-Orbital Separation in a Three-Band Hund Metal.

    PubMed

    Stadler, K M; Yin, Z P; von Delft, J; Kotliar, G; Weichselbaum, A

    2015-09-25

    We show that the numerical renormalization group is a viable multi-band impurity solver for dynamical mean-field theory (DMFT), offering unprecedented real-frequency spectral resolution at arbitrarily low energies and temperatures. We use it to obtain a numerically exact DMFT solution to the Hund metal problem for a three-band model on a Bethe lattice at 1/3 filling. The ground state is a Fermi liquid. The one-particle spectral function undergoes a coherence-incoherence crossover with increasing temperature, with spectral weight being transferred from low to high energies. Further, it exhibits a strong particle-hole asymmetry. In the incoherent regime, the self-energy displays approximate power-law behavior for positive frequencies only. The spin and orbital spectral functions show "spin-orbital separation": spin screening occurs at much lower energies than orbital screening. The renormalization group flows clearly reveal the relevant physics at all energy scales.

  20. Dynamical Mean-Field Theory Plus Numerical Renormalization-Group Study of Spin-Orbital Separation in a Three-Band Hund Metal

    NASA Astrophysics Data System (ADS)

    Stadler, K. M.; Yin, Z. P.; von Delft, J.; Kotliar, G.; Weichselbaum, A.

    2015-09-01

    We show that the numerical renormalization group is a viable multi-band impurity solver for dynamical mean-field theory (DMFT), offering unprecedented real-frequency spectral resolution at arbitrarily low energies and temperatures. We use it to obtain a numerically exact DMFT solution to the Hund metal problem for a three-band model on a Bethe lattice at 1 /3 filling. The ground state is a Fermi liquid. The one-particle spectral function undergoes a coherence-incoherence crossover with increasing temperature, with spectral weight being transferred from low to high energies. Further, it exhibits a strong particle-hole asymmetry. In the incoherent regime, the self-energy displays approximate power-law behavior for positive frequencies only. The spin and orbital spectral functions show "spin-orbital separation": spin screening occurs at much lower energies than orbital screening. The renormalization group flows clearly reveal the relevant physics at all energy scales.

  1. Density functional theory study of interaction, bonding and affinity of group IIb transition metal cations with nucleic acid bases

    NASA Astrophysics Data System (ADS)

    Bagchi, Sabyasachi; Mandal, Debasish; Ghosh, Deepanwita; Das, Abhijit K.

    2012-05-01

    The structure, bonding, and energetics of the complexes obtained from the interaction between the most stable tautomeric forms of free DNA and RNA bases and Zn2+, Cd2+ and Hg2+ cations have been studied using density functional B3LYP method. The 6-311+G (2df, 2p) basis set along with LANL2DZ pseudopotentials for the cations are used in the calculations. The tautomerization paths of the nucleobases are investigated and transition states between the tautomeric forms of the free bases are located. The relative stability of the complexes and the tautomers of the free nucleobases are discussed referring to MIA and relative energy values. For uracil, thymine and adenine, interaction of the metal cations with the most stable tautomers form the least stable molecular complexes. For cytosine and guanine, the stability of the metalated complexes differs significantly. The enthalpy (ΔH), entropy (TΔS) and free energy (ΔG) of the complexes at 298 K have also been calculated.

  2. Theory of the metal-insulator transition in Pr Ru4 P12 and Pr Fe4 P12

    NASA Astrophysics Data System (ADS)

    Curnoe, S. H.; Harima, H.; Takegahara, K.; Ueda, K.

    2004-12-01

    All symmetry-allowed couplings between the 4f2 -electron ground state doublet of trivalent praseodymium in PrRu4P12 and PrFe4P12 and displacements of the phosphorus, iron, or ruthenium ions are considered. Two types of displacements can change the crystal lattice from body-centred cubic to simple orthorhombic or to simple cubic. The first type lowers the point group symmetry from tetrahedral to orthorhombic, while the second type leaves it unchanged, with corresponding space group reductions Im3¯→Pmmm and Im3¯→Pm3¯ , respectively. In former case, the lower point group symmetry splits the degeneracy of the 4f2 doublet into states with opposite quadrupole moment, which then leads to antiquadrupolar ordering, as in PrFe4P12 . Either kind of displacement may conspire with nesting of the Fermi surface to cause the metal-insulator or partial metal-insulator transition observed in PrFe4P12 and PrRu4P12 . We investigate this scenario using band-structure calculations, and it is found that displacements of the phosphorus ions in PrRu4P12 (with space-group reduction Im3¯→Pm3¯ ) open a gap everywhere on the Fermi surface.

  3. Affinity selection of histidine-containing peptides using metal chelate methacrylate monolithic disk for targeted LC-MS/MS approach in high-throughput proteomics.

    PubMed

    Prasanna, Rajasekar R; Sidhik, Sinash; Kamalanathan, Agamudi S; Bhagavatula, Krishna; Vijayalakshmi, Mookambeswaran A

    2014-04-01

    In recent years, bottom-up approach has become the popular method of choice for large scale analysis of complex proteome samples. Peptide fractionation determines the efficiency of the bottom-up method and often the resolving power of reverse phase liquid chromatography (RPLC) is insufficient for efficient protein identification in case of complex biological samples. To overcome the inherent limitation of proteomics associated with sample complexity, we evaluated fast flow metal chelate methacrylate monolithic system - CIM (Convective Interaction Media) disk chelated with Cu(II) for targeted affinity selection of histidine-containing peptides. Initially the Cu(II)-IMAC using CIM disk was evaluated using tryptic digest of protein mixtures of 8 model proteins and was found to be highly efficient in capturing His-containing peptides with high degree of specificity and selectivity. Further the efficiency of His-peptide enrichment using CIM-IMAC was also demonstrated using complex biological samples like total Escherichia coli cell lysate. The analysis of the Cu(II)-IMAC retained peptides from tryptic digests of model protein mixture and E. coli not only demonstrated a significant reduction in sample complexity but also subsequently enabled the identification of additional peptides. His-peptide enrichment also enabled the identification of low abundant proteins that were not detected in the analysis of total E. coli digest.

  4. Modelling the metal atom positions of the Photosystem II water oxidising complex: a density functional theory appraisal of the 1.9 Å resolution crystal structure.

    PubMed

    Petrie, Simon; Gatt, Phillip; Stranger, Rob; Pace, Ron J

    2012-08-28

    Density functional theory (DFT) calculations are reported for a set of model compounds intended to represent the structure of the Photosystem II (PSII) water oxidising complex (WOC) as determined by the recent 1.9 Å resolution single crystal X-ray diffraction (XRD) study of Umena et al. In contrast with several other theoretical studies addressing this structure, we find that it is not necessary to invoke photoreduction of the crystalline sample below the S(1)'resting state' in order to rationalise the observed WOC geometry. Our results are consistent with crystallised PSII in the S(1) state, with S(1) corresponding to either (Mn(III))(4) or (Mn(III))(2)(Mn(IV))(2) as required by the two competing paradigms for the WOC oxidation state pattern. Of these two paradigms, the 'low-oxidation-state' paradigm provides a better match for the crystal structure, with the comparatively long Mn(2)-Mn(3) distance in particular proving difficult to reconcile with the 'high-oxidation-state' model. Best agreement with the set of metal-metal distances is obtained with a S(1) model featuring μ-O, μ-OH bridging between Mn(3) and Mn(4) and deprotonation of one water ligand on Mn(4). Theoretical modelling of the 1.9 Å structure is an important step in assessing the validity of this recent crystal structure, with implications for our understanding of the mechanism of water oxidation by PSII.

  5. Structures and spectroscopic properties of nonperipherally and peripherally substituted metal-free phthalocyanines: a substitution effect study based on density functional theory calculations.

    PubMed

    Zhong, Aimin; Zhang, Yuexing; Bian, Yongzhong

    2010-11-01

    The molecular structures, molecular orbitals, atomic charges, electronic absorption spectra, and infrared (IR) and Raman spectra of a series of substituted metal-free phthalocyanine compounds with four (1, 3, 5, 7) or eight (2, 4, 6, 8) methoxyl (1, 2, 5, 6) or methylthio groups (3, 4, 7, 8) on the nonperipheral (1-4) or peripheral positions (5-8) of the phthalocyanine ring are studied by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The calculated structural parameters and simulated electronic absorption and IR spectra are compared with the X-ray crystallography structures and the experimentally observed electronic absorption and IR spectra of the similar molecules, and good agreement between the calculated and experimental results is found. The substitution of the methoxyl or methylthio groups at the nonperipheral positions of the phthalocyanine ring has obvious effects on the molecular structure and spectroscopic properties of the metal-free phthalocyanine. Nonperipheral substitution has a more significant influence than peripheral substitution. The substitution effect increases with an increase in the number of substituents. The methylthio group shows more significant influence than the methoxyl group, despite the stronger electron-donating property of the methoxyl group than the methylthio group. The octa-methylthio-substituted metal-free phthalocyanine compounds have nonplanar structures whose low-lying occupied molecular orbitals and electronic absorption spectra are significantly changed by the substituents. The present systematical study will be helpful for understanding the relationship between structures and properties in phthalocyanine compounds and designing phthalocyanines with typical properties.

  6. Interaction of H 2 with simple metal surfaces: a model based on the anisotropic effective medium theory

    NASA Astrophysics Data System (ADS)

    Karimi, M.; Ila, D.; Dalins, I.; Vidali, G.

    1990-12-01

    Calculations are presented for the interaction of H 2 with surfaces of Cu, Ag, Au and Al. The repulsive part of the potential is evaluated using the results of anisotropic effective medium theory (AEMT) while the attractive part is calculated from anisotropic damped dipole-dipole and damped dipole-quadrupole interactions. The model does not have any fitting parameters and its predictions are in excellent agreement with the available experimental data. The anisotropy of H 2 is included in the model but our results show that this effect is very small.

  7. Interaction of H2 with simple metal surfaces - A model based on the anisotropic effective medium theory

    NASA Technical Reports Server (NTRS)

    Karimi, M.; Ila, D.; Dalins, I.; Vidali, G.

    1990-01-01

    Calculations are presented for the interaction of H2 with surfaces of Cu, Ag, Au and Al. The repulsive part of the potential is evaluated using the results of anisotropic effective medium theory (AEMT) while the attractive part is calculated from anisotropic damped dipole-dipole and damped dipole-quadrupole interactions. The model does not have any fitting parameters and its predictions are in excellent agreement with the available experimental data. The anisotropy of H2 is included in the model but our results show that this effect is very small.

  8. Towards an ab initio theory for metal L-edge soft X-ray spectroscopy of molecular aggregates

    PubMed Central

    Preuße, Marie; Bokarev, Sergey I.; Aziz, Saadullah G.; Kühn, Oliver

    2016-01-01

    The Frenkel exciton model was adapted to describe X-ray absorption and resonant inelastic scattering spectra of polynuclear transition metal complexes by means of the restricted active space self-consistent field method. The proposed approach allows to substantially decrease the requirements on computational resources if compared to a full supermolecular quantum chemical treatment. This holds true, in particular, in cases where the dipole approximation to the electronic transition charge density can be applied. The computational protocol was applied to the calculation of X-ray spectra of the hemin complex, which forms dimers in aqueous solution. The aggregation effects were found to be comparable to the spectral alterations due to the replacement of the axial ligand by solvent molecules. PMID:27679809

  9. Compressibility and hardness of Co-based bulk metallic glass: A combined experimental and density functional theory study

    SciTech Connect

    Wang Jianfeng; Li Ran; Xu Tao; Li Yan; Liu Zengqian; Huang Lu; Hua Nengbin; Zhang Tao; Xiao Ruijuan; Li Gong; Li Yanchun

    2011-10-10

    An incompressible Co{sub 54}Ta{sub 11}B{sub 35} bulk metallic glass (BMG) was investigated using in situ high-pressure synchrotron diffraction and nanoindendation. The elastic constants were deduced from the experiments based on the isotropic model. The Vickers hardness was measured to be 17.1 GPa. The elastic moduli and hardness are the highest values known in BMGs. The theoretically calculated elastic properties by density-functional study were well consistent with experimental measurements. The analysis of charge density and bonding character indicates the covalent character of Co-B and B-B bonds, underlying the unusually high elastic modulus and hardness in this material.

  10. Natural Orbitals in Relation to Quantum Information Theory: from Model Light Atoms Through to Emergent Metallic Properties

    NASA Astrophysics Data System (ADS)

    March, N. H.; Angilella, G. G. N.; Pucci, R.

    2013-10-01

    The review begins with a consideration of three forms of quantum information entropy associated with Shannon and Jaynes. For model two-electron spin compensated systems, some analytic progress is first reported. The Jaynes entropy is clearly related to correlation kinetic energy. A way of testing the usefulness of a known uncertainty principle inequality is proposed for a whole class of model two-electron atoms with harmonic confinement but variable electron-electron interaction. Emerging properties are then studied by reference to bcc Na at ambient pressure and its modeling by "jellium". Jellium itself has collective behavior with changes of the density, especially noteworthy being the discontinuity of the momentum distribution at the Fermi surface. This has almost reduced to zero at rs = 100 a.u., the neighborhood in which the quantal Wigner electron solid transition is known to occur. However, various workers have studied crystalline Na under pressure and their results are compared and contrasted. Work by DFT on K, Rb and Cs is discussed, but now with reduced density from the ambient pressure value. The crystalline results for the cohesive energy of these metals as a function of lattice parameters and local coordination number are shown to be closely reproduced by means of ground and excited states for dimer potential energy curves. Then, pair potentials for liquid Na and Be are reviewed, and compared with the results of computer simulations from the experimental structure factor for Na. Finally, magnetic field effects are discussed. First a phenomenological model of the metal-to-insulator transition is presented with an order parameter which is the discontinuity in the Fermi momentum distribution. Lastly, experiments on a two-dimensional electron assembly in a GaAs/AlGaAs heterojunction in a perpendicular magnetic field are briefly reviewed and then interpreted.

  11. Bio-inspired transition metal-organic hydride conjugates for catalysis of transfer hydrogenation: experiment and theory.

    PubMed

    McSkimming, Alex; Chan, Bun; Bhadbhade, Mohan M; Ball, Graham E; Colbran, Stephen B

    2015-02-09

    Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI(+) ) organic hydride-acceptor domain has been coupled with a 1,10-phenanthroline (phen) metal-binding domain to afford a novel multifunctional ligand (L(BI+) ) with hydride-carrier capacity (L(BI+) +H(-) ⇌L(BI) H). Complexes of the type [Cp*M(L(BI) )Cl][PF6 ]2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the Ir(III) congener, X-ray crystallography. [Cp*Rh(L(BI) )Cl][PF6 ]2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir(L(BI) )Cl][PF6 ] and [Cp*M(phen)Cl][PF6 ] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate-driven RhH formation (90 kJ mol(-1) free-energy barrier), transfer of hydride between the Rh and BI(+) centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back-transfer of hydride from the BIH organic hydride donor to the Rh-activated imine substrate (89 kJ mol(-1) barrier), and exergonic protonation of the metal-bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed.

  12. Four-Component Damped Density Functional Response Theory Study of UV/Vis Absorption Spectra and Phosphorescence Parameters of Group 12 Metal-Substituted Porphyrins.

    PubMed

    Fransson, Thomas; Saue, Trond; Norman, Patrick

    2016-05-10

    The influences of group 12 (Zn, Cd, Hg) metal-substitution on the valence spectra and phosphorescence parameters of porphyrins (P) have been investigated in a relativistic setting. In order to obtain valence spectra, this study reports the first application of the damped linear response function, or complex polarization propagator, in the four-component density functional theory framework [as formulated in Villaume et al. J. Chem. Phys. 2010 , 133 , 064105 ]. It is shown that the steep increase in the density of states as due to the inclusion of spin-orbit coupling yields only minor changes in overall computational costs involved with the solution of the set of linear response equations. Comparing single-frequency to multifrequency spectral calculations, it is noted that the number of iterations in the iterative linear equation solver per frequency grid-point decreases monotonously from 30 to 0.74 as the number of frequency points goes from one to 19. The main heavy-atom effect on the UV/vis-absorption spectra is indirect and attributed to the change of point group symmetry due to metal-substitution, and it is noted that substitutions using heavier atoms yield small red-shifts of the intense Soret-band. Concerning phosphorescence parameters, the adoption of a four-component relativistic setting enables the calculation of such properties at a linear order of response theory, and any higher-order response functions do not need to be considered-a real, conventional, form of linear response theory has been used for the calculation of these parameters. For the substituted porphyrins, electronic coupling between the lowest triplet states is strong and results in theoretical estimates of lifetimes that are sensitive to the wave function and electron density parametrization. With this in mind, we report our best estimates of the phosphorescence lifetimes to be 460, 13.8, 11.2, and 0.00155 s for H2P, ZnP, CdP, and HgP, respectively, with the corresponding transition

  13. Compared electronic structures of negative ions M p C{/n -}: II. Transition metals in Hückel theory

    NASA Astrophysics Data System (ADS)

    Leleyter, M.

    1991-03-01

    SIMS experiments on transition metal carbides produce negative cluster ions M p C{/n -} ( n < 10) where the transition metal M is Ti, Zr, V, Cr, W, Fe and Ni with p=1 and V with p=2. The M p C{/n -} ions show very pronounced alternations in their emission intensities I( M p C{/n -}) versus n with strong maxima for even n whatever M. Since such phenomena are due to the stability properties of the clusters themselves (correspondence rule), it means that the negative ions are the most stable ones for even n. It is thus possible to get the general outlines of their electronic structures from the Pitzer and Clementi model ( sp hybridization in Hückel approximation): the clusters are assumed to be linear chains of “cumulene”-type :=C=..C=C= M and the alternations in the relative stabilities of these chains are due to the fact that the HOMO (highest occupied molecular orbital) of the clusters lies in a double degenerate π level band. Now HOMO may be either full (or almost full) or half-filled (or nearly half-filled), and an aggregate with a complete (or almost complete) HOMO is more stable than an aggregate with a half-filled HOMO. Consequently, the number of π electrons is governing the parity effect in the stability alternations. However, this number is depending on the number of σ electrons of the chain and on the existence of one dδ level (due to the M atom) which is either empty for deficient d electron elements (Ti, Zr, V, Cr, W) or filled for rich d electron elements (half-filled for Fe or full up for Ni). As the MC{/n -} chain must have a full (or nearly full) HOMO if n is even, it is then possible to infer a likely electronic configurations of these clusters, and hence to determine their relative stabilities, and to verify that “even” clusters are more stable than “odd” ones. Thus such Hückel model results can be used as a guide for more sophisticated calculations (ab initio, etc...).

  14. Beyond the usual suspects: target group- and behavior-specific factors add to a theory-based sun protection intervention for teenagers.

    PubMed

    Schüz, Natalie; Eid, Michael

    2013-10-01

    Sun protection standards among teenagers are low while sun exposure peaks in this age group. Study 1 explores predictors of adolescent protection intentions and exposure behavior. Study 2 tests the effectiveness of an intervention based on these predictors. Study 1(cross-sectional, N = 207, ages 15-18) and Study 2 (RCT, N = 253, ages 13-19) were conducted in schools. Path models were used to analyze data. Self-efficacy (β = .26, p < .001) and time perspective (β = .17, p = .014) were the strongest predictors of intentions; appearance motivation (β = .54, p < .001) and intention (β = -.18, p = .015) predicted behavior. The intervention effected changes in all predictors except self-efficacy. Changes in outcome expectancies (β = .19, p < .001) and time perspective (β = .09, p = .039) predicted changes in intention, while changes in intention (β = -.17, p = .002) and appearance motivation (β = .29, p < .001) predicted behavior changes. Target group- and behavior-specific intervention components are as important for changes in intentions and behavior as components derived from common health behavior theories.

  15. Theory of defects in non-metallic solids. Progress report, 1 August 1985-31 July 1986

    SciTech Connect

    Kunz, A.B.

    1986-07-01

    A general method based on ab initio quantum mechanical modelling and also utilizing semi-classical modelling of a type introduced by Mott-Littleton in 1938 is being implemented to describe the effects of a point defector impurity and/or their interaction in a solid system in a self consistent way. The initial thrust has been to define the scope of the model: in particular, trying to obtain a general model sufficient for describing any point defect of impurity problem in any non-metallic solid system, in the validation of the several concepts necessary for such a model, in the generalization of some necessary theoretical formalism, and finally in a series of initial studies designed to test both the concepts and the validity of the implementation of them. These latter studies include a study of the excitonic spectrum of several alkali halides, the study of a charged neutral defect system in the alkali halides and a study of whether or not these methodologies are capable of predicting the lattice geometries of several of the alkali halides. These studies are significant in several ways. They establish among other things the size of cluster needed for such a study, the utility norm conserving core replacing pseudopotentials, the need for treating relativistic effects including spin orbit, Darwin and mass velocity terms and the necessity of including multiplet structure in an appropriate way for localized excitations.

  16. Exploding-wire experiments and theory for metal conductivity evaluation in the sub-eV regime

    NASA Astrophysics Data System (ADS)

    Stephens, J.; Neuber, A.

    2012-12-01

    Copper and silver wires are subjected to pulsed high current densities producing high density metal plasma in the sub-eV regime with atmospheric air as a background gas. Numerical simulation via application of the one-dimensional magnetohydrodynamic partial differential equations solved simultaneously with the constraining circuit equations is presented. The simulations require accurate knowledge of the material equation of state (EOS) and transport properties; the LANL sesame database is applied for the EOS in all cases. Two electrical conductivity models are applied. First, the Lee-More-Desjarlais (LMD) and its modification, the quantum LMD (QLMD) conductivity, which have been well proven at higher temperatures, are applied. Simulations with the LMD and QLMD data indicate that the conductivity data as well as the MHD methodology are accurate in the sub-eV regime of interest. A less computationally involved, empirical conductivity model is applied in the same regime to explore its temperature-density range of applicability compared to the more sophisticated model.

  17. Theory of B(2)O and BeB(2) nanotubes: new semiconductors and metals in one dimension.

    PubMed

    Zhang, Peihong; Crespi, Vincent H

    2002-07-29

    We describe two new boron-based nanotubes: B(2)O and BeB(2). Both are isoelectronic to graphite, have reasonable curvature energies, and have already been made in their bulk planar forms. The lowest energy allotrope of planar single-layer B(2)O is a semiconductor with a moderate band gap. The local density approximation band gap of the corresponding (3,0) B(2)O nanotube [similar in size to (9,0) carbon nanotube tube] is direct and around 1.6 eV, within a range inaccessible to previous C or BN nanotubes. Single-layer BeB(2) has a fascinating structure: the Be atoms rest above the boron hexagonal faces, nearly coplanar to the boron sheet. The unusual K-point pi-pi(*) Fermi-level degeneracy of graphite survives, while a new nearly pointlike Fermi surface appears at the M point. As a result, BeB(2) nanotubes are uniformly metallic.

  18. Exploding-wire experiments and theory for metal conductivity evaluation in the sub-eV regime.

    PubMed

    Stephens, J; Neuber, A

    2012-12-01

    Copper and silver wires are subjected to pulsed high current densities producing high density metal plasma in the sub-eV regime with atmospheric air as a background gas. Numerical simulation via application of the one-dimensional magnetohydrodynamic partial differential equations solved simultaneously with the constraining circuit equations is presented. The simulations require accurate knowledge of the material equation of state (EOS) and transport properties; the LANL sesame database is applied for the EOS in all cases. Two electrical conductivity models are applied. First, the Lee-More-Desjarlais (LMD) and its modification, the quantum LMD (QLMD) conductivity, which have been well proven at higher temperatures, are applied. Simulations with the LMD and QLMD data indicate that the conductivity data as well as the MHD methodology are accurate in the sub-eV regime of interest. A less computationally involved, empirical conductivity model is applied in the same regime to explore its temperature-density range of applicability compared to the more sophisticated model.

  19. A Thermodynamic Model for Predicting Phosphorus Partition between CaO-based Slags and Hot Metal during Hot Metal Dephosphorization Pretreatment Process Based on the Ion and Molecule Coexistence Theory

    NASA Astrophysics Data System (ADS)

    Yang, Xue-min; Li, Jin-yan; Chai, Guo-ming; Duan, Dong-ping; Zhang, Jian

    2016-08-01

    A thermodynamic model for predicting phosphorus partition L P between a CaO-based slags and hot metal during hot metal dephosphorization pretreatment process has been developed based on the ion and molecule coexistence theory (IMCT), i.e., the IMCT- L P model. The reaction abilities of structural units or ion couples in the CaO-based slags have been represented by the calculated mass action concentrations N i through the developed IMCT- N i model based on the IMCT. The developed IMCT- L P model has been verified to be valid through comparing with the measured L P as well as the predicted L P by two reported L P models from the literature. Besides the total phosphorus partition L P between the CaO-based slag and hot metal, the respective phosphorus partitions L P, i of nine dephosphorization products as P2O5, 3FeO·P2O5, 4FeO·P2O5, 2CaO·P2O5, 3CaO·P2O5, 4CaO·P2O5, 2MgO·P2O5, 3MgO·P2O5, and 3MnO·P2O5 can also be accurately predicted by the developed IMCT- L P model. The formed 3CaO·P2O5 accounts for 99.20 pct of dephosphorization products comparing with the generated 4CaO·P2O5 for 0.08 pct. The comprehensive effect of CaO+Fe t O, which can be described by the mass percentage ratio (pct Fe t O)/(pct CaO) or the mass action concentration ratio N_{Fe}t O/N_{Fe}t O N_{CaO}. N_{CaO}} as well as the mass percentage product (pct Fe t O) × (pct CaO) or the mass action concentration product N_{{{{Fe}}t {{O}}}}5 × N_{{CaO}}3 , controls dephosphorization ability of the CaO-based slags. A linear relationship of L P against (pct Fe t O)/(pct CaO) can be correlated compared with a parabolic relationship of L P against N_{Fe}t O/N_{Fe}t O N_{CaO}. N_{CaO}, while the linear relationship of L P against (pct Fe t O) × (pct CaO) or N_{Fe}t O5 × N_{CaO}3 can be established. Thus, the mass percentage product (pct Fe t O) × (pct CaO) and the mass action concentration product N_{Fe}t O5 × N_{CaO}3 are recommended to represent the comprehensive effect of CaO+Fe t O on

  20. Theory of late-transition-metal alkyl and heteroatom bonding: analysis of Pt, Ru, Ir, and Rh complexes.

    PubMed

    Devarajan, Deepa; Gunnoe, T Brent; Ess, Daniel H

    2012-06-18

    Density functional and correlated ab initio methods were used to calculate, compare, and analyze bonding interactions in late-transition-metal alkyl and heteroatom complexes (M-X). The complexes studied include: (DMPE)Pt(CH(3))(X) (DMPE = 1,2-bis(dimethylphosphino)ethane), Cp*Ru(PMe(3))(2)(X) (Cp* = pentamethylcyclopentadienyl), (DMPE)(2)Ru(H)(X), (Tp)(CO)Ru(Py)(X) (Tp = trispyrazolylborate), (PMe(3))(2)Rh(C(2)H(4))(X), and cis-(acac)(2)Ir(Py)(X) (acac = acetylacetonate). Seventeen X ligands were analyzed that include alkyl (CR(3)), amido (NR(2)), alkoxo (OR), and fluoride. Energy decomposition analysis of these M-X bonds revealed that orbital charge transfer stabilization provides a straightforward model for trends in bonding along the alkyl to heteroatom ligand series (X = CH(3), NH(2), OH, F). Pauli repulsion (exchange repulsion), which includes contributions from closed-shell d(π)-p(π) repulsion, generally decreases along the alkyl to heteroatom ligand series but depends on the exact M-X complexes. It was also revealed that stabilizing electrostatic interactions generally decrease along this ligand series. Correlation between M-X and H-X bond dissociation energies is good with R(2) values between 0.7 and 0.9. This correlation exists because for both M-X and H-X bonds the orbital stabilization energies are a function of the orbital electronegativity of the X group. The greater than 1 slope when correlating M-X and H-X bond dissociation energies was traced back to differences in Pauli repulsion and electrostatic stabilization.

  1. Benchmark Calculations of Energetic Properties of Groups 4 and 6 Transition Metal Oxide Nanoclusters Including Comparison to Density Functional Theory

    SciTech Connect

    Fang, Zongtang; Both, Johan; Li, Shenggang; Yue, Shuwen; Aprà, Edoardo; Keçeli, Murat; Wagner, Albert F.; Dixon, David A.

    2016-08-09

    The heats of formation and the normalized clustering energies (NCEs) for the group 4 and group 6 transition metal oxide (TMO) trimers and tetramers have been calculated by the Feller-Peterson-Dixon (FPD) method. The heats of formation predicted by the FPD method do not differ much from those previously derived from the NCEs at the CCSD(T)/aT level except for the CrO3 nanoclusters. New and improved heats of formation for Cr3O9 and Cr4O12 were obtained using PW91 orbitals instead of Hartree-Fock (HF) orbitals. Diffuse functions are necessary to predict accurate heats of formation. The fluoride affinities (FAs) are calculated with the CCSD(T) method. The relative energies (REs) of different isomers, NCEs, electron affinities (EAs), and FAs of (MO2)n ( M = Ti, Zr, Hf, n = 1 – 4 ) and (MO3)n ( M = Cr, Mo, W, n = 1 – 3) clusters have been benchmarked with 55 exchange-correlation DFT functionals including both pure and hybrid types. The absolute errors of the DFT results are mostly less than ±10 kcal/mol for the NCEs and the EAs, and less than ±15 kcal/mol for the FAs. Hybrid functionals usually perform better than the pure functionals for the REs and NCEs. The performance of the two types of functionals in predicting EAs and FAs is comparable. The B1B95 and PBE1PBE functionals provide reliable energetic properties for most isomers. Long range corrected pure functionals usually give poor FAs. The standard deviation of the absolute error is always close to the mean errors and the probability distributions of the DFT errors are often not Gaussian (normal). The breadth of the distribution of errors and the maximum probability are dependent on the energy property and the isomer.

  2. Performance of density functional theory for 3d transition metal-containing complexes: utilization of the correlation consistent basis sets.

    PubMed

    Tekarli, Sammer M; Drummond, Michael L; Williams, T Gavin; Cundari, Thomas R; Wilson, Angela K

    2009-07-30

    The performance of 44 density functionals used in conjunction with the correlation consistent basis sets (cc-pVnZ where n = T and Q) has been assessed for the gas-phase enthalpies of formation at 298.15 K of 3d transition metal (TM) containing systems. Nineteen molecules were examined: ScS, VO, VO(2), Cr(CO)(6), MnS, MnCl(2), Mn(CO)(5)Cl, FeCl(3), Fe(CO)(5), CoH(CO)(4), NiCl(2), Ni(CO)(4), CuH, CuF, CuCl, ZnH, ZnO, ZnCl, and Zn(CH(3))(2). Of the functionals examined, the functionals that resulted in the smallest mean absolute deviation (MAD, in parentheses, kcal mol(-1)) from experiment were B97-1 (6.9), PBE1KCIS (8.1), TPSS1KCIS (9.6), B97-2 (9.7), and B98 (10.7). All five of these functionals include some degree of Hartree-Fock (HF) exchange. The impact of increasing the basis set from cc-pVTZ to cc-pVQZ was found to be slight for the generalized gradient approximation (GGA) and meta-GGA (MGGA) functionals studied, indicating basis set saturation at the triple-zeta level. By contrast, for most of the generalized gradient exchange (GGE), hybrid GGA (HGGA), and hybrid meta-GGA (HMGGA) functionals considered, improvements in the average MAD of 2-3 kcal mol(-1) were seen upon progressing to a quadruple-zeta level basis set. Overall, it was found that the functionals that include Hartree-Fock exchange performed best overall, but those with greater than 40% HF exchange exhibit significantly poor performance for the prediction of enthalpies of formation for 3d TM complexes. Carbonyl-containing complexes, a mainstay in organometallic TM chemistry, are demonstrated to be exceedingly difficult to describe accurately with all but 2 of the 44 functionals considered. The most accurate functional, for both CO-containing and CO-free compounds, is B97-1/cc-pVQZ, which is shown to be capable of yielding results within 1 kcal mol(-1) of high-level ab initio composite methodologies.

  3. An efficient way to evidence and to measure the metal ion fraction in high power impulse magnetron sputtering (HiPIMS) post-discharge with Pt, Au, Pd and mixed targets

    NASA Astrophysics Data System (ADS)

    Cuynet, S.; Lecas, T.; Caillard, A.; Brault, P.

    2016-12-01

    The proportion of metal ions in a high power impulse magnetron sputtering discharge is key information for the potential development of new materials and new layer architectures deposited by this technique. This paper aims to measure this proportion by using a homemade system consisting of a quartz crystal microbalance and a grid energy analyser assembly. Such a system yields relevant results on the composition of the post-discharge depending on the nature of the gas (Ar, Kr, Xe) and the target materials (Pt, Pd, Au, 50\\text{Au}50$ and 5\\text{Pd}95$ ). In our conditions, the highest proportion of metal ions in the post-discharge are obtained by using Ar gas and reaches 10 %, 12 %, 50 %, 19 % and 88 % for Pt, Au, Pd, 50\\text{Au}50$ and 5\\text{Pd}95$ targets, respectively.

  4. Metal Preferences and Metallation*

    PubMed Central

    Foster, Andrew W.; Osman, Deenah; Robinson, Nigel J.

    2014-01-01

    The metal binding preferences of most metalloproteins do not match their metal requirements. Thus, metallation of an estimated 30% of metalloenzymes is aided by metal delivery systems, with ∼25% acquiring preassembled metal cofactors. The remaining ∼70% are presumed to compete for metals from buffered metal pools. Metallation is further aided by maintaining the relative concentrations of these pools as an inverse function of the stabilities of the respective metal complexes. For example, magnesium enzymes always prefer to bind zinc, and these metals dominate the metalloenzymes without metal delivery systems. Therefore, the buffered concentration of zinc is held at least a million-fold below magnesium inside most cells. PMID:25160626

  5. CO2 capture properties of alkaline earth metal oxides and hydroxides: A combined density functional theory and lattice phonon dynamics study

    NASA Astrophysics Data System (ADS)

    Duan, Yuhua; Sorescu, Dan C.

    2010-08-01

    By combining density functional theory and lattice phonon dynamics, the thermodynamic properties of CO2 absorption/desorption reactions with alkaline earth metal oxides MO and hydroxides M(OH)2 (where M=Be,Mg,Ca,Sr,Ba) are analyzed. The heats of reaction and the chemical potential changes of these solids upon CO2 capture reactions have been calculated and used to evaluate the energy costs. Relative to CaO, a widely used system in practical applications, MgO and Mg(OH)2 systems were found to be better candidates for CO2 sorbent applications due to their lower operating temperatures (600-700 K). In the presence of H2O, MgCO3 can be regenerated into Mg(OH)2 at low temperatures or into MgO at high temperatures. This transition temperature depends not only on the CO2 pressure but also on the H2O pressure. Based on our calculated results and by comparing with available experimental data, we propose a general computational search methodology which can be used as a general scheme for screening a large number of solids for use as CO2 sorbents.

  6. Adsorption and ring-opening of lactide on the chiral metal surface Pt(321){sup S} studied by density functional theory

    SciTech Connect

    Franke, J.-H.; Kosov, D. S.

    2015-01-28

    We study the adsorption and ring-opening of lactide on the naturally chiral metal surface Pt(321){sup S}. Lactide is a precursor for polylactic acid ring-opening polymerization, and Pt is a well known catalyst surface. We study, here, the energetics of the ring-opening of lactide on a surface that has a high density of kink atoms. These sites are expected to be present on a realistic Pt surface and show enhanced catalytic activity. The use of a naturally chiral surface also enables us to study potential chiral selectivity effects of the reaction at the same time. Using density functional theory with a functional that includes the van der Waals forces in a first-principles manner, we find modest adsorption energies of around 1.4 eV for the pristine molecule and different ring-opened states. The energy barrier to be overcome in the ring-opening reaction is found to be very small at 0.32 eV and 0.30 eV for LL- and its chiral partner DD-lactide, respectively. These energies are much smaller than the activation energy for a dehydrogenation reaction of 0.78 eV. Our results thus indicate that (a) ring-opening reactions of lactide on Pt(321) can be expected already at very low temperatures, and Pt might be a very effective catalyst for this reaction; (b) the ring-opening reaction rate shows noticeable enantioselectivity.

  7. [The practical theory of occupational health planning: Part One--The theoretical background of the target population setting and needs assessment procedures (OPST research report 2)].

    PubMed

    Jahng, D J; Hashimoto, H; Furuki, K

    1996-09-01

    The OPSS is an 8 stage program which was developed as a practical tool for occupational health services planning. This paper examines the theoretical aspects of the first two stages. The OPSS is a planning tool with a theoretical grounding in OHP (The practical theory of Occupational Health Planning). The target population setting has two functions. The first is to establish the physician's first-hypothesis to design a program. The other is deciding the group which has an occupational health problem in a company. The Needs Assessment helps to clarify the physician's hypothesis, which may be weak due to the limited knowledge of various demands of the employees and senior management. On the other hand, the risks and needs vary according to what kind of expert looks at a situation. To date, occupational physicians have been limited to their medical background in determining only risks and needs. However, understanding the various stakeholders in a particular environment means that any project will be more relevant to all concerned. Another limitation of the occupational physicians hypothesis can be the lack of objective data to support it. This makes it difficult to persuade senior management to sign on to a program. The Needs Assessment procedure with OHQ steps is useful in a number of ways. The Observation step allows for finding risks and needs from various situations in the company from the occupational physician's viewpoint (prehypothesis setting). Hearing is for understanding the subject's demands and finding common themes in the company (final hypothesis setting). Finally, the questionnaire step is for providing objectivity of these common themes and quantitative data for the next Priority Setting procedure. The BITOP (Budget, Information, Time, Order, key Person) has been proposed as a way to diagnose the structural and functional aspects of an organization's procedures. Budget tracks the financial flow through the organization, while Information identifies

  8. Atomic and molecular adsorption on transition-metal carbide (111) surfaces from density-functional theory: a trend study of surface electronic factors.

    PubMed

    Vojvodic, A; Ruberto, C; Lundqvist, B I

    2010-09-22

    This study explores atomic and molecular adsorption on a number of early transition-metal carbides (TMCs) in NaCl structure by means of density-functional theory calculations. The investigated substrates are the TM-terminated TMC(111) surfaces, of interest because of the presence of different types of surface resonances (SRs) on them and because of their technological importance in growth processes. Also, TM compounds have shown potential in catalysis applications. Trend studies are conducted with respect to both period and group in the periodic table, choosing the substrates ScC, TiC, VC, ZrC, NbC, δ-MoC, TaC, and WC (in NaCl structure) and the adsorbates H, B, C, N, O, F, NH, NH(2), and NH(3). Trends in adsorption strength are explained in terms of surface electronic factors, by correlating the calculated adsorption-energy values with the calculated surface electronic structures. The results are rationalized by use of a concerted-coupling model (CCM), which has previously been applied successfully to the description of adsorption on TiC(111) and TiN(111) surfaces (Ruberto et al 2007 Solid State Commun. 141 48). First, the clean TMC(111) surfaces are characterized by calculating surface energies, surface relaxations, Bader charges, and surface-localized densities of states (DOSs). Detailed comparisons between surface and bulk DOSs reveal the existence of transition-metal localized SRs (TMSRs) in the pseudogap and of several C-localized SRs (CSRs) in the upper valence band on all considered TMC(111) surfaces. The spatial extent and the dangling bond nature of these SRs are supported by real-space analyses of the calculated Kohn-Sham wavefunctions. Then, atomic and molecular adsorption energies, geometries, and charge transfers are presented. An analysis of the adsorbate-induced changes in surface DOSs reveals a presence of both adsorbate-TMSR and adsorbate-CSRs interactions, of varying strengths depending on the surface and the adsorbate. These variations are

  9. The thermal-mechanical analysis of targets for the high volume production of molybdenum-99 using a low-enriched uranium metal foil

    NASA Astrophysics Data System (ADS)

    Turner, Kyler Kriens

    Molybdenum-99 diagnostic imaging is the most commonly practiced procedure in nuclear medicine today with the majority molybdenum-99 produced with proliferation sensitive HEU. International and domestic efforts to develop non-HEU production techniques have taking the first steps toward establishing a new non-HEU molybdenum-99 based supply chain. The focus of the research presented in this work is on the analysis of a new high U-235 density LEU based molybdenum-99 production target. Converting directly to LEU using current manufacturing techniques greatly reduces the molybdenum-99 yield per target making high volume production uneconomical. The LEU based foil target analyzed in this research increases the yield per target making economic high volume production with LEU possible. The research analyzed the thermal-mechanical response of an LEU foil target during irradiation. Thermal-mechanical studies focused on deflections and stresses to assess the probability of target failure. Simpler analytical models were used to determine the proper shape of the target and to benchmark the numerical modeling software. Numerical studies using Abaqus focused on analyzing various heating and cooling conditions and assessing the effects of curvature on the target. Finally, experiments were performed to simulate low power heating and further benchmark the models. The results from all of these analyses indicate a LEU foil target could survive irradiation depending on the conditions seen during irradiation.

  10. Binding energy of transition-metal complexes with large pi-conjugate systems. Density functional theory vs post-Hartree-Fock methods.

    PubMed

    Ikeda, Atsushi; Nakao, Yoshihide; Sato, Hirofumi; Sakaki, Shigeyoshi

    2007-08-02

    We systematically evaluated the binding energies of d10, d8, and d6 transition-metal complexes with various pi-conjugate systems such as Pt(PH3)2{C2H4-n(CH=CH2)n}, Pd(PH3)2{C2H4-n(CH=CH2)n}, [PtCl3{C2H4-n-(CH=CH2)n}]-, [PdCl3{C2H4-n(CH=CH2)n}]-, and [PtCl5{C2H4-n(CH=CH2)n}]- (n = 0-4) using the MP2 to MP4, CCSD(T), and density functional theory (DFT) methods. The MP4(SDQ) and CCSD(T) methods present a reliable binding energy, whereas the DFT method significantly underestimates the binding energy when the size of the pi-conjugate system is large. The underestimation occurs independently of the coordinate bonding nature; the pi-back-donation is stronger than the sigma-donation in the Pt(0) complexes, as expected, they are comparable in the Pt(II) complexes, and only the sigma-donation participates in the coordinate bond of the Pt(IV) complexes. The DFT method provides moderately stronger charge-transfer (CT) interaction than the MP4(SDQ) method, suggesting that the underestimation of the binding energy by the DFT method does not arise from the insufficient description of the CT interaction. From theoretical investigation of several model systems, it is concluded that the underestimation arises from the insufficient description of electron correlation effects.

  11. Inner hydrogen atom transfer in benzo-fused low symmetrical metal-free tetraazaporphyrin and phthalocyanine analogues: density functional theory studies.

    PubMed

    Qi, Dongdong; Zhang, Yuexing; Cai, Xue; Jiang, Jianzhuang; Bai, Ming

    2009-02-01

    Density functional theory (DFT) calculations were carried out to study the inner hydrogen atom transfer in low symmetrical metal-free tetrapyrrole analogues ranging from tetraazaporphyrin H(2)TAP (A(0)B(0)C(0)D(0)) to naphthalocyanine H(2)Nc (A(2)B(2)C(2)D(2)) via phthalocyanine H(2)Pc (A(1)B(1)C(1)D(1)). All the transition paths of sixteen different compounds (A(0)B(0)C(0)D(0)-A(2)B(2)C(2)D(2) and A(0)B(0)C(m)D(n), m

  12. Evaluating the Outcomes and Implementation of a TaMHS (Targeting Mental Health in Schools) Project in Four West Midlands (UK) Schools Using Activity Theory

    ERIC Educational Resources Information Center

    Cane, Fiona Eloise; Oland, Louise

    2015-01-01

    Government guidance in 2008 endorsed the "Targeting Mental Health in Schools" (TaMHS) agenda, which sets out to promote mental health in schools through the delivery of universal and targeted interventions. This paper initially defines mental health and outlines the TaMHS initiative. It then offers empirical findings from four focus…

  13. Medical CT image reconstruction accuracy in the presence of metal objects using x-rays up to 1 MeV with x-ray targets of beryllium, carbon, aluminum, copper, and tungsten

    NASA Astrophysics Data System (ADS)

    Clayton, James; Ganguly, Arundhuti; Virshup, Gary

    2012-04-01

    Flat panels imagers based on amorphous silicon technology (a-Si) for digital radiography have been accepted by the medical community as having several advantages over film-based systems. Radiotherapy treatment planning systems employ computed tomographic (CT) data sets and projection images to delineate tumor targets and normal structures that are to be spared from radiation treatment. The accuracy of CT numbers is crucial for radiotherapy dose calculations. Conventional CT scanners operating at kilovoltage X-ray energies typically exhibit significant image reconstruction artifacts in the presence of metal implants in human body. Megavoltage X-ray energies have problems maintaining contrast sensitivity for the same dose as kV X-ray systems. We intend to demonstrate significant improvement in metal artifact reductions and electron density measurements using an amorphous silicon a-Si imager obtained with an X-ray source that can operate at energies up to 1 MeV. We will investigate the ability to maintain contrast sensitivity at this higher X-ray energy by using targets with lower atomic numbers and appropriate amounts of Xray filtration than are typically used as X-ray production targets and filters.

  14. HYDROGEN ISOTOPE TARGETS

    DOEpatents

    Ashley, R.W.

    1958-08-12

    The design of targets for use in the investigation of nuclear reactions of hydrogen isotopes by bombardment with accelerated particles is described. The target con struction eomprises a backing disc of a metal selected from the group consisting of molybdenunn and tungsten, a eoating of condensed titaniunn on the dise, and a hydrogen isotope selected from the group consisting of deuterium and tritium absorbed in the coatiag. The proeess for preparing these hydrogen isotope targets is described.

  15. Extending DFT-based genetic algorithms by atom-to-place re-assignment via perturbation theory: A systematic and unbiased approach to structures of mixed-metallic clusters

    SciTech Connect

    Weigend, Florian

    2014-10-07

    Energy surfaces of metal clusters usually show a large variety of local minima. For homo-metallic species the energetically lowest can be found reliably with genetic algorithms, in combination with density functional theory without system-specific parameters. For mixed-metallic clusters this is much more difficult, as for a given arrangement of nuclei one has to find additionally the best of many possibilities of assigning different metal types to the individual positions. In the framework of electronic structure methods this second issue is treatable at comparably low cost at least for elements with similar atomic number by means of first-order perturbation theory, as shown previously [F. Weigend, C. Schrodt, and R. Ahlrichs, J. Chem. Phys. 121, 10380 (2004)]. In the present contribution the extension of a genetic algorithm with the re-assignment of atom types to atom sites is proposed and tested for the search of the global minima of PtHf{sub 12} and [LaPb{sub 7}Bi{sub 7}]{sup 4−}. For both cases the (putative) global minimum is reliably found with the extended technique, which is not the case for the “pure” genetic algorithm.

  16. Extending DFT-based genetic algorithms by atom-to-place re-assignment via perturbation theory: a systematic and unbiased approach to structures of mixed-metallic clusters.

    PubMed

    Weigend, Florian

    2014-10-07

    Energy surfaces of metal clusters usually show a large variety of local minima. For homo-metallic species the energetically lowest can be found reliably with genetic algorithms, in combination with density functional theory without system-specific parameters. For mixed-metallic clusters this is much more difficult, as for a given arrangement of nuclei one has to find additionally the best of many possibilities of assigning different metal types to the individual positions. In the framework of electronic structure methods this second issue is treatable at comparably low cost at least for elements with similar atomic number by means of first-order perturbation theory, as shown previously [F. Weigend, C. Schrodt, and R. Ahlrichs, J. Chem. Phys. 121, 10380 (2004)]. In the present contribution the extension of a genetic algorithm with the re-assignment of atom types to atom sites is proposed and tested for the search of the global minima of PtHf12 and [LaPb7Bi7](4-). For both cases the (putative) global minimum is reliably found with the extended technique, which is not the case for the "pure" genetic algorithm.

  17. Influence of the reactive atmosphere on the formation of nanoparticles in the plasma plume induced by nanosecond pulsed laser irradiation of metallic targets at atmospheric pressure and high repetition rate

    NASA Astrophysics Data System (ADS)

    Girault, M.; Le Garrec, J.-L.; Mitchell, J. B. A.; Jouvard, J.-M.; Carvou, E.; Menneveux, J.; Yu, J.; Ouf, F.-X.; Carles, S.; Potin, V.; Pillon, G.; Bourgeois, S.; Perez, J.; Marco de Lucas, M. C.; Lavisse, L.

    2016-06-01

    The influence of a reactive atmosphere on the formation of nanoparticles (NPs) in the plasma plume generated by nanosecond pulsed laser irradiation of metal targets (Ti, Al, Ag) was probed in situ using Small Angle X-ray Scattering (SAXS). Air and different O2-N2 gas mixtures were used as reactive gas within atmospheric pressure. SAXS results showed the formation of NPs in the plasma-plume with a mean radius varying in the 2-5 nm range. A decrease of the NPs size with increasing the O2 percentage in the O2-N2 gas mixture was also showed. Ex situ observations by transmission electron microscopy and structural characterizations by X-ray diffraction and Raman spectroscopy were also performed for powders collected in experiments done using air as ambient gas. The stability of the different metal oxides is discussed as being a key parameter influencing the formation of NPs in the plasma-plume.

  18. Smearing origin of zero-bias conductance peak in Ag-SiO-Bi2Sr2CaCu2O8+δ planar tunnel junctions: influence of diffusive normal metal verified with the circuit theory

    NASA Astrophysics Data System (ADS)

    Shigeta, I.; Tanaka, Y.; Ichikawa, F.; Asano, Y.

    2006-11-01

    We propose a new approach of smearing origins of a zero-bias conductance peak (ZBCP) in high-Tc superconductor tunnel junctions through the analysis based on the circuit theory for a d-wave pairing symmetry. The circuit theory has been recently developed from conventional superconductors to unconventional superconductors. The ZBCP frequently appears in line shapes for this theory, in which the total resistance was constructed by taking account of the effects between a d-wave superconductor and a diffusive normal metal (DN) at a junction interface, including the midgap Andreev resonant states (MARS), the coherent Andreev reflection (CAR) and the proximity effect. Therefore, we have analyzed experimental spectra with the ZBCP of Ag-SiO-Bi2Sr2CaCu2O8+δ (Bi-2212) planar tunnel junctions for the {110}-oriented direction by using a simplified formula of the circuit theory for d-wave superconductors. The fitting results reveal that the spectral features of the ZBCP are well explained by the circuit theory not only excluding the Dynes's broadening factor but also considering only the MARS and the DN resistance. Thus, the ZBCP behaviors are understood to be consistent with those of recent studies on the circuit theory extended to the systems containing d-wave superconductor tunnel junctions.

  19. Human health risks from metals and metalloid via consumption of food animals near gold mines in Tarkwa, Ghana: estimation of the daily intakes and target hazard quotients (THQs).

    PubMed

    Bortey-Sam, Nesta; Nakayama, Shouta M M; Ikenaka, Yoshinori; Akoto, Osei; Baidoo, Elvis; Yohannes, Yared Beyene; Mizukawa, Hazuki; Ishizuka, Mayumi

    2015-01-01

    Heavy metal and metalloid contamination in food resulting from mining is of major concern due to the potential risk involved. Food consumption is the most likely route of human exposure to metals. This study was therefore to assess metals in different organs and different animal species near gold mines used for human consumption (free-range chicken, goat and sheep) in Tarkwa, Ghana, and to estimate the daily intake and health risk. The concentrations of Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd, and Pb were measured with an inductively coupled plasma-mass spectrometer and Hg analysis was done using the mercury analyzer. Principal component analysis of the results showed a clear separation between chicken, grouped on one side, and the ruminants clustered on another side in both offal and muscle. Interestingly, As, Cd, Hg, Mn and Pb made one cluster in the offal of chicken. Chicken muscle also showed similar distribution with As, Hg and Pb clustered together. The daily intake of metals (μg/kg body weight/day) were in the following ranges; As [0.002 (kidneys of goat and sheep)-0.19 (chicken gizzard)], Cd [0.003 (chicken muscle)-0.55 (chicken liver)], Hg [0.002 (goat muscle)-0.29 (chicken liver)], Pb [0.01 (muscles and kidneys of goat and sheep)-0.96 (chicken gizzard)] and Mn [0.13 (goat kidney)-8.92 (sheep liver)]. From the results, daily intakes of As, Cd, Hg, Pb and Mn in these food animals were low compared to the provisional tolerable daily intake guidelines. The THQs although less than one, indicated that contributions of chicken gizzard and liver to toxic metal exposure in adults and especially children could be significant.

  20. Metals and metal derivatives in medicine.

    PubMed

    Colotti, Gianni; Ilari, Andrea; Boffi, Alberto; Morea, Veronica

    2013-02-01

    Several chemical elements are required by living organisms in addition to the four elements carbon, hydrogen, nitrogen and oxygen usually present in common organic molecules. Many metals (e.g. sodium, potassium, magnesium, calcium, iron, zinc, copper, manganese, chromium, molybdenum and selenium) are known to be required for normal biological functions in humans. Disorders of metal homeostasis and of metal bioavailability, or toxicity caused by metal excess, are responsible for a large number of human diseases. Metals are also extensively used in medicine as therapeutic and/or diagnostic agents. In the past 5000 years, metals such as arsenic, gold and iron have been used to treat a variety of human diseases. Nowadays, an ever-increasing number of metal-based drugs is available. These contain a broad spectrum of metals, many of which are not among those essential for humans, able to target proteins and/or DNA. This mini-review describes metal-containing compounds targeting DNA or proteins currently in use, or designed to be used, as therapeutics against cancer, arthritis, parasitic and other diseases, with a special focus on the available information, often provided by X-ray studies, about their mechanism of action at a molecular level. In addition, an overview of metal complexes used for diagnosing diseases is presented.

  1. Metallic Hydrogen

    NASA Astrophysics Data System (ADS)

    Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

    2015-03-01

    Hydrogen is the simplest and most abundant element in the Universe. At high pressure it is predicted to transform to a metal with remarkable properties: room temperature superconductivity, a metastable metal at ambient conditions, and a revolutionary rocket propellant. Both theory and experiment have been challenged for almost 80 years to determine its condensed matter phase diagram, in particular the insulator-metal transition. Hydrogen is predicted to dissociate to a liquid atomic metal at multi-megabar pressures and T =0 K, or at megabar pressures and very high temperatures. Thus, its predicted phase diagram has a broad field of liquid metallic hydrogen at high pressure, with temperatures ranging from thousands of degrees to zero Kelvin. In a bench top experiment using static compression in a diamond anvil cell and pulsed laser heating, we have conducted measurements on dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K. We observe a first-order phase transition in the liquid phase, as well as sharp changes in optical transmission and reflectivity when this phase is entered. The optical signature is that of a metal. The mapping of the phase line of this transition is in excellent agreement with recent theoretical predictions for the long-sought plasma phase transition to metallic hydrogen. Research supported by the NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H.

  2. Adaptive infrared target detection

    NASA Astrophysics Data System (ADS)

    McBride, Jonah C.; Stevens, Mark R.; Eaton, Ross S.; Snorrason, Magnus S.

    2004-09-01

    Automatic Target Recognition (ATR) algorithms are extremely sensitive to differences between the operating conditions under which they are trained and the extended operating conditions (EOCs) in which the fielded algorithms are tested. These extended operating conditions can cause a target's signature to be drastically different from training exemplars/models. For example, a target's signature can be influenced by: the time of day, the time of year, the weather, atmospheric conditions, position of the sun or other illumination sources, the target surface and material properties, the target composition, the target geometry, sensor characteristics, sensor viewing angle and range, the target surroundings and environment, and the target and scene temperature. Recognition rates degrade if an ATR is not trained for a particular EOC. Most infrared target detection techniques are based on a very simple probabilistic theory. This theory states that a pixel should be assigned the label of "target" if a set of measurements (features) is more likely to have come from an assumed (or learned) distribution of target features than from the distribution of background features. However, most detection systems treat these learned distributions as static and they are not adapted to changing EOCs. In this paper, we present an algorithm for assigning a pixel the label of target or background based on a statistical comparison of the distributions of measurements surrounding that pixel in the image. This method provides a feature-level adaptation to changing EOCs. Results are demonstrated on infrared imagery containing several military vehicles.

  3. In-situ small-angle x-ray scattering study of nanoparticles in the plasma plume induced by pulsed laser irradiation of metallic targets

    SciTech Connect

    Lavisse, L.; Jouvard, J.-M.; Girault, M.; Potin, V.; Andrzejewski, H.; Marco de Lucas, M. C.; Bourgeois, S.; Le Garrec, J.-L.; Carles, S.; Mitchell, J. B. A.; Hallo, L.; Perez, J.; Decloux, J.

    2012-04-16

    Small angle x-ray scattering was used to probe in-situ the formation of nanoparticles in the plasma plume generated by pulsed laser irradiation of a titanium metal surface under atmospheric conditions. The size and morphology of the nanoparticles were characterized as function of laser irradiance. Two families of nanoparticles were identified with sizes on the order of 10 and 70 nm, respectively. These results were confirmed by ex-situ transmission electron microscopy experiments.

  4. Formation of a fine-dispersed liquid-metal target under the action of femto- and picosecond laser pulses for a laser-plasma radiation source in the extreme ultraviolet range

    SciTech Connect

    Vinokhodov, A Yu; Krivokorytov, M S; Koshelev, K N; Krivtsun, V M; Sidelnikov, Yu V; Medvedev, V V; Kompanets, V O; Melnikov, A A; Chekalin, S V

    2016-01-31

    We report the results of studying the dynamics of deformation and fragmentation of liquid-metal droplets under the action of ultrashort laser pulses. The experiments have been performed to optimise the shape of the droplet target used in extreme ultraviolet (EUV) radiation sources based on the laser-produced plasma using the pre-pulse technology. The pre-pulse is generated by a system incorporating a master Ti : sapphire oscillator and a regenerative amplifier, allowing one to vary the pulse duration from 50 fs to 50 ps. The power density of laser radiation at the droplet target, averaged over the pulse duration and spatial coordinates, has reached 3 × 10{sup 15} W cm{sup -2}. The production of liquid-metal droplets has been implemented by means of a droplet generator based on a nozzle with a ring piezoceramic actuator. The droplet material is the eutectic indium – tin alloy. The droplet generator could operate in the droplet and jet regime with a maximal rate of stable operation 5 and 150 kHz, respectively. The spatial stability of droplet position σ = 1% – 2% of its diameter is achieved. The size of the droplets varied within 30 – 70 μm, their velocity was 2 – 8 m s{sup -1} depending on the operation regime. (interaction of laser radiation with matter. laser plasma)

  5. A structural equation model of soil metal bioavailability to earthworms: confronting causal theory and observations using a laboratory exposure to field-contaminated soils.

    PubMed

    Beaumelle, Léa; Vile, Denis; Lamy, Isabelle; Vandenbulcke, Franck; Gimbert, Frédéric; Hedde, Mickaël

    2016-11-01

    Structural equation models (SEM) are increasingly used in ecology as multivariate analysis that can represent theoretical variables and address complex sets of hypotheses. Here we demonstrate the interest of SEM in ecotoxicology, more precisely to test the three-step concept of metal bioavailability to earthworms. The SEM modeled the three-step causal chain between environmental availability, environmental bioavailability and toxicological bioavailability. In the model, each step is an unmeasured (latent) variable reflected by several observed variables. In an exposure experiment designed specifically to test this SEM for Cd, Pb and Zn, Aporrectodea caliginosa was exposed to 31 agricultural field-contaminated soils. Chemical and biological measurements used included CaC12-extractable metal concentrations in soils, free ion concentration in soil solution as predicted by a geochemical model, dissolved metal concentration as predicted by a semi-mechanistic model, internal metal concentrations in total earthworms and in subcellular fractions, and several biomarkers. The observations verified the causal definition of Cd and Pb bioavailability in the SEM, but not for Zn. Several indicators consistently reflected the hypothetical causal definition and could thus be pertinent measurements of Cd and Pb bioavailability to earthworm in field-contaminated soils. SEM highlights that the metals present in the soil solution and easily extractable are not the main source of available metals for earthworms. This study further highlights SEM as a powerful tool that can handle natural ecosystem complexity, thus participating to the paradigm change in ecotoxicology from a bottom-up to a top-down approach.

  6. The impact of sediment bioturbation by secondary organisms on metal bioavailability, bioaccumulation and toxicity to target organisms in benthic bioassays: Implications for sediment quality assessment.

    PubMed

    Remaili, Timothy M; Simpson, Stuart L; Amato, Elvio D; Spadaro, David A; Jarolimek, Chad V; Jolley, Dianne F

    2016-01-01

    Bioturbation alters the properties of sediments and modifies contaminant bioavailability to benthic organisms. These naturally occurring disturbances are seldom considered during the assessment of sediment quality. We investigated how the presence (High bioturbation) and absence (Low bioturbation) of a strongly bioturbating amphipod within three different sediments influenced metal bioavailability, survival and bioaccumulation of metals to the bivalve Tellina deltoidalis. The concentrations of dissolved copper decreased and manganese increased with increased bioturbation. For copper a strong correlation was observed between increased bivalve survival (53-100%) and dissolved concentrations in the overlying water. Increased bioturbation intensity resulted in greater tissue concentrations for chromium and zinc in some test sediments. Overall, the results highlight the strong influence that the natural bioturbation activities from one organism may have on the risk contaminants pose to other organisms within the local environment. The characterisation of field-based exposure conditions concerning the biotic or abiotic resuspension of sediments and the rate of attenuation of released contaminants through dilution or readsorption may enable laboratory-based bioassay designs to be adapted to better match those of the assessed environment.

  7. Low substrate temperature fabrication of high-performance metal oxide thin-film by magnetron sputtering with target self-heating

    SciTech Connect

    Yang, W. F.; Liu, Z. G.; Wu, Z. Y.; Hong, M. H.; Wang, C. F.; Lee, Alex Y. S.; Gong, H.

    2013-03-18

    Al-doped ZnO (AZO) films with high transmittance and low resistivity were achieved on low temperature substrates by radio frequency magnetron sputtering using a high temperature target. By investigating the effect of target temperature (T{sub G}) on electrical and optical properties, the origin of electrical conduction is verified as the effect of the high T{sub G}, which enhances crystal quality that provides higher mobility of electrons as well as more effective activation for the Al dopants. The optical bandgap increases from 3.30 eV for insulating ZnO to 3.77 eV for conducting AZO grown at high T{sub G}, and is associated with conduction-band filling up to 1.13 eV due to the Burstein-Moss effect.

  8. Thermodynamic prediction of glass formation tendency, cluster-in-jellium model for metallic glasses, ab initio tight-binding calculations, and new density functional theory development for systems with strong electron correlation

    SciTech Connect

    Yao, Yongxin

    2009-01-01

    Solidification of liquid is a very rich and complicated field, although there is always a famous homogeneous nucleation theory in a standard physics or materials science text book. Depending on the material and processing condition, liquid may solidify to single crystalline, polycrystalline with different texture, quasi-crystalline, amorphous solid or glass (Glass is a kind of amorphous solid in general, which has short-range and medium-range order). Traditional oxide glass may easily be formed since the covalent directional bonded network is apt to be disturbed. In other words, the energy landcape of the oxide glass is so complicated that system need extremely long time to explore the whole configuration space. On the other hand, metallic liquid usually crystalize upon cooling because of the metallic bonding nature. However, Klement et.al., (1960) reported that Au-Si liquid underwent an amorphous or “glassy” phase transformation with rapid quenching. In recent two decades, bulk metallic glasses have also been found in several multicomponent alloys[Inoue et al., (2002)]. Both thermodynamic factors (e.g., free energy of various competitive phase, interfacial free energy, free energy of local clusters, etc.) and kinetic factors (e.g., long range mass transport, local atomic position rearrangement, etc.) play important roles in the metallic glass formation process. Metallic glass is fundamentally different from nanocrystalline alloys. Metallic glasses have to undergo a nucleation process upon heating in order to crystallize. Thus the short-range and medium-range order of metallic glasses have to be completely different from crystal. Hence a method to calculate the energetics of different local clusters in the undercooled liquid or glasses become important to set up a statistic model to describe metalllic glass formation. Scattering techniques like x-ray and neutron have widely been used to study the structues of metallic glasses. Meanwhile, computer simulation

  9. The Theory of Electricity

    NASA Astrophysics Data System (ADS)

    Livens, G. H.

    2016-10-01

    Preface; 1. The electric field; 2. Dielectric theory; 3. Electric currents; 4. The magnetic field; 5. The dynamics of the magnetic field; 6. Maxwell's electromagnetic theory; 7. Electromagnetic oscillations and waves; 8. The electrodynamics of moving media; Appendix 1. On the mechanism of magnetic induction; Appendix 2. On the mechanism of metallic conduction; Index.

  10. Molecular and vibrational structure of tetroxo d0 metal complexes in their excited states. a study based on time-dependent density functional calculations and Franck-Condon theory.

    PubMed

    Jose, Linta; Seth, Michael; Ziegler, Tom

    2012-02-23

    We have applied time dependent density functional theory to study excited state structures of the tetroxo d(0) transition metal complexes MnO(4)(-), TcO(4)(-), RuO(4), and OsO(4). The excited state geometry optimization was based on a newly implemented scheme [Seth et al. Theor. Chem. Acc. 2011, 129, 331]. The first excited state has a C(3v) geometry for all investigated complexes and is due to a "charge transfer" transition from the oxygen based HOMO to the metal based LUMO. The second excited state can uniformly be characterized by "charge transfer" from the oxygen HOMO-1 to the metal LUMO with a D(2d) geometry for TcO(4)(-), RuO(4), and OsO(4) and two C(2v) geometries for MnO(4)(-). It is finally found that the third excited state of MnO(4)(-) representing the HOMO to metal based LUMO+1 orbital transition has a D(2d) geometry. On the basis of the calculated excited state structures and vibrational modes, the Franck-Condon method was used to simulate the vibronic structure of the absorption spectra for the tetroxo d(0) transition metal complexes. The Franck-Condon scheme seems to reproduce the salient features of the experimental spectra as well as the simulated vibronic structure for MnO(4)(-) generated from an alternative scheme [Neugebauer J. J. Phys. Chem. A 2005, 109, 1168] that does not apply the Franck-Condon approximation.

  11. Precipitation and surface adsorption of metal complexes during electropolishing. Theory and characterization with X-ray nanotomography and surface tension isotherms.

    PubMed

    Nave, Maryana I; Chen-Wiegart, Yu-chen Karen; Wang, Jun; Kornev, Konstantin G

    2015-09-21

    Electropolishing of metals often leads to supersaturation conditions resulting in precipitation of complex compounds. The solubility diagrams and Gibbs adsorption isotherms of the electropolishing products are thus very important to understand the thermodynamic mechanism of precipitation of reaction products. Electropolishing of tungsten wires in aqueous solutions of potassium hydroxide is used as an example illustrating the different thermodynamic scenarios of electropolishing. Electropolishing products are able to form highly viscous films immiscible with the surrounding electrolyte or porous shells adhered to the wire surface. Using X-ray nanotomography, we discovered a gel-like phase formed at the tungsten surface during electropolishing. The results of these studies suggest that the electropolishing products can form a rich library of compounds. The surface tension of the electrolyte depends on the metal oxide ions and alkali-metal complexes.

  12. To neither target, capture, surveille, nor wage war: On-going need for attention to metaphor theory in care and prevention for people who use drugs.

    PubMed

    Perlman, David C; Jordan, Ashly E

    2017-01-01

    Metaphors, and the frames they evoke, potently influence how people understand issues. These concepts of discourse, metaphor, and framing have been productively used in a range of studies including in the field of addiction. In public health and clinical discourse on people who use drugs, use of terms such as "targeting," "surveilling," and "capturing," along with "war on drugs" frames and referring to drug treatment as "substitution" may reinforce negative perceptions of people who use drugs. Avoiding military metaphors and explicitly leveraging metaphors that emphasize humanity, social cohesion, and agency have the potential to improve public health for people who use drugs.

  13. Fusion Energy Science Joint Facilities and Theory Research Target 2011: Final Report for the Period October 1, 2010 through September 30, 2011

    SciTech Connect

    Groebner, R. J.; Chang, C. S.; Diamond, P. H.; Hughes, J. W.; Maingi, R.; Snyder, P. B.; Xu, X. Q.

    2011-10-01

    Briefly stated, the goal of this combined experiment/theory milestone was to improve our knowledge of the physics processes that control the H-mode pedestal by applying models of these mechanisms to experimental data. A concerted and coordinated effort of experimental, theory and modeling activities has examined several physics mechanisms of interest, and has met the goals of the milestone. A few noteworthy results will be noted here. The activity has applied peeling-ballooning theory to all three machines, and increased confidence that the theory predicts the ultimate limits to pedestal height in an ELMing plasma. The activity has expanded the range of conditions for testing of the EPED model, and increased confidence in the ability of the model to compute the pedestal pressure height in medium aspect ratio tokamaks. Kinetic neoclassical models have been used to verify that an important analytic model for the pedestal bootstrap current has good accuracy in many regimes of interest but needs correction at high collisionality. A benchmarking effort between electromagnetic gyrokinetic codes has provided increased understanding of how to use these codes in the pedestal, and has laid the groundwork for using these codes to study linear stability of gyrokinetic modes in and on top of the pedestal. Comparisons of data and models have led to successful simulations of a quasi-coherent mode in C-Mod and to the tentative identification of a high frequency mode in DIII-D. A kinetic neoclassical model qualitatively agrees with some features of pedestal density profiles. A paleoclassical transport model quantitatively predicts some features of the electron temperature profiles in NSTX and DIII-D. The milestone activity also laid the groundwork for future advancements in understanding and predicting the pedestal. All three machines obtained a wealth of pedestal data under a wide variety of operating conditions. Some of these data have been analyzed already, and the analysis and

  14. Valence-Bond Concepts in Coordination Chemistry and the Nature of Metal-Metal Bonds.

    ERIC Educational Resources Information Center

    Pauling, Linus; Herman, Zelek S.

    1984-01-01

    Discusses the valence-bond method, applying it to some coordination compounds of metals, especially those involving metal-metal bonds. Suggests that transition metals can form as many as nine covalent bonds, permitting valence-theory to be extended to transition metal compounds in a more effective way than has been possible before. (JN)

  15. Combined atomistic-continuum model for simulation of laser interaction with metals: application in the calculation of melting thresholds in Ni targets of varying thickness

    NASA Astrophysics Data System (ADS)

    Ivanov, D. S.; Zhigilei, L. V.

    The threshold laser fluence for the onset of surface melting is calculated for Ni films of different thicknesses and for a bulk Ni target using a combined atomistic-continuum computational model. The model combines the classical molecular dynamics (MD) method for simulation of non-equilibrium processes of lattice superheating and fast phase transformations with a continuum description of the laser excitation and subsequent relaxation of the conduction band electrons based on the two-temperature model (TTM). In the hybrid TTM-MD method, MD substitutes the TTM equation for the lattice temperature, and the diffusion equation for the electron temperature is solved simultaneously with MD integration of the equations of motion of atoms. The dependence of the threshold fluence on the film thickness predicted in TTM-MD simulations qualitatively agrees with TTM calculations, while the values of the thresholds for thick films and bulk targets are 10% higher in TTM-MD. The quantitative differences between the predictions of TTM and TTM-MD demonstrate that the kinetics of laser melting as well as the energy partitioning between the thermal energy of atomic vibrations and energy of the collective atomic motion driven by the relaxation of the laser-induced pressure should be taken into account in interpretation of experimental results on surface melting.

  16. Growth of Cu2ZnSnSe4 thin films by selenization of sputtered single-layered Cu-Zn-Sn metallic precursors from a Cu-Zn-Sn alloy target

    NASA Astrophysics Data System (ADS)

    Kim, Kyoo-Ho; Amal, Ikhlasul

    2011-09-01

    Cu2ZnSnSe4 (CZTSe) thin films were prepared by the simple process of selenization of single-layered metallic Cu-Zn-Sn precursors. These metallic precursors were deposited by radio frequency magnetron sputtering of a ternary Cu-Zn-Sn alloy target. Successive selenization was performed at various temperatures between 250°C and 500°C for 30 min. X-ray diffraction and Raman analysis showed that a single phase of the CZTSe compound can be obtained by selenization at 400°C, while increasing the selenization temperature to 500°C improves the grain size and crystal quality. The direct optical band gap of CZTSe films was calculated to be 1.06 eV to 1.09 eV with a high absorption coefficient on the order of 104 cm-1 for samples selenized at 400°C to 500°C. The obtained films are p-type semiconductors with bulk carrier concentrations of 2.41 to 7.96 × 1018 cm3, mobilities of 1.30 cm2 V-1 s-1 to 9.27 cm2 V-1 s-1, and resistivities of 0.20 Ωcm to 1.95 Ωcm.

  17. A d-band bonding theory of the relative heats of solution of transition metal alloys and its relationship to solubility limits

    SciTech Connect

    Watson, R.E.; Bennett, L.H.; Goodman, D.A.

    1983-08-01

    The relative heats of solution of a transition metal in another and vice versa are derived within a Friedel d-band bonding model. The trend found in the heats parallels the trend observed previously in experimental relative solubilities. The implication of the solubility trend for surface segregation is also discussed.

  18. Potential Role of Energy Band Theory in Finite Solids and in Resonant Phenomena Involving Metal-Induced Fusion and the Fleischmann-Pons Effect

    NASA Astrophysics Data System (ADS)

    Chubb, Scott

    2009-03-01

    Considerable confusion occurred from a speculative conjecture that Talbot Chubb and I suggested in 1989, concerning the potential role of conventional energy band theory in the ``cold fusion'' claims, suggested by Fleischmann and Pons.ootnotetextDavid Lindley, Nature 344, 375 (1990).. Two important reasons for this are related to: 1. Misconceptions, about what was taking place in the experiments, and 2. Limitations of conventional energy band theory. In particular, Talbot Chubb and I proposed the idea that deuterium nuclei (deuterons) could occupy energy band states or have overlap with these kinds of states with ``unforeseen'' consequences, including, the possibility of nuclear fusion. Conventional energy band theory has limitations, associated with the underlying quantum mechanics. Talbot Chubb and I have investigated an important problem, relating to extending conventional energy band theory, as it applies to infinitely-repeating ordered crystals, to finite crystal lattices, where energy band theory can be re-expressed more precisely through resonant or nearly-resonant effects and the ``conventional'' Coulomb Barrier problem of fusion can be replaced by a considerably richer problem.

  19. Effect of metal in M3(btc)2 and M2(dobdc) MOFs for O2/N2 separations: A combined density functional theory and experimental study

    SciTech Connect

    Parkes, Marie V.; Sava Gallis, Dorina F.; Greathouse, Jeffery A.; Nenoff, Tina M.

    2015-03-02

    Computational screening of metal-organic framework (MOF) materials for selective oxygen adsorption from air could lead to new sorbents for the oxyfuel combustion process feedstock streams. A comprehensive study on the effect of MOF metal chemistry on gas binding energies in two common but structurally disparate metal-organic frameworks has been undertaken. Dispersion-corrected density functional theory methods were used to calculate the oxygen and nitrogen binding energies with each of fourteen metals, respectively, substituted into two MOF series, M2(dobdc) and M3(btc)2. The accuracy of DFT methods was validated by comparing trends in binding energy with experimental gas sorption measurements. A periodic trend in oxygen binding energies was found, with greater oxygen binding energies for early transition-metal-substituted MOFs compared to late transition metal MOFs; this was independent of MOF structural type. The larger binding energies were associated with oxygen binding in a side-on configuration to the metal, with concomitant lengthening of the O-O bond. In contrast, nitrogen binding energies were similar across the transition metal series, regardless of both MOF structural type and metal identity. Altogether, these findings suggest that early transition metal MOFs are best suited to separating oxygen from nitrogen, and that the MOF structural type is less important than the metal identity.

  20. Search for Two Categories of Target Produces Fewer Fixations to Target-Color Items

    ERIC Educational Resources Information Center

    Menneer, Tamaryn; Stroud, Michael J.; Cave, Kyle R.; Li, Xingshan; Godwin, Hayward J.; Liversedge, Simon P.; Donnelly, Nick

    2012-01-01

    Searching simultaneously for metal threats (guns and knives) and improvised explosive devices (IEDs) in X-ray images is less effective than 2 independent single-target searches, 1 for metal threats and 1 for IEDs. The goals of this study were to (a) replicate this dual-target cost for categorical targets and to determine whether the cost remains…

  1. Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals - II. Application to Fe2+ --> Ti4+ charge transfer transitions in oxides and silicates

    USGS Publications Warehouse

    Sherman, David M.

    1987-01-01

    A molecular orbital description, based on Xα-Scattered wave calculations on a (FeTiO10)14− cluster, is given for Fe2+ → Ti4+ charge transfer transitions in minerals. The calculated energy for the lowest Fe2+ → Ti4+ metal-metal charge transfer transition is 18040 cm−1 in reasonable agreement with energies observed in the optical spectra of Fe-Ti oxides and silicates. As in the case of Fe2+ → Fe3+ charge transfer in mixed-valence iron oxides and silicates, Fe2+ → Ti4+ charge transfer is associated with Fe-Ti bonding across shared polyhedral edges. Such bonding results from the overlap of the Fe(t 2g ) and Ti(t 2g ) 3d orbitals.

  2. Energies, charges, and sizes of clusters under ion sputtering of a metal

    SciTech Connect

    Matveev, V. I. Kochkin, S. A.

    2010-04-15

    A theory of ion sputtering of a metal in the form of neutral and singly charged clusters with a number of atoms of N {>=} 5 has been developed. This theory is based on simple physical assumptions and agrees well with experiment. The results are presented in the form of expressions convenient for practical use. The energy spectra of clusters, charge distributions, ionization coefficients, and total yields of neutral and singly charged clusters at different target temperatures are calculated in terms of the proposed theory as an example.

  3. Zeolitic polyoxometalate-based metal-organic frameworks (Z-POMOFs): computational evaluation of hypothetical polymorphs and the successful targeted synthesis of the redox-active Z-POMOF1.

    PubMed

    Rodriguez-Albelo, L Marleny; Ruiz-Salvador, A Rabdel; Sampieri, Alvaro; Lewis, Dewi W; Gómez, Ariel; Nohra, Brigitte; Mialane, Pierre; Marrot, Jérôme; Sécheresse, Francis; Mellot-Draznieks, Caroline; Ngo Biboum, Rosa; Keita, Bineta; Nadjo, Louis; Dolbecq, Anne

    2009-11-11

    The targeted design and simulation of a new family of zeolitic metal-organic frameworks (MOFs) based on benzenedicarboxylate (BDC) as the ligand and epsilon-type Keggin polyoxometalates (POMs) as building units, named here Z-POMOFs, have been performed. A key feature is the use of the analogy between the connectivity of silicon in dense minerals and zeolites with that of the epsilon-type Keggin POMs capped with Zn(II) ions. Handling the epsilon-Keggin as a building block, a selection of 21 zeotype structures, together with a series of dense minerals were constructed and their relative stabilities computed. Among these Z-POMOFs, the cristobalite-like structure was predicted to be the most stable structure. This prediction has been experimentally validated by the targeted synthesis of the first experimental Z-POMOF structure, which was strikingly found to possess the cristobalite topology, with three interpenetrated networks. Crystals of [NBu(4)](3)[PMo(V)(8)Mo(VI)(4)O(36)(OH)(4)Zn(4)(BDC)(2)].2H(2)O (Z-POMOF1) have been isolated under hydrothermal conditions from the reduction of ammonium heptamolybdate in the presence of phosphorous acid and Zn(II) ions. Tetrabutylammonium cations play the role of counterions and space-filling agents in this tridimensional interpenetrated framework. Moreover, the electrochemistry of the epsilon-Keggin POM is maintained and can be exploited in the insoluble Z-POMOF1 framework, as demonstrated by the electrocatalytic reduction of bromate.

  4. Circuit theory of Andreev conductance

    NASA Astrophysics Data System (ADS)

    Nazarov, Yuli V.

    1994-09-01

    Conductance of small normal metal structures adjacent to a superconductor is determined by coherent Andreev reflection. We show that under certain limitations the conductance can be found by means of an extended circuit theory. The theory deals with two types of elements: tunnel junctions and diffusive conductors and provides the basis for practical calculations. A new device proposed illustrates the advantages of the theory.

  5. Investigation of the encapsulation of metal cations (Cu(2+), Zn(2+), Ca(2+) and Ba(2+)) by the dipeptide Phe-Phe using natural bond orbital theory and molecular dynamics simulation.

    PubMed

    Bhunia, Snehasis; Singh, Ajeet; Ojha, Animesh K

    2017-03-01

    Complexes of the dipeptide phenylalanine-phenylalanine (Phe-Phe) with divalent metal cations (Cu(2+), Zn(2+), Ca(2+) and Ba(2+)) were studied at the B3LYP and MP2 levels of theory with the basis sets 6-311++G(d,p) and 6-31 + G(d) in the gas phase. The relative energies of these complexes indicated that cation-π bidentate/tridentate conformations are more favourable than other conformations with uncoordinated rings. These findings were confirmed by the calculated values of thermodynamic parameters such as the Gibbs free energy. Natural bond orbital (NBO) analysis was carried out to explore the metal-ligand coordination in Phe-Phe-Cu(2+)/Zn(2+) complexes. Possible orbital transitions, types of orbitals and their occupancies were determined for a range of Phe-Phe-Cu(2+)/Zn(2+) complexes. The charge transfer involved in various orbital transitions was explored by considering the second-order perturbation energy. NBO analysis revealed that the change transfer is stronger when the metal cation uses both the 4s + 4p subshells rather than just its 4p subshell. We also performed molecular dynamics (MD) simulations to check the stability and consistency of the most favourable binding motifs of Cu(2+), Zn(2+), Ca(2+) and Ba(2+) with Phe-Phe over time. The structures of the Phe-Phe-Cu(2+)/Zn(2+)/Ca(2+)/Ba(2+) complexes obtained using MD simulation were found to be in good agreement with those obtained in the DFT-based calculations. Graphical Abstract Conformational search on encapsulation of divalent metal cations (Ca(2+), Zn(2+), Ca(2+), Ba(2+)) by the Phe-Phe dipeptide.

  6. Effects of the adsorption of alkali metal oxides on the electronic, optical, and thermodynamic properties of the Mg12O12nanocage: a density functional theory study.

    PubMed

    Mohammadi Hesari, Asghar; Shamlouei, Hamid Reza; Raoof Toosi, Ali

    2016-08-01

    The effect of alkali metal oxides M n O (M = Li, Na, K; n = 2, 3, 4) on the geometric, electronic, and linear and nonlinear optical properties of the Mg12O12 nanocage was investigated by density-functional-based methods. According to the computational results, these alkali metal oxides are adsorbed on the Mg12O12 nanocage because this adsorption reduces its energy gap. The static first hyperpolarizability (β 0) of the nanocage is dramatically increased in the presence of the alkali metal oxides, with the greatest increase seen in the presence of the superalkalis (i.e., M3O; M = Li, Na, and K). The highest first hyperpolarizability (β 0 ≈ 600,000 a.u.) was calculated for K3O@Mg12O12, which was considerably more than that for Mg12O12. The thermodynamic properties and relative stabilities of these inorganic compounds are discussed. Graphical Abstract Optimized structure and DOS spectrum of K3O(e@Mg12O12).

  7. Metallated metal-organic frameworks

    DOEpatents

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-02-07

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  8. Determination of the structure factor of simple liquid metals from the pseudopotential theory and optimized random-phase approximation: Application to Al and Ga

    NASA Astrophysics Data System (ADS)

    Bretonnet, J. L.; Regnaut, C.

    1985-04-01

    We present the results of calculations of the static structure factor S(q) of liquid Al and Ga at the melting point. These calculations were motivated because many simple liquid metals exhibit structure anomalies taking the form of a shoulder on the main peak or even an asymmetry in the peak itself, while other liquid metals are correctly predicted by the standard models of liquid structure. Al and Ga have similar valence, electronic density, and size of their ionic radius; therefore, their pair potentials are somewhat similar. Despite this, their structure factors display most of the differences that can be observed among the variety of liquid metals. Starting from the Shaw optimized model potential [Phys. Rev. 174, 769 (1968)], a pair potential is constructed. A comparative examination of the electron-gas response function of Vashishta and Singwi [Phys. Rev. B 6, 875 (1972)] and of Ichimaru and Utsumi [Phys. Rev. B 24, 7385 (1981)] is carried out. Different depletion hole distributions are also used and full nonlocality is taken into account through effective masses. So S(q) is calculated by means of the optimized random-phase approximation. Particular attention is also devoted to the low-q region. By comparison with Monte Carlo computation, we show the limitation of various thermodynamic perturbation methods, such as the random-phase approximation or the soft-sphere model. The study of S(q) provides a stringent test of the model potential, where the electron-ion pseudopotential and the local-field correction are of prime importance, but where effective masses and depletion hole distribution may also have a role to play.

  9. Photoemission spectra and density functional theory calculations of 3d transition metal-aqua complexes (Ti-Cu) in aqueous solution.

    PubMed

    Yepes, Diana; Seidel, Robert; Winter, Bernd; Blumberger, Jochen; Jaque, Pablo

    2014-06-19

    Photoelectron spectroscopy measurements and density functional calculations are combined to determine the lowest electron binding energies of first-row transition-metal aqua ions, titanium through copper, with 3d(1) through 3d(9) electronic configurations, in their most common oxidation states. Vertical ionization energies are found to oscillate considerably between 6.76 and 9.65 eV for the dications and between 7.05 and 10.28 eV for the respective trivalent cations. The metal cations are modeled as [M(H2O)n](q+) clusters (q = 2, 3, and 4; n = 6 and 18) surrounded by continuum solvent. The performance of 10 exchange-correlation functionals, two GGAs, three MGGAs, two HGGAs and three HMGGAs, combined with the MDF10(ECP)/6-31+G(d,p) basis set is assessed for 11 M-O bond distances, 10 vertical ionization energies, 6 adiabatic ionization energies, and the associated reorganization free energies. We find that for divalent cations the HGGA and HMGGA functionals in combination with the 18 water model show the best agreement with experimental vertical ionization energies and geometries; for trivalent ions, the MGGA functionals perform best. The corresponding reorganization free energies (λo) of the oxidized ions are significantly underestimated with all DFT functionals and cluster models. This indicates that the structural reorganization of the solvation shell upon ionization is not adequately accounted for by the simple solvation models used, emphasizing the importance of extended sampling of thermally accessible solvation structures for an accurate computation of this quantity. The photoelectron spectroscopy measurements reported herein provide a comprehensive set of transition-metal redox energetic quantities for future electronic structure benchmarks.

  10. Theory of solid effect and cross effect dynamic nuclear polarization with half-integer high-spin metal polarizing agents in rotating solids.

    PubMed

    Corzilius, Björn

    2016-10-21

    Dynamic nuclear polarization (DNP) is a powerful method to enhance sensitivity especially of solid-state magic-angle spinning (MAS) NMR by up to several orders of magnitude. The increased interest both from a practical as well as theoretical viewpoint has spawned several fields of active research such as the development of new polarizing agents with improved or unique properties and description of the underlying DNP mechanisms such as solid effect (SE) and cross effect (CE). Even though a novel class of unique polarizing agents based on high-spin metal ions such as Gd(iii) and Mn(ii) has already been utilized for MAS DNP a theoretical description of the involved DNP mechanism is still incomplete. Here, we review several aspects of DNP-relevant electron-paramagnetic resonance (EPR) properties of the general class of these half-integer high-spin metal ions with isotropic Zeeman interaction but significant zero-field splitting (ZFS). While the SE can be relatively easily described similar to that of a S = 1/2 system and is assumed to be effective only for polarizing agents featuring a narrow central EPR transitions (i.e., mS = -1/2 → +1/2) with respect to the nuclear Larmor frequency, the CE between two high-spin ions requires a more detailed theoretical investigation due to a multitude of possible transitions and matching conditions. This is especially interesting in light of recent understanding of CE being induced by MAS-driven level anti-crossings (LACs) between dipolar-coupled electron spins. We discuss the requirements of such CE-enabling LACs to occur due to anisotropy of ZFS, the expected adiabaticity, and the resulting possibilities of high-spin metal ion pairs to act as polarizing agents for DNP. This theoretical description serves as a framework for a detailed experimental study published directly following this work.

  11. Astrophysical materials science: Theory

    NASA Technical Reports Server (NTRS)

    Ashcroft, N. W.

    1984-01-01

    A method of structural expansions for use in determining the equation of state of metallic hydrogen (and indeed other metals) up to the 4th order in the perturbation theory was developed. The electrical and thermal transport properties of the planetary interior of Jupiter were calculated. The nature of the interaction between molecules at short range and the importance of multicenter terms in arriving at an adequate description of the thermodynamic functions of condensed molecular hydrogen were also investigated.

  12. Mass Producing Targets for Nuclear Fusion

    NASA Technical Reports Server (NTRS)

    Wang, T. G.; Elleman, D. D.; Kendall, J. M.

    1983-01-01

    Metal-encapsulating technique advances prospects of controlling nuclear fusion. Prefilled fusion targets form at nozzle as molten metal such as tin flows through outer channel and pressurized deuterium/tritium gas flows through inner channel. Molten metal completely encloses gas charge as it drops off nozzle.

  13. Inertial-confinement-fusion targets

    SciTech Connect

    Hendricks, C.D.

    1981-11-16

    Inertial confinement fusion (ICF) targets are made as simple flat discs, as hollow shells or as complicated multilayer structures. Many techniques have been devised for producing the targets. Glass and metal shells are made by using drop and bubble techniques. Solid hydrogen shells are also produced by adapting old methods to the solution of modern problems. Some of these techniques, problems and solutions are discussed. In addition, the applications of many of the techniques to fabrication of ICF targets is presented.

  14. Tin Oxide Crystals Exposed by Low-Energy {110} Facets for Enhanced Electrochemical Heavy Metal Ions Sensing: X-ray Absorption Fine Structure Experimental Combined with Density-Functional Theory Evidence.

    PubMed

    Jin, Zhen; Yang, Meng; Chen, Shao-Hua; Liu, Jin-Huai; Li, Qun-Xiang; Huang, Xing-Jiu

    2017-02-21

    Herein, we revealed that the electrochemical behaviors on the detection of heavy metal ions (HMIs) would largely rely on the exposed facets of SnO2 nanoparticles. Compared to the high-energy {221} facet, the low-energy {110} facet of SnO2 possessed better electrochemical performance. The adsorption/desorption tests, density-functional theory (DFT) calculations, and X-ray absorption fine structure (XAFS) studies showed that the lower barrier energy of surface diffusion on {110} facet was critical for the superior electrochemical property, which was favorable for the ions diffusion on the electrode, and further leading the enhanced electrochemical performance. Through the combination of experiments and theoretical calculations, a reliable interpretation of the mechanism for electroanalysis of HMIs with nanomaterials exposed by different crystal facets has been provided. Furthermore, it provides a deep insight into understanding the key factor to improve the electrochemical performance for HMIs detection, so as to design high-performance electrochemical sensors.

  15. Electronic localization and bad-metallicity in pure and electron-doped troilite: A local-density-approximation plus dynamical-mean-field-theory study of FeS for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Craco, L.; Faria, J. L. B.

    2016-02-01

    Iron sulfides are promising candidates for the next generation of rechargeable lithium-ion battery materials. Motivated thereby, we present a detailed study of correlation- and doping-induced electronic reconstruction in troilite. Based on local-density-approximation plus dynamical-mean-field-theory, we stress the importance of multi-orbital Coulomb interactions in concert with first-principles band structure calculations for a consistent understanding of intrinsic Mott-Hubbard insulating state in FeS. We explore the anomalous nature of electron doping-induced insulator-bad metal transition, showing that it is driven by orbital-selective dynamical spectral weight transfer. Our results are relevant for understanding charge dynamics upon electrochemical lithiation of iron monosulfides electrode materials for lithium-ion batteries.

  16. Target-triggered signal turn-on detection of prostate specific antigen based on metal-enhanced fluorescence of Ag@SiO2@SiO2-RuBpy composite nanoparticles

    NASA Astrophysics Data System (ADS)

    Deng, Yun-Liang; Xu, Dang-Dang; Pang, Dai-Wen; Tang, Hong-Wu

    2017-02-01

    A three-layer core-shell nanostructure consisting of a silver core, a silica spacer, and a fluorescent dye RuBpy-doped outer silica layer was fabricated, and the optimal metal-enhanced fluorescence (MEF) distance was explored through adjusting the thickness of the silica spacer. The results show that the optimal distance is ˜10.4 nm with the maximum fluorescence enhancement factor 2.12. Then a new target-triggered MEF ‘turn-on’ strategy based on the optimized composite nanoparticles was successfully constructed for quantitative detection of prostate specific antigen (PSA), by using RuBpy as the energy donor and BHQ-2 as the acceptor. The hybridization of the complementary DNA of PSA-aptamer immobilized on the surface of the MEF nanoparticles with PSA-aptamer modified with BHQ-2, brought BHQ-2 in close proximity to RuBpy-doped silica shell and resulted in the decrease of fluorescence. In the presence of target PSA molecules, the BHQ-PSA aptamer is dissociated from the surface of the nanoparticles with the fluorescence switched on. Therefore, the assay of PSA was achieved by measuring the varying fluorescence intensity. The results show that PSA can be detected in the range of 1-100 ng ml-1 with a detection limit of 0.20 ng ml-1 (6.1 pM), which is 6.7-fold increase of that using hollow RuBpy-doped silica nanoparticles. Moreover, satisfactory results were obtained when PSA was detected in 1% serum.

  17. Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT)

    NASA Astrophysics Data System (ADS)

    Maurer, Reinhard J.; Reuter, Karsten

    2013-07-01

    Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)], 10.1103/PhysRevB.78.075441 presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

  18. Metallic field effect transistors

    NASA Astrophysics Data System (ADS)

    Farooq, Hassan

    This thesis investigates the principle of operation behind metallic-field effect transistors (METFETs) through a systematic study of atomistic simulations performed on metallic bulk, nanowire and transistor structures. In particular, density functional theory (DFT) and non-equilibrium green's function (NEGF) based models were used to study the effect on the bandstructure and density of states of highly scaled metallic nanowires with varying parameters such as crystal orientation, cross-sectional area, and applied external bias. Similarly, the effect of varying similar parameters on the transfer and output characteristics of highly scaled metallic transistors was studied. Furthermore, oxide interfaces with metallic channels were investigated. The simulation results show that a gold METFET in the [100] crystal orientation has an I ON /IOFF ratio of 41, ION of 29.5microA and fT of 6.7THz, outperforming similarly sized MOSFETs as a promising alternative for use in high-frequency circuits.

  19. Separations chemistry of toxic metals

    SciTech Connect

    Smith, P.; Barr, M.; Barrans, R.

    1996-04-01

    Sequestering and removing toxic metal ions from their surroundings is an increasingly active area of research and is gaining importance in light of current environmental contamination problems both within the DOE complex and externally. One method of separating metal ions is to complex them to a molecule (a ligand or chelator) which exhibits specific binding affinity for a toxic metal, even in the presence of other more benign metals. This approach makes use of the sometimes subtle differences between toxic and non-toxic metals resulting from variations in size, charge and shape. For example, toxic metals such as chromium, arsenic, and technetium exist in the environment as oxyanions, negatively charged species with a characteristic tetrahedral shape. Other toxic metals such as actinides and heavy metals are positively charged spheres with specific affinities for particular donor atoms such as oxygen (for actinides) and nitrogen (for heavy metals). In most cases the toxic metals are found in the presence of much larger quantities of less toxic metals such as sodium, calcium and iron. The selectivity of the chelators is critical to the goal of removing the toxic metals from their less toxic counterparts. The approach was to build a ligand framework that complements the unique characteristics of the toxic metal (size, charge and shape) while minimizing interactions with non-toxic metals. The authors have designed ligands exhibiting specificity for the target metals; they have synthesized, characterized and tested these ligands; and they have shown that they exhibit the proposed selectivity and cooperative binding effects.

  20. Ab initio and coupled-perturbed density functional theory estimation of zero-field splittings in MnII transition metal complexes.

    PubMed

    Zein, Samir; Neese, Frank

    2008-08-28

    The paper presents a method comparison for the prediction of zero-field splitting (ZFS) parameters in a series of Mn (II) coordination complexes. The test set consists of Mn (II) complexes that are experimentally well-characterized by X-ray diffraction and high-field electron paramagnetic resonance. Their ZFS parameters have been calculated using density functional theory (DFT) as well as complete active space self-consistent field (CASSCF) methods. It is shown that the recently introduced coupled-perturbed spin-orbit coupling (CP-SOC) approach [ Neese, F. J. Chem. Phys. 2007, 127, 164112 ] together with hybrid-DFT functionals leads to a slope of the correlation line (plot of experimental vs calculated D values) that is essentially unity provided that the direct spin-spin interaction is properly included in the treatment. This is different from our previous DFT study on the same series of complexes where a severe overestimation of the D parameter has been found [ Zein, S. ; Duboc, C. ; Lubitz, W. ; Neese, F. Inorg. Chem. 2008, 47, 134 ]. CASSCF methods have been used to evaluate the ZFS in an "ab initio ligand-field" type treatment. The study demonstrates that a substantial part of the relevant physics is lost in such a treatment since only excitations within the manganese d-manifold are accounted for. Thus, a severe underestimation of the D parameter has been found. Because the CASSCF calculations in combination with quasidegenerate perturbation theory treats the SOC to all orders, we have nevertheless verified that second-order perturbation theory is an adequate approximation in the case of the high-spin d (5) configuration.

  1. Impact of d -band filling on the dislocation properties of bcc transition metals: The case of tantalum-tungsten alloys investigated by density-functional theory

    NASA Astrophysics Data System (ADS)

    Li, Hong; Draxl, Claudia; Wurster, Stefan; Pippan, Reinhard; Romaner, Lorenz

    2017-03-01

    We address the impact of tantalum alloying on dislocation properties of tungsten. To that aim, we calculate elastic constants, atomic-row displacement energy, dislocation core energy, and Peierls stress for different degrees of alloying within the framework of density-functional theory. We show that the elastic shear constants decrease monotonously with Ta content. Conversely, atomic-row displacement energy and, consequently, core energy and Peierls stress show a nonmonotonous behavior. These quantities peak at 25 at% Ta, indicating a tendency for embrittlement of W at such alloying concentrations. Our findings are in agreement with the experimental literature.

  2. Sputter target

    DOEpatents

    Gates, Willard G.; Hale, Gerald J.

    1980-01-01

    The disclosure relates to an improved sputter target for use in the deposition of hard coatings. An exemplary target is given wherein titanium diboride is brazed to a tantalum backing plate using a gold-palladium-nickel braze alloy.

  3. Metals Sector

    EPA Pesticide Factsheets

    Find environmental regulatory information about the metals sector (NAICS 331 & 332), including NESHAPs for metal coatings, effluent guidelines for metal products, combustion compliance assistance, and information about foundry sand recycling.

  4. Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

    DOEpatents

    Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

    2017-01-24

    The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

  5. Metal aminoboranes

    DOEpatents

    Burrell, Anthony K.; Davis, Benjamin J.; Thorn, David L.; Gordon, John C.; Baker, R. Thomas; Semelsberger, Troy Allen; Tumas, William; Diyabalanage, Himashinie Vichalya Kaviraj; Shrestha, Roshan P.

    2010-05-11

    Metal aminoboranes of the formula M(NH.sub.2BH.sub.3).sub.n have been synthesized. Metal aminoboranes are hydrogen storage materials. Metal aminoboranes are also precursors for synthesizing other metal aminoboranes. Metal aminoboranes can be dehydrogenated to form hydrogen and a reaction product. The reaction product can react with hydrogen to form a hydrogen storage material. Metal aminoboranes can be included in a kit.

  6. Nuclear target development

    SciTech Connect

    Greene, J.P.; Thomas, G.E.

    1995-08-01

    The Physics Division operates a target development laboratory that produces thin foil targets needed for experiments performed at the ATLAS and Dynamitron accelerators. Targets are not only produced for the Physics Division but also for other divisions and occasionally for other laboratories and universities. In the past year, numerous targets were fabricated by vacuum evaporation either as self-supporting foils or on various substrates. Targets produced included Ag, Au, {sup 10,11}B, {sup 138}Ba, Be, {sup 12}C, {sup 40}Ca, {sup 116}Cd, {sup 155,160}Gd, {sup 76}Ge, In, LID, {sup 6}LiH, Melamine, Mg, {sup 142,150}Nd, {sup 58}Ni, {sup 206,208}Pb, {sup 194}Pt, {sup 28}Si, {sup 144,148}Sm, {sup 120,122,124}Sn, Ta, {sup 130}Te, ThF{sub 4}, {sup 46,50}Ti, TiH, U, UF{sub 4}, {sup 182}W and {sup 170}Yb. Polypropylene and aluminized polypropylene, along with metallized Mylar were produced for experiments at ATLAS. A number of targets of {sup 11}B of various thickness were made for the DEP 2-MeV Van de Graff accelerator. An increased output of foils fabricated using our small rolling mill included targets of Au, C, {sup 50}Cr, Cu, {sup 155,160}Gd, Mg, {sup 58}Ni, {sup 208}Pb, {sup 105,110}Pd. Sc, Ti, and {sup 64,66}Zn.

  7. Time dependent density functional theory study of the near-edge x-ray absorption fine structure of benzene in gas phase and on metal surfaces.

    PubMed

    Asmuruf, Frans A; Besley, Nicholas A

    2008-08-14

    The near-edge x-ray absorption fine structure of benzene in the gas phase and adsorbed on the Au(111) and Pt(111) surfaces is studied with time dependent density functional theory. Excitation energies computed with hybrid exchange-correlation functionals are too low compared to experiment. However, after applying a constant shift the spectra are in good agreement with experiment. For benzene on the Au(111) surface, two bands arising from excitation to the e(2u)(pi(*)) and b(2g)(pi(*)) orbitals of benzene are observed for photon incidence parallel to the surface. On Pt(111) surface, a broader band arises from excitation to benzene orbitals that are mixed with the surface and have both sigma(*)(Pt-C) and pi(*) characters.

  8. Assessment of density functional theory optimized basis sets for gradient corrected functionals to transition metal systems: the case of small Nin (n

    PubMed

    López Arvizu, Gregorio; Calaminici, Patrizia

    2007-05-21

    Density functional calculations have been performed for small nickel clusters, Ni(n), Ni(n) (+), and Ni(n)(-) (ntheory approach. Newly developed nickel all-electron basis sets optimized for generalized gradient approximation (GGA) as well as an all-electron basis set optimized for the local density approximation were employed. For both neutral and charged systems, several isomers and different multiplicities were studied in order to determine the lowest energy structures. A vibrational analysis was performed in order to characterize these isomers. Structural parameters, harmonic frequencies, binding energies, ionization potentials, and electron affinities are reported. This work shows that the employed GGA basis sets for the nickel atom are important for the correct prediction of the ground state structures of small nickel clusters and that the structural assignment of these systems can be performed, with a good resolution, over the ionization potential.

  9. Spin-rotational-invariant theory of transition-metal magnetism at finite temperatures: Systematic study of a single-site model

    NASA Astrophysics Data System (ADS)

    Pastor, G. M.; Dorantes-Dávila, J.

    2016-06-01

    A spin-rotational-invariant approach to the spin-fluctuation theory of itinerant-electron magnetism is proposed and evaluated in the framework of a d -band model Hamiltonian including intra-atomic exchange interactions J and the coupling to a local magnetic field B . Using a vector-field Hubbard-Stratonovich transformation, we obtain a static approximation to the density matrix operator from which the equilibrium properties are directly derived. The method is applied to a single-site model taking Fe as a representative example. Exact and approximate analytical results are given for the local magnetic moments, their longitudinal and transversal components, the field-induced magnetizations, entropy, and heat capacity. Goals and limitations of various approximations are discussed as a function of J ,B , and temperature. The quantum-mechanical origin of some important drawbacks found in previous vector-field static approaches is identified. The significant improvements achieved with the static density operator are demonstrated.

  10. Anticancer Activity of Metal Complexes: Involvement of Redox Processes

    PubMed Central

    Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K.; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

    2012-01-01

    Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology. PMID:21275772

  11. CONDENSED MATTER: ELECTRONIC STRUCTURE, ELECTRICAL, MAGNETIC, AND OPTICAL PROPERTIES: Study of Thermodynamics of Liquid Noble-Metals Alloys Through a Pseudopotential Theory

    NASA Astrophysics Data System (ADS)

    Vora, Aditya M.

    2010-09-01

    The Gibbs-Bogoliubov (GB) inequality is applied to investigate the thermodynamic properties of some equiatomic noble metal alloys in liquid phase such as Au-Cu, Ag-Cu, and Ag-Au using well recognized pseudopotential formalism. For description of the structure, well known Percus-Yevick (PY) hard sphere model is used as a reference system. By applying a variation method the best hard core diameters have been found which correspond to minimum free energy. With this procedure the thermodynamic properties such as entropy and heat of mixing have been computed. The influence of local field correction function viz; Hartree (H), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F), and Sarkar et al. (S) is also investigated. The computed results of the excess entropy compares favourably in the case of liquid alloys while the agreement with experiment is poor in the case of heats of mixing. This may be due to the sensitivity of the heats of mixing with the potential parameters and the dielectric function.

  12. Integrating intervention targets offered by homeostatic theory

    PubMed Central

    Annunziato, Rachel A; Grossman, Stephanie L

    2016-01-01

    Marks presents “homeostatic theory” which proposes that weight gain is fostered by a “Circle of Discontent” consisting of body dissatisfaction, negative affect, and overconsumption. This innovative framework offers potential intervention approaches, including victim-blaming, stigma, and discrimination, as well as devalorizing the thin-ideal. Our article discusses possible ways that clinical health psychologists based in university settings may be uniquely positioned to consider and implement large-scale programs that have shown great promise for addressing these core issues. PMID:28070390

  13. Tune-out wavelengths of alkali-metal atoms and their applications

    SciTech Connect

    Arora, Bindiya; Safronova, M. S.; Clark, Charles W.

    2011-10-15

    Using first-principles calculations, we identify ''tune-out'' optical wavelengths, {lambda}{sub zero}, for which the ground-state frequency-dependent polarizabilities of alkali-metal atoms vanish. Our approach uses high-precision, relativistic all-order method in which all single, double, and partial triple excitations of the Dirac-Fock wave functions are included to all orders of perturbation theory. We discuss the use of tune-out wavelengths for sympathetic cooling in two-species mixtures of alkali metals with group II and other elements of interest. Special cases in which these wavelengths coincide with strong resonance transitions in a target system are identified.

  14. Benchmarking density functional theory predictions of framework structures and properties in a chemically diverse test set of metal-organic frameworks

    SciTech Connect

    Nazarian, Dalar; Ganesh, P.; Sholl, David S.

    2015-01-01

    We compiled a test set of chemically and topologically diverse Metal–Organic Frameworks (MOFs) with high accuracy experimentally derived crystallographic structure data. The test set was used to benchmark the performance of Density Functional Theory (DFT) functionals (M06L, PBE, PW91, PBE-D2, PBE-D3, and vdW-DF2) for predicting lattice parameters, unit cell volume, bonded parameters and pore descriptors. On average PBE-D2, PBE-D3, and vdW-DF2 predict more accurate structures, but all functionals predicted pore diameters within 0.5 Å of the experimental diameter for every MOF in the test set. The test set was also used to assess the variance in performance of DFT functionals for elastic properties and atomic partial charges. The DFT predicted elastic properties such as minimum shear modulus and Young's modulus can differ by an average of 3 and 9 GPa for rigid MOFs such as those in the test set. Moreover, we calculated the partial charges by vdW-DF2 deviate the most from other functionals while there is no significant difference between the partial charges calculated by M06L, PBE, PW91, PBE-D2 and PBE-D3 for the MOFs in the test set. We find that while there are differences in the magnitude of the properties predicted by the various functionals, these discrepancies are small compared to the accuracy necessary for most practical applications.

  15. Pressure-induced loss of electronic interlayer state and metallization in the ionic solid Li[subscript 3]N: Experiment and theory

    SciTech Connect

    Lazicki, A.; Yoo, C.W.; Evans, W.J.; Hu, M.Y.; Chow, P.; Pickett, W.E.

    2008-12-08

    Results of x-ray diffraction and nitrogen K-edge x-ray Raman scattering (XRS) investigations of the crystal and electronic structure of ionic compound Li{sub 3}N across two high-pressure phase transitions [A. Lazicki et al., Phys. Rev. Lett. 95, 165503 (2005)] are interpreted using density-functional theory. A low-energy peak in the XRS spectrum which is observed in both low-pressure hexagonal phases of Li3N and absent in the high-pressure cubic phase is found to originate from an interlayer band similar to the important free-electron-like state present in the graphite and graphite intercalated systems, but not observed previously in ionic insulators. XRS detection of the interlayer state is made possible because of its strong hybridization with the nitrogen p bands. A pressure-induced increase in the band gap of the high-pressure cubic phase of Li{sub 3}N is explained by the differing pressure dependencies of different quantum-number bands and is shown to be a feature of several low-Z closed-shell ionic materials.

  16. Density Functional Theory Based Kinetic Monte Carlo Approach for Understanding Atomistic Mechanisms for Reversible Hydrogen Storage in Metal Hydrides: Application to Alane Formation on Ti Doped Al Surfaces

    NASA Astrophysics Data System (ADS)

    Karim, A.; Muckerman, J.; Sutter, P.; Muller, E.

    2008-03-01

    We describe a density functional kinetic Monte Carlo approach enabling us to study and simulate the steady-state situation of dissociative adsorption of hydrogen along with diffusion and reaction of Al and H atoms leading towards the formation of alane species on Ti-doped Al surfaces. In the first step, density functional theory is used in conjunction with the nudged elastic band/drag method to obtain the energetics of the relevant atomistic processes of Al and H diffusion and their reactions on Al surfaces with different concentration of dopant Ti atoms. Subsequently, the kinetic Monte Carlo method is employed, which accounts for the spatial distribution, fluctuations, and evolution of chemical species at Ti-doped Al surfaces under steady-state conditions. This DFT-based KMC approach provides an insight into the kinetics of alanes at technologically relevant pressure and temperature conditions. Our computed production rates of AlH3 on Al surfaces are in agreement with experimental data. We also obtained temperature programmed desorption spectra of different alane species, which is agreeing well with experiments.

  17. String Theory and Gauge Theories

    SciTech Connect

    Maldacena, Juan

    2009-02-20

    We will see how gauge theories, in the limit that the number of colors is large, give string theories. We will discuss some examples of particular gauge theories where the corresponding string theory is known precisely, starting with the case of the maximally supersymmetric theory in four dimensions which corresponds to ten dimensional string theory. We will discuss recent developments in this area.

  18. Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

    SciTech Connect

    Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, Nils; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira

    2013-05-30

    Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.

  19. Benchmarking density functional theory predictions of framework structures and properties in a chemically diverse test set of metal-organic frameworks

    DOE PAGES

    Nazarian, Dalar; Ganesh, P.; Sholl, David S.

    2015-01-01

    We compiled a test set of chemically and topologically diverse Metal–Organic Frameworks (MOFs) with high accuracy experimentally derived crystallographic structure data. The test set was used to benchmark the performance of Density Functional Theory (DFT) functionals (M06L, PBE, PW91, PBE-D2, PBE-D3, and vdW-DF2) for predicting lattice parameters, unit cell volume, bonded parameters and pore descriptors. On average PBE-D2, PBE-D3, and vdW-DF2 predict more accurate structures, but all functionals predicted pore diameters within 0.5 Å of the experimental diameter for every MOF in the test set. The test set was also used to assess the variance in performance of DFT functionalsmore » for elastic properties and atomic partial charges. The DFT predicted elastic properties such as minimum shear modulus and Young's modulus can differ by an average of 3 and 9 GPa for rigid MOFs such as those in the test set. Moreover, we calculated the partial charges by vdW-DF2 deviate the most from other functionals while there is no significant difference between the partial charges calculated by M06L, PBE, PW91, PBE-D2 and PBE-D3 for the MOFs in the test set. We find that while there are differences in the magnitude of the properties predicted by the various functionals, these discrepancies are small compared to the accuracy necessary for most practical applications.« less

  20. Targets for the production of radioisotopes and method of assembly

    DOEpatents

    Quinby, Thomas C.

    1976-01-01

    A target for preparation of radioisotopes by nuclear bombardment, and a method for its assembly are provided. A metallic sample to be bombarded is enclosed within a metallic support structure and the resulting target subjected to heat and pressure to effect diffusion bonds therebetween. The bonded target is capable of withstanding prolonged exposure to nuclear bombardment without thermal damage to the sample.

  1. Liquid metal enabled pump

    PubMed Central

    Tang, Shi-Yang; Khoshmanesh, Khashayar; Sivan, Vijay; Petersen, Phred; O’Mullane, Anthony P.; Abbott, Derek; Mitchell, Arnan; Kalantar-zadeh, Kourosh

    2014-01-01

    Small-scale pumps will be the heartbeat of many future micro/nanoscale platforms. However, the integration of small-scale pumps is presently hampered by limited flow rate with respect to the input power, and their rather complicated fabrication processes. These issues arise as many conventional pumping effects require intricate moving elements. Here, we demonstrate a system that we call the liquid metal enabled pump, for driving a range of liquids without mechanical moving parts, upon the application of modest electric field. This pump incorporates a droplet of liquid metal, which induces liquid flow at high flow rates, yet with exceptionally low power consumption by electrowetting/deelectrowetting at the metal surface. We present theory explaining this pumping mechanism and show that the operation is fundamentally different from other existing pumps. The presented liquid metal enabled pump is both efficient and simple, and thus has the potential to fundamentally advance the field of microfluidics. PMID:24550485

  2. Density Functional Theory in Transition-Metal Chemistry: Relative Energies of Low-Lying States of Iron Compounds and the Effect of Spatial Symmetry Breaking

    SciTech Connect

    Sorkin, Anastassia; Iron, Mark A.; Truhlar, Donald G.

    2008-02-01

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The ground and lower excited states of Fe2, Fe2 -, and FeO+ were studied using a number of density functional theory (DFT) methods. Specific attention was paid to the relative state energies, the internuclear distances (re), and the harmonic vibrational frequencies (öe). A number of factors influencing the calculated values of these properties were examined. These include basis sets, the nature of the density functional chosen, the percentage of Hartree- Fock exchange in the density functional, and constraints on orbital symmetry. A number of different types of generalized gradient approximation (GGA) density functionals (straight GGA, hybrid GGA, meta-GGA, and hybrid meta-GGA) were examined, and it was found that the best results were obtained with hybrid GGA or hybrid meta-GGA functionals that contain nonzero fractions of HF exchange; specifically, the best overall results were obtained with B3LYP, M05, and M06, closely followed by B1LYP. One significant observation was the effect of enforcing symmetry on the orbitals. When a degenerate orbital (ð or ä) is partially occupied in the 4¼ excited state of FeO+, reducing the enforced symmetry (from C6v to C4v to C2v) results in a lower energy since these degenerate orbitals are split in the lower symmetries. The results obtained were compared to higher level ab initio results from the literature and to recent PBE+U plane wave results by Kulik et al. (Phys. Rev. Lett. 2006, 97, 103001). It was found that some of the improvements that were afforded by the semiempirical +U correction can also be accomplished by improving the form of the DFT functional and, in one case, by not enforcing high symmetry on the orbitals.

  3. Hydrogen interactions with metals

    NASA Technical Reports Server (NTRS)

    Mclellan, R. B.; Harkins, C. G.

    1975-01-01

    Review of the literature on the nature and extent of hydrogen interactions with metals and the role of hydrogen in metal failure. The classification of hydrogen-containing systems is discussed, including such categories as covalent hydrides, volatile hydrides, polymeric hydrides, and transition metal hydride complexes. The use of electronegativity as a correlating parameter in determining hydride type is evaluated. A detailed study is made of the thermodynamics of metal-hydrogen systems, touching upon such aspects as hydrogen solubility, the positions occupied by hydrogen atoms within the solvent metal lattice, the derivation of thermodynamic functions of solid solutions from solubility data, and the construction of statistical models for hydrogen-metal solutions. A number of theories of hydrogen-metal bonding are reviewed, including the rigid-band model, the screened-proton model, and an approach employing the augmented plane wave method to solve the one-electron energy band problem. Finally, the mechanism of hydrogen embrittlement is investigated on the basis of literature data concerning stress effects and the kinetics of hydrogen transport to critical sites.

  4. Geographical Theories.

    ERIC Educational Resources Information Center

    Golledge, Reginald G.

    1996-01-01

    Discusses the origin of theories in geography and particularly the development of location theories. Considers the influence of economic theory on agricultural land use, industrial location, and geographic location theories. Explores a set of interrelated activities that show how the marketing process illustrates process theory. (MJP)

  5. Adsorption and migration of single metal atoms on the calcite (10.4) surface.

    PubMed

    Pinto, H; Haapasilta, V; Lokhandwala, M; Öberg, S; Foster, Adam S

    2017-04-05

    Transition metal atoms are one of the key ingredients in the formation of functional 2D metal organic coordination networks. Additionally, the co-deposition of metal atoms can play an important role in anchoring the molecular structures to the surface at room temperature. To gain control of such processes requires the understanding of adsorption and diffusion properties of the different transition metals on the target surface. Here, we used density functional theory to investigate the adsorption of 3d (Ti, Cr, Fe, Ni, Cu), 4d (Zr, Nb, Mo, Pd, Ag) and 5d (Hf, W, Ir, Pt, Au) transition metal adatoms on the insulating calcite (10.4) surface. We identified the most stable adsorption sites and calculated binding energies and corresponding ground state structures. We find that the preferential adsorption sites are the Ca-Ca bridge sites. Apart from the Cr, Mo, Cu, Ag and Au all the studied metals bind strongly to the calcite surface. The calculated migration barriers for the representative Ag and Fe atoms indicates that the metal adatoms are mobile on the calcite surface at room temperature. Bader analysis suggests that there is no significant charge transfer between the metal adatoms and the calcite surface.

  6. Adsorption and migration of single metal atoms on the calcite (10.4) surface

    NASA Astrophysics Data System (ADS)

    Pinto, H.; Haapasilta, V.; Lokhandwala, M.; Öberg, S.; Foster, Adam S.

    2017-04-01

    Transition metal atoms are one of the key ingredients in the formation of functional 2D metal organic coordination networks. Additionally, the co-deposition of metal atoms can play an important role in anchoring the molecular structures to the surface at room temperature. To gain control of such processes requires the understanding of adsorption and diffusion properties of the different transition metals on the target surface. Here, we used density functional theory to investigate the adsorption of 3d (Ti, Cr, Fe, Ni, Cu), 4d (Zr, Nb, Mo, Pd, Ag) and 5d (Hf, W, Ir, Pt, Au) transition metal adatoms on the insulating calcite (10.4) surface. We identified the most stable adsorption sites and calculated binding energies and corresponding ground state structures. We find that the preferential adsorption sites are the Ca–Ca bridge sites. Apart from the Cr, Mo, Cu, Ag and Au all the studied metals bind strongly to the calcite surface. The calculated migration barriers for the representative Ag and Fe atoms indicates that the metal adatoms are mobile on the calcite surface at room temperature. Bader analysis suggests that there is no significant charge transfer between the metal adatoms and the calcite surface.

  7. The Application of DFT to Systems Containing Metal Atoms

    NASA Technical Reports Server (NTRS)

    Ricca, Alessandra; Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)

    1996-01-01

    The application of density functional theory (DFT) to a series of metal containing systems will be described. The focus will be on the calculation of accurate bond energies, especially metal-ligand successive bond energies. The DFT results will be compared with experiment and other levels of theory. If time permits, metal clusters will also be discussed.

  8. Targets and processes for fabricating same

    SciTech Connect

    Cowna, Thomas; Malekos, Steven; Korgan, Grant; Adams, Jesse; Sentoku, Yasuhiko; LeGalloudec, Nathalie

    2014-06-10

    In particular embodiments, the present disclosure provides targets including a metal layer and defining a hollow inner surface. The hollow inner surface has an internal apex. The distance between at least two opposing points of the internal apex is less than about 15 .mu.m. In particular examples, the distance is less than about 1 .mu.m. Particular implementations of the targets are free standing. The targets have a number of disclosed shaped, including cones, pyramids, hemispheres, and capped structures. The present disclosure also provides arrays of such targets. Also provided are methods of forming targets, such as the disclosed targets, using lithographic techniques, such as photolithographic techniques. In particular examples, a target mold is formed from a silicon wafer and then one or more sides of the mold are coated with a target material, such as one or more metals.

  9. Targets and processes for fabricating same

    DOEpatents

    Adams, Jesse D; Malekos, Steven; Le Galloudec, Nathalie; Korgan, Grant; Cowan, Thomas; Sentoku, Yasuhiko

    2016-05-17

    In particular embodiments, the present disclosure provides targets including a metal layer and defining a hollow inner surface. The hollow inner surface has an internal apex. The distance between at least two opposing points of the internal apex is less than about 15 .mu.m. In particular examples, the distance is less than about 1 .mu.m. Particular implementations of the targets are free standing. The targets have a number of disclosed shaped, including cones, pyramids, hemispheres, and capped structures. The present disclosure also provides arrays of such targets. Also provided are methods of forming targets, such as the disclosed targets, using lithographic techniques, such as photolithographic techniques. In particular examples, a target mold is formed from a silicon wafer and then one or more sides of the mold are coated with a target material, such as one or more metals.

  10. Targets and processes for fabricating same

    DOEpatents

    Cowan, Thomas [Dresden, DE; Malekos, Steven [Reno, NV; Korgan, Grant [Reno, NV; Adams, Jesse [Reno, NV; Sentoku, Yasuhiko [Reno, NV; Le Galloudec, Nathalie [Reno, NV; Fuchs, Julien [Paris, FR

    2012-07-24

    In particular embodiments, the present disclosure provides targets including a metal layer and defining a hollow inner surface. The hollow inner surface has an internal apex. The distance between at least two opposing points of the internal apex is less than about 15 .mu.m. In particular examples, the distance is less than about 1 .mu.m. Particular implementations of the targets are free standing. The targets have a number of disclosed shaped, including cones, pyramids, hemispheres, and capped structures. The present disclosure also provides arrays of such targets. Also provided are methods of forming targets, such as the disclosed targets, using lithographic techniques, such as photolithographic techniques. In particular examples, a target mold is formed from a silicon wafer and then one or more sides of the mold are coated with a target material, such as one or more metals.

  11. Metal inks

    DOEpatents

    Ginley, David S; Curtis, Calvin J; Miedaner, Alex; van Hest, Marinus Franciscus Antonius Maria; Kaydanova, Tatiana

    2014-02-04

    Self-reducing metal inks and systems and methods for producing and using the same are disclosed. In an exemplary embodiment, a method may comprise selecting metal-organic (MO) precursor, selecting a reducing agent, and dissolving the MO precursor and the reducing agent in an organic solvent to produce a metal ink that remains in a liquid phase at room temperature. Metal inks, including self-reducing and fire-through metal inks, are also disclosed, as are various applications of the metal inks.

  12. Buried metalic object identification by EMI sensor

    NASA Astrophysics Data System (ADS)

    Sezgin, Mehmet; Kaplan, Gülay; Birim, Melih; Bahadırlar, Yıldırım

    2007-04-01

    Electromagnetic Induction sensor (Metal Detector) has wide application areas for buried metallic object searching, such as detection of buried pipes, mine and mine like-targets, etc. In this paper, identification of buried metallic objects was studied. The distinctive features of the signal were obtained, than classification process was performed. Identification process was realized by utilizing k-Nearest neighbor and Neural Network Classifiers.

  13. Double circular erosion patterns on dielectric target in magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Suzaki, Yoshifumi; Miyagawa, Hayato; Ejima, Seiki

    2009-10-01

    In rf magnetron sputtering, a circular erosion pattern forms on the surface of a circular metal conductor target with permanent magnets on its back. In this case, the theory behind the erosion pattern has been established. However, in the case of a dielectric target, a double circular erosion pattern is formed. So far, this pattern has been phenomenologically recognized by experimenters; however, it has not yet been investigated. In this study, we performed a magnetron sputtering experiment with a SiO2 dielectric target, and confirmed the formation of a double circular erosion pattern. The dimensions of the double circular erosion pattern varied depending on the insulation resistance or the thickness of the SiO2 target. Furthermore, we found that the dimensions of a double circular erosion pattern changed by making a gap between the SiO2 target and guard ring. Based on the experimental results, we have proposed a qualitative model to explain the formation mechanism of double circular erosion patterns.

  14. Educational Theory

    ERIC Educational Resources Information Center

    Schubert, Leo

    1973-01-01

    Briefly describes two antagonistic learning theories: the Association Theory proposed by Skinner and the Field or Cognitive Theory supported by Piaget. Suggests the need for consistency in theoretical approach in the teaching of science at the college level. (JR)

  15. Supported Molten Metal Membranes for Hydrogen Separation

    SciTech Connect

    Datta, Ravindra; Ma, Yi Hua; Yen, Pei-Shan; Deveau, Nicholas; Fishtik, Ilie; Mardilovich, Ivan

    2013-09-30

    We describe here our results on the feasibility of a novel dense metal membrane for hydrogen separation: Supported Molten Metal Membrane, or SMMM.1 The goal in this work was to develop these new membranes based on supporting thin films of low-melting, non- precious group metals, e.g., tin (Sn), indium (In), gallium (Ga), or their alloys, to provide a flux and selectivity of hydrogen that rivals the conventional but substantially more expensive palladium (Pd) or Pd alloy membranes, which are susceptible to poisoning by the many species in the coal-derived syngas, and further possess inadequate stability and limited operating temperature range. The novelty of the technology presented numerous challenges during the course of this project, however, mainly in the selection of appropriate supports, and in the fabrication of a stable membrane. While the wetting instability of the SMMM remains an issue, we did develop an adequate understanding of the interaction between molten metal films with porous supports that we were able to find appropriate supports. Thus, our preliminary results indicate that the Ga/SiC SMMM at 550 ºC has a permeance that is an order of magnitude higher than that of Pd, and exceeds the 2015 DOE target. To make practical SMM membranes, however, further improving the stability of the molten metal membrane is the next goal. For this, it is important to better understand the change in molten metal surface tension and contact angle as a function of temperature and gas-phase composition. A thermodynamic theory was, thus, developed, that is not only able to explain this change in the liquid-gas surface tension, but also the change in the solid-liquid surface tension as well as the contact angle. This fundamental understanding has allowed us to determine design characteristics to maintain stability in the face of changing gas composition. These designs are being developed. For further progress, it is also important to understand the nature of solution and

  16. METAL PHTHALOCYANINES

    DOEpatents

    Frigerio, N.A.

    1962-03-27

    A process is given for preparing heavy metal phthalocyanines, sulfonated or not. The process comprises mixing an inorganic metal salt with dimethyl formamide or methyl sulfoxide; separating the metal complex formed from the solution; mixing the complex with an equimolar amount of sodium, potassium, lithium, magnesium, or beryllium sulfonated or unsulfonated phthalocyanine whereby heavy-metal phthalocyanine crystals are formed; and separating the crystals from the solution. Uranyl, thorium, lead, hafnium, and lanthanide rare earth phthalocyanines can be produced by the process. (AEC)

  17. Silicone metalization

    SciTech Connect

    Maghribi, Mariam N.; Krulevitch, Peter; Hamilton, Julie

    2008-12-09

    A system for providing metal features on silicone comprising providing a silicone layer on a matrix and providing a metal layer on the silicone layer. An electronic apparatus can be produced by the system. The electronic apparatus comprises a silicone body and metal features on the silicone body that provide an electronic device.

  18. Silicone metalization

    SciTech Connect

    Maghribi, Mariam N.; Krulevitch, Peter; Hamilton, Julie

    2006-12-05

    A system for providing metal features on silicone comprising providing a silicone layer on a matrix and providing a metal layer on the silicone layer. An electronic apparatus can be produced by the system. The electronic apparatus comprises a silicone body and metal features on the silicone body that provide an electronic device.

  19. Target manifold formation using a quadratic SDF

    NASA Astrophysics Data System (ADS)

    Hester, Charles F.; Risko, Kelly K. D.

    2013-05-01

    Synthetic Discriminant Function (SDF) formulation of correlation filters provides constraints for forming target subspaces for a target set. In this paper we extend the SDF formulation to include quadratic constraints and use this solution to form nonlinear manifolds in the target space. The theory for forming these manifolds will be developed and demonstrated with data.

  20. Inelastic low energy electron diffraction at metal surfaces

    NASA Astrophysics Data System (ADS)

    Nazarov, V. U.; Nishigaki, S.

    2001-06-01

    The role of incident electrons penetration under a metal surface in electron energy loss spectroscopy is considered within the fully quantum-mechanical approach. The stabilized jellium model of the surface in the semi-infinite geometry and the time-dependent local density approximation for the dynamical response are used. The travel of the projectile electron inside the target metal is treated within the kinematic low energy electron diffraction theory. Confirming our simplified hard-wall reflection model results [Phys. Rev. B 59 (1999) 9866], the dramatic enhancement of the multipole plasmon peak as compared with the dipole-mode calculations is obtained for Na and Cs, which is in a qualitative agreement with the experiment. However, for K the calculation fails to explain the experiment, which discrepancy is discussed and the future improvements of the method are outlined.