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Sample records for 2p valence band

  1. Irradiation-induced degradation of PTB7 investigated by valence band and S 2p photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Darlatt, Erik; Muhsin, Burhan; Roesch, Roland; Lupulescu, Cosmin; Roth, Friedrich; Kolbe, Michael; Gottwald, Alexander; Hoppe, Harald; Richter, Mathias

    2016-08-01

    Monochromatic radiation with known absolute radiant power from an undulator at the electron storage ring Metrology Light Source (MLS) was used to irradiate PTB7 (a thieno[3, 4-b]thiophene-alt-benzodithiophene polymer) thin films at wavelengths (photon energies) of 185 nm (6.70 eV), 220 nm (5.64 eV), 300 nm (4.13 eV), 320 nm (3.88 eV), 356 nm (3.48 eV) and 675 nm (1.84 eV) under ultra-high vacuum conditions for the investigation of radiation-induced degradation effects. The characterization of the thin films is focused at ultraviolet photoelectron spectroscopy (UPS) of valence bands and is complemented by S 2p x-ray photoelectron spectroscopy (S 2p XPS) before and after the irradiation procedure. The radiant exposure was determined for each irradiation by means of photodiodes traceably calibrated to the international system of units SI. The valence band spectra show the strongest changes for the shortest wavelengths and no degradation effect at 356 nm and 675 nm even with the highest radiant exposure applied. In the spectral range where the Sun appears bright on the Earth’s surface, no degradation effects are observed.

  2. Measurement of valence band structure in arbitrary dielectric films

    SciTech Connect

    Uhm, Han S.; Choi, Eun H.

    2012-10-15

    A new way of measuring the band structure of various dielectric materials using the secondary electron emission from Auger neutralization of ions is introduced. The first example of this measurement scheme is the magnesium oxide (MgO) films with respect to the application of the films in the display industries. The density of state in the valence bands of MgO film and MgO film with a functional layer (FL) deposited over a dielectric surface reveals that the density peak of film with a FL is considerably less than that of film, thereby indicating a better performance of MgO film with functional layer in display devices. The second example of the measurement is the boron-zinc oxide (BZO) films with respect to the application of the films to the development of solar cells. The measurement of density of state in BZO film suggests that a high concentration of boron impurity in BZO films may enhance the transition of electrons and holes through the band gap from the valence to the conduction band in zinc oxide crystals; thereby improving the conductivity of the film. Secondary electron emission by the Auger neutralization of ions is highly instrumental for the determination of the density of states in the valence band of dielectric materials.

  3. Studies of Valence Band Alignment Between Nitrided GaPN/GaP (111) Interface Using X-ray Photoelectron Spectroscopy

    SciTech Connect

    Khamari, Shailesh K.; Sinha, A. K.; Oak, S. M.; Banik, S.; Barman, S. R.; Dixit, V. K.

    2011-07-15

    The analysis of core levels positions of Ga{sub 3}d, N{sub 1s} and P{sub 2}p at different etching depth from the plasma nitrided GaP (111) surface shows that the nitrogen ions interact with both Gallium and Phosphorous ions with nearly equal probability. The analysis of valence band spectra shows the type-II band alignment between GaPN{sub 0.22}/GaP and the valence band offset is {approx}2.2{+-}0.1 eV.

  4. Inter-Valence-Subband/Conduction-Band-Transport IR Detectors

    NASA Technical Reports Server (NTRS)

    Ting, David; Gunapala, Sarath; Bandara, Sumith

    2004-01-01

    Infrared (IR) detectors characterized by a combination of (1) high-quantum-efficiency photoexcitation of inter-valence-subband transitions of charge carriers and (2) high-mobility conduction- band transport of the thus-excited charge carriers have been proposed in an effort to develop focal-plane arrays of such devices for infrared imaging. Like many prior quantum-well infrared photodetectors (QWIPs), the proposed devices would be made from semiconductor heterostructures. In order to obtain the combination of characteristics mentioned above, the proposed devices would be designed and fabricated in novel InAs/GaSb superlattice configurations that would exploit a phenomenon known in the semiconductor art as type-II broken-gap band offset.

  5. Valence band dependence on thermal treatment of gold doped glasses and glass ceramics

    NASA Astrophysics Data System (ADS)

    Radu, T.; Benea, D.; Ciceo-Lucacel, R.; Ponta, O.; Simon, S.

    2012-02-01

    This paper reports x-ray photoemission spectroscopy results regarding the nucleation and growing process of gold nanoparticles (AuNPs) in CaO-SiO2-P2O5 bioactive glasses heat treated at different temperatures. The analysis of the valence band (VB) spectra is discussed in terms of the AuNPs' shape, size, and distribution at the sample surface at different temperatures. Moreover, the theoretical VB photoemission spectra of the investigated samples are presented, and their agreement with experimentally obtained spectra is discussed in detail.

  6. Thermoelectric transport in the coupled valence-band model

    NASA Astrophysics Data System (ADS)

    Ramu, Ashok T.; Cassels, Laura E.; Hackman, Nathan H.; Lu, Hong; Zide, Joshua M. O.; Bowers, John E.

    2011-02-01

    The Boltzmann transport equation (BTE) is applied to the problem of thermoelectric transport in p-type semiconductors whose valence band-structure is describable in terms of two bands degenerate at the Γ point. The Seebeck coefficient and mobility are calculated from the solution to two coupled BTEs, one for each band, with interband scattering and scattering by inelastic mechanisms treated exactly by the application of an algorithm developed by the authors in an earlier work. Most treatments of this problem decouple the two bands by neglecting certain terms in the BTE, greatly simplifying the mathematics: the error in the Seebeck coefficient and mobility introduced by this approximation is quantified by comparing with the exact solution. Degenerate statistics has been assumed throughout, and the resulting formalism is therefore valid at high hole concentrations. Material parameters are used that have been deduced from optical, strain and other experiments often not directly related to hole transport. The formulations in this work thus do not use adjustable or fitting parameters. The transport coefficients of heavily doped gallium antimonide, a typical high-efficiency p-type thermoelectric material, are calculated and agreement to experimentally determined values is found to be satisfactory.

  7. Evidence of Eu{sup 2+} 4f electrons in the valence band spectra of EuTiO{sub 3} and EuZrO{sub 3}

    SciTech Connect

    Kolodiazhnyi, T.; Valant, M.; Williams, J. R.; Bugnet, M.; Botton, G. A.; Ohashi, N.; Sakka, Y.

    2012-10-15

    We report on optical band gap and valence electronic structure of two Eu{sup 2+}-based perovskites, EuTiO{sub 3} and EuZrO{sub 3} as revealed by diffuse optical scattering, electron energy loss spectroscopy, and valence-band x-ray photoelectron spectroscopy. The data show good agreement with the first-principles studies in which the top of the valence band structure is formed by the narrow Eu 4f{sup 7} electron band. The O 2p band shows the features similar to those of the Ba(Sr)TiO{sub 3} perovskites except that it is shifted to higher binding energies. Appearance of the Eu{sup 2+} 4f{sup 7} band is a reason for narrowing of the optical band gap in the title compounds as compared to their Sr-based analogues.

  8. Valence Band Control of Metal Silicide Films via Stoichiometry.

    PubMed

    Streller, Frank; Qi, Yubo; Yang, Jing; Mangolini, Filippo; Rappe, Andrew M; Carpick, Robert W

    2016-07-01

    The unique electronic and mechanical properties of metal silicide films render them interesting for advanced materials in plasmonic devices, batteries, field-emitters, thermoelectric devices, transistors, and nanoelectromechanical switches. However, enabling their use requires precisely controlling their electronic structure. Using platinum silicide (PtxSi) as a model silicide, we demonstrate that the electronic structure of PtxSi thin films (1 ≤ x ≤ 3) can be tuned between metallic and semimetallic by changing the stoichiometry. Increasing the silicon content in PtxSi decreases the carrier density according to valence band X-ray photoelectron spectroscopy and theoretical density of states (DOS) calculations. Among all PtxSi phases, Pt3Si offers the highest DOS due to the modest shift of the Pt5d manifold away from the Fermi edge by only 0.5 eV compared to Pt, rendering it promising for applications. These results, demonstrating tunability of the electronic structure of thin metal silicide films, suggest that metal silicides can be designed to achieve application-specific electronic properties. PMID:27322019

  9. Valence Band Control of Metal Silicide Films via Stoichiometry.

    PubMed

    Streller, Frank; Qi, Yubo; Yang, Jing; Mangolini, Filippo; Rappe, Andrew M; Carpick, Robert W

    2016-07-01

    The unique electronic and mechanical properties of metal silicide films render them interesting for advanced materials in plasmonic devices, batteries, field-emitters, thermoelectric devices, transistors, and nanoelectromechanical switches. However, enabling their use requires precisely controlling their electronic structure. Using platinum silicide (PtxSi) as a model silicide, we demonstrate that the electronic structure of PtxSi thin films (1 ≤ x ≤ 3) can be tuned between metallic and semimetallic by changing the stoichiometry. Increasing the silicon content in PtxSi decreases the carrier density according to valence band X-ray photoelectron spectroscopy and theoretical density of states (DOS) calculations. Among all PtxSi phases, Pt3Si offers the highest DOS due to the modest shift of the Pt5d manifold away from the Fermi edge by only 0.5 eV compared to Pt, rendering it promising for applications. These results, demonstrating tunability of the electronic structure of thin metal silicide films, suggest that metal silicides can be designed to achieve application-specific electronic properties.

  10. Spontaneous volume magnetostriction and non-Stoner behavior of the valence band in pure hcp Gd

    NASA Astrophysics Data System (ADS)

    Khmelevskyi, S.; Turek, I.; Mohn, P.

    2004-10-01

    Employing the disordered local moment formalism in combination with first-principles band-structure calculations, we study the behavior of the valence band in pure hcp Gd upon disorder of the local 4f GD moments. We show that the large value of the spontaneous volume magnetostriction in Gd is entirely due to changes in the magnetic state of the valence band at Tc and can be calculated in good agreement with experiment. The local exchange splitting of the valence band persists above Tc , which is in strong disagreement with the conventional Stoner picture. The analysis of our results provides a theoretical background for the discussion of recent photoemission experiments.

  11. Valence band structure of binary chalcogenide vitreous semiconductors by high-resolution XPS

    SciTech Connect

    Kozyukhin, S.; Golovchak, R.; Kovalskiy, A.; Shpotyuk, O.; Jain, H.

    2011-04-15

    High-resolution X-ray photoelectron spectroscopy (XPS) is used to study regularities in the formation of valence band electronic structure in binary As{sub x}Se{sub 100-x}, As{sub x}S{sub 100-x}, Ge{sub x}Se{sub 100-x} and Ge{sub x}S{sub 100-x} chalcogenide vitreous semiconductors. It is shown that the highest occupied energetic states in the valence band of these materials are formed by lone pair electrons of chalcogen atoms, which play dominant role in the formation of valence band electronic structure of chalcogen-rich glasses. A well-expressed contribution from chalcogen bonding p electrons and more deep s orbitals are also recorded in the experimental valence band XPS spectra. Compositional dependences of the observed bands are qualitatively analyzed from structural and compositional points of view.

  12. Valence-band electronic structure of iron phthalocyanine: An experimental and theoretical photoelectron spectroscopy study

    NASA Astrophysics Data System (ADS)

    Brena, Barbara; Puglia, Carla; de Simone, Monica; Coreno, Marcello; Tarafder, Kartick; Feyer, Vitaly; Banerjee, Rudra; Göthelid, Emmanuelle; Sanyal, Biplab; Oppeneer, Peter M.; Eriksson, Olle

    2011-02-01

    The electronic structure of iron phthalocyanine (FePc) in the valence region was examined within a joint theoretical-experimental collaboration. Particular emphasis was placed on the determination of the energy position of the Fe 3d levels in proximity of the highest occupied molecular orbital (HOMO). Photoelectron spectroscopy (PES) measurements were performed on FePc in gas phase at several photon energies in the interval between 21 and 150 eV. Significant variations of the relative intensities were observed, indicating a different elemental and atomic orbital composition of the highest lying spectral features. The electronic structure of a single FePc molecule was first computed by quantum chemical calculations by means of density functional theory (DFT). The hybrid Becke 3-parameter, Lee, Yang and Parr (B3LYP) functional and the semilocal 1996 functional of Perdew, Burke and Ernzerhof (PBE) of the generalized gradient approximation (GGA-)type, exchange-correlation functionals were used. The DFT/B3LYP calculations find that the HOMO is a doubly occupied π-type orbital formed by the carbon 2p electrons, and the HOMO-1 is a mixing of carbon 2p and iron 3d electrons. In contrast, the DFT/PBE calculations find an iron 3d contribution in the HOMO. The experimental photoelectron spectra of the valence band taken at different energies were simulated by means of the Gelius model, taking into account the atomic subshell photoionization cross sections. Moreover, calculations of the electronic structure of FePc using the GGA+U method were performed, where the strong correlations of the Fe 3d electronic states were incorporated through the Hubbard model. Through a comparison with our quantum chemical calculations we find that the best agreement with the experimental results is obtained for a Ueff value of 5 eV.

  13. High-pressure synchrotron Mössbauer and X-ray diffraction studies: Exploring the structure-related valence fluctuation in EuNi2P2

    NASA Astrophysics Data System (ADS)

    Li, Chunyu; Yu, Zhenhai; Bi, Wenli; Zhao, Jiyong; Hu, Michael Y.; Zhao, Jinggeng; Wu, Wei; Luo, Jianlin; Yan, Hao; Alp, Esen E.; Liu, Haozhe

    2016-11-01

    The high-pressure effect on valence fluctuation of the ThCr2Si2-type intermetallic compound EuNi2P2 has been investigated using in situ synchrotron Mössbauer spectroscopy (SMS). The isomer shift of 151Eu in EuNi2P2 increases monotonically with increasing pressure up to 50 GPa, suggesting a valence transition of the Eu from mixed toward trivalent. The synchrotron angle-dispersive X-ray diffraction (AD-XRD) experiment shows that EuNi2P2 remains in the tetragonal structure up to 32.5 GPa at room temperature. We propose that the evolutions of bonding distance with pressure have an obvious effect on the valence fluctuation.

  14. Valence band hybridization in N-rich GaN1-xAsx alloys

    SciTech Connect

    Wu, J.; Walukiewicz, W.; Yu, K.M.; Denlinger, J.D.; Shan, W.; Ager III, J.W.; Kimura, A.; Tang, H.F.; Kuech, T.F.

    2004-05-04

    We have used photo-modulated transmission and optical absorption spectroscopies to measure the composition dependence of interband optical transitions in N-rich GaN{sub 1-x}As{sub x} alloys with x up to 0.06. The direct bandgap gradually decreases as x increases. In the dilute x limit, the observed band gap approaches 2.8 eV; this limiting value is attributed to a transition between the As localized level, which has been previously observed in As-doped GaN at 0.6 eV above the valence band maximum in As-doped GaN, and the conduction band minimum. The structure of the valence band of GaN{sub 1-x}As{sub x} is explained by the hybridization of the localized As states with the extended valence band states of GaN matrix. The hybridization is directly confirmed by soft x-ray emission experiments. To describe the electronic structure of the GaN{sub 1-x}As{sub x} alloys in the entire composition range a linear interpolation is used to combine the effects of valence band hybridization in N-rich alloys with conduction band anticrossing in As-rich alloys.

  15. Determination of the valence band structure of an alkali phosphorus oxynitride glass: A synchrotron XPS study on LiPON

    NASA Astrophysics Data System (ADS)

    Schwöbel, André; Precht, Ruben; Motzko, Markus; Carrillo Solano, Mercedes A.; Calvet, Wolfram; Hausbrand, René; Jaegermann, Wolfram

    2014-12-01

    Lithium phosphorus oxynitride (LiPON) is a solid state electrolyte commonly used in thin film batteries (TFBs). Advanced TFBs face the issue of detrimental electrode-electrolyte interlayer formation, related to the electronic structure of the interface. In this contribution, we study the valence band structure of LiPON using resonant photoemission and synchrotron photoemission with variable excitation energies. The identification of different valence band features is done according to the known valence band features of meta- and orthophosphates. Additionally we compare our results with partial density of states simulations from literature. We find that the valence band structure is similar to the known metaphosphates with an additional contribution of nitrogen states at the top of the valence band. From the results we conclude that synchrotron X-ray photoemission (XPS) is a useful tool to study the valence band structure of nitridated alkali phosphate glasses.

  16. Observation of valence band electron emission from n-type silicon field emitter arrays

    NASA Astrophysics Data System (ADS)

    Ding, Meng; Kim, Han; Akinwande, Akintunde I.

    1999-08-01

    Electron emission from the valence band of n-type Si field emitter arrays is reported. High electrostatic field at the surface of Si was achieved by reducing the radius of the emitter tip. Using oxidation sharpening, 1 μm aperture polycrystalline Si gate, n-type Si field emitter arrays with small tip radius (˜10 nm) were fabricated. Three distinct emission regions were observed: conduction band emission at low gate voltages, saturated current emission from the conduction band at intermediate voltages, and valence band plus conduction band emission at high gate voltages. Emission currents at low and high voltages obey the Fowler-Nordheim theory. The ratio of the slopes of the corresponding Fowler-Nordheim fits for these two regions is 1.495 which is in close agreement with the theoretical value of 1.445.

  17. Composition dependent valence band order in c-oriented wurtzite AlGaN layers

    SciTech Connect

    Neuschl, B. Helbing, J.; Knab, M.; Lauer, H.; Madel, M.; Thonke, K.; Feneberg, M.

    2014-09-21

    The valence band order of polar wurtzite aluminum gallium nitride (AlGaN) layers is analyzed for a dense series of samples, grown heteroepitaxially on sapphire substrates, covering the complete composition range. The excitonic transition energies, found by temperature dependent photoluminescence (PL) spectroscopy, were corrected to the unstrained state using input from X-ray diffraction. k∙p theory yields a critical relative aluminum concentration x{sub c}=(0.09±0.05) for the crossing of the uppermost two valence bands for strain free material, shifting to higher values for compressively strained samples, as supported by polarization dependent PL. The analysis of the strain dependent valence band crossing reconciles the findings of other research groups, where sample strain was neglected. We found a bowing for the energy band gap to the valence band with Γ₉ symmetry of b{sub Γ₉}=0.85eV, and propose a possible bowing for the crystal field energy of b{sub cf}=-0.12eV. A comparison of the light extraction efficiency perpendicular and parallel to the c axis of Al{sub x}Ga{sub 1-x}N/Al{sub y}Ga{sub 1-y}N quantum well structures is discussed for different compositions.

  18. Rotational bands terminating at maximal spin in the valence space

    SciTech Connect

    Ragnarsson, I.; Afanasjev, A.V.

    1996-12-31

    For nuclei with mass A {le} 120, the spin available in {open_quotes}normal deformation configurations{close_quotes} is experimentally accessible with present detector systems. Of special interest are the nuclei which show collective features at low or medium-high spin and where the corresponding rotational bands with increasing spin can be followed in a continuous way to or close to a non-collective terminating state. Some specific features in this context are discussed for nuclei in the A = 80 region and for {sup 117,118}Xe.

  19. Chalcogen doping at anionic site: A scheme towards more dispersive valence band in CuAlO2

    NASA Astrophysics Data System (ADS)

    Mazumder, Nilesh; Sen, Dipayan; Chattopadhyay, Kalyan Kumar

    2013-02-01

    Using first-principles calculations, we propose to enhance the dispersion of the top of valence band at high-symmetry points by selective introduction of chalcogen (Ch) impurities at oxygen site. As ab-plane hole mobility of CuAlO2 is large enough to support a band-conduction model over a polaronic one at room temperature [M. S. Lee et al. Appl. Phys. Lett. 79, 2029, (2001); J. Tate et al. Phys. Rev. B 80, 165206, (2009)], we examine its electronic and optical properties normal to c-axis. Intrinsic indirectness of energy-gap at Γ-point can be effectively removed along with substantial increase in density of states near Fermi level (EF) upon Ch addition. This can be attributed to S 2p-Cu 3d interaction just at or below EF, which should result in significantly improved carrier mobility and conductivity profile for this important p-type TCO.

  20. Valence-band ordering and magneto-optic exciton fine structure in ZnO

    NASA Astrophysics Data System (ADS)

    Lambrecht, Walter R.; Rodina, Anna V.; Limpijumnong, Sukit; Segall, B.; Meyer, Bruno K.

    2002-02-01

    Using first-principles linear muffin-tin orbital density functional band structure calculations, the ordering of the states in the wurtzite ZnO valence-band maximum, split by crystal-field and spin-orbit coupling effects, is found to be Γ7(5)>Γ9(5)>Γ7(1), in which the number in parentheses indicates the parent state without spin-orbit coupling. This results from the negative spin-orbit splitting, which in turn is due to the participation of the Zn 3d band. The result is found to be robust even when effects beyond the local density approximation on the Zn 3d band position are included. Using a Kohn-Luttinger model parametrized by our first-principles calculations, it is furthermore shown that the binding energies of the excitons primarily derived from each valence band differ by less than the valence-band splittings even when interband coupling effects are included. The binding energies of n=2 and n=1 excitons, however, are not in a simple 1/4 ratio. Our results are shown to be in good agreement with the recent magneto-optical experimental data by Reynolds et al. [Phys. Rev. B 60, 2340 (1999)], in spite of the fact that on the basis of these data these authors claimed that the valence-band maximum would have Γ9 symmetry. The differences between our and Reynolds' analysis of the data are discussed and arise from the sign of the Landé g factor for holes, which is here found to be negative for the upper Γ7 band.

  1. Crossover and valence band Kβ X-rays of chromium oxides

    NASA Astrophysics Data System (ADS)

    Fazinić, Stjepko; Mandić, Luka; Kavčič, Matjaž; Božičević, Iva

    2011-06-01

    Kβ X-ray spectra of chromium metal and selected chromium oxides were measured twice using medium resolution flat crystal spectrometer and high resolution spectrometer employing Johansson geometry after excitation with 2 MeV proton beams. The positions and intensities of crossover ( Kβ″) and valence ( Kβ2,5) band X-rays relative to the primary Kβ X-ray components were extracted in a consistent way. The results were compared with the existing data obtained by proton and photon induced ionization mechanisms and theoretical predictions. The obtained results in peak relative positions and intensities were analyzed in order to study dependence on the chromium oxidation states and chromium-oxygen bond lengths in selected chromium oxides. Our results obtained by both spectrometers confirm that the linear trend observed for the valence peak relative energy shift as a function of chromium oxidation number does not depend on the experimental resolution. Experimental results for normalized intensities (i.e. relative intensities divided with the number of chromium-oxygen pairs) of crossover and valence band X-rays obtained by both spectrometers are in very good agreement, and follow exponential relationship with the average Cr―O bond lengths in corresponding chromium oxides. The observed trends in crossover and valence X-rays normalized intensities could be used to measure the average chromium-oxygen bond length in various chromium oxides, with the sum of both crossover and valence X-ray normalized intensities being the most sensitive measure.

  2. Accurate determination of the valence band edge in hard x-ray photoemission spectra using GW theory

    NASA Astrophysics Data System (ADS)

    Lischner, Johannes; Nemšák, Slavomír; Conti, Giuseppina; Gloskovskii, Andrei; Pálsson, Gunnar Karl; Schneider, Claus M.; Drube, Wolfgang; Louie, Steven G.; Fadley, Charles

    2016-04-01

    We introduce a new method for determining accurate values of the valence-band maximum in x-ray photoemission spectra. Specifically, we align the sharpest peak in the valence-band region of the experimental spectrum with the corresponding feature of a theoretical valence-band density of states curve from ab initio GW theory calculations. This method is particularly useful for soft and hard x-ray photoemission studies of materials with a mixture of valence-band characters, where strong matrix element effects can render standard methods for extracting the valence-band maximum unreliable. We apply our method to hydrogen-terminated boron-doped diamond, which is a promising substrate material for novel solar cell devices. By carrying out photoemission experiments with variable light polarizations, we verify the accuracy of our analysis and the general validity of the method.

  3. Revisiting the Valence and Conduction Band Size Dependence of PbS Quantum Dot Thin Films.

    PubMed

    Miller, Elisa M; Kroupa, Daniel M; Zhang, Jianbing; Schulz, Philip; Marshall, Ashley R; Kahn, Antoine; Lany, Stephan; Luther, Joseph M; Beard, Matthew C; Perkins, Craig L; van de Lagemaat, Jao

    2016-03-22

    We use a high signal-to-noise X-ray photoelectron spectrum of bulk PbS, GW calculations, and a model assuming parabolic bands to unravel the various X-ray and ultraviolet photoelectron spectral features of bulk PbS as well as determine how to best analyze the valence band region of PbS quantum dot (QD) films. X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) are commonly used to probe the difference between the Fermi level and valence band maximum (VBM) for crystalline and thin-film semiconductors. However, we find that when the standard XPS/UPS analysis is used for PbS, the results are often unrealistic due to the low density of states at the VBM. Instead, a parabolic band model is used to determine the VBM for the PbS QD films, which is based on the bulk PbS experimental spectrum and bulk GW calculations. Our analysis highlights the breakdown of the Brillioun zone representation of the band diagram for large band gap, highly quantum confined PbS QDs. We have also determined that in 1,2-ethanedithiol-treated PbS QD films the Fermi level position is dependent on the QD size; specifically, the smallest band gap QD films have the Fermi level near the conduction band minimum and the Fermi level moves away from the conduction band for larger band gap PbS QD films. This change in the Fermi level within the QD band gap could be due to changes in the Pb:S ratio. In addition, we use inverse photoelectron spectroscopy to measure the conduction band region, which has similar challenges in the analysis of PbS QD films due to a low density of states near the conduction band minimum. PMID:26895310

  4. Revisiting the Valence and Conduction Band Size Dependence of PbS Quantum Dot Thin Films.

    PubMed

    Miller, Elisa M; Kroupa, Daniel M; Zhang, Jianbing; Schulz, Philip; Marshall, Ashley R; Kahn, Antoine; Lany, Stephan; Luther, Joseph M; Beard, Matthew C; Perkins, Craig L; van de Lagemaat, Jao

    2016-03-22

    We use a high signal-to-noise X-ray photoelectron spectrum of bulk PbS, GW calculations, and a model assuming parabolic bands to unravel the various X-ray and ultraviolet photoelectron spectral features of bulk PbS as well as determine how to best analyze the valence band region of PbS quantum dot (QD) films. X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) are commonly used to probe the difference between the Fermi level and valence band maximum (VBM) for crystalline and thin-film semiconductors. However, we find that when the standard XPS/UPS analysis is used for PbS, the results are often unrealistic due to the low density of states at the VBM. Instead, a parabolic band model is used to determine the VBM for the PbS QD films, which is based on the bulk PbS experimental spectrum and bulk GW calculations. Our analysis highlights the breakdown of the Brillioun zone representation of the band diagram for large band gap, highly quantum confined PbS QDs. We have also determined that in 1,2-ethanedithiol-treated PbS QD films the Fermi level position is dependent on the QD size; specifically, the smallest band gap QD films have the Fermi level near the conduction band minimum and the Fermi level moves away from the conduction band for larger band gap PbS QD films. This change in the Fermi level within the QD band gap could be due to changes in the Pb:S ratio. In addition, we use inverse photoelectron spectroscopy to measure the conduction band region, which has similar challenges in the analysis of PbS QD films due to a low density of states near the conduction band minimum.

  5. Measurement of valence band structure in boron-zinc-oxide films by making use of ion beams

    SciTech Connect

    Uhm, Han S.; Kwon, Gi C.; Choi, Eun H.

    2011-12-26

    Measurement of valence band structure in the boron-zinc oxide (BZO) films was developed using the secondary electron emission due to the Auger neutralization of ions. The energy distribution profile of the electrons emitted from boron-zinc-oxide films was measured and rescaled so that Auger self-convolution arose; thus, revealing the detailed structure of the valence band and suggesting that a high concentration of boron impurity in BZO films may enhance the transition of electrons and holes through the band gap from the valence to the conduction band in zinc oxide crystals; thereby improving the conductivity of the film.

  6. Heterogeneous and hyperfine interactions between valence states of molecular iodine correlating with the I(2P1/2) + I(2P1/2) dissociation limit

    NASA Astrophysics Data System (ADS)

    Baturo, Vera V.; Cherepanov, Igor N.; Lukashov, Sergey S.; Poretsky, Sergey A.; Pravilov, Anatoly M.; Zhironkin, Anatoly I.

    2016-05-01

    Detailed analysis of interactions between all 0g + , 1u, and 0u - weakly bound states of iodine molecule correlating with the I(2P1/2) + I(2P1/2) (bb) dissociation limit has been performed. For this purpose, the 0u - (bb) state has been described using analysis of rotationally resolved excitation spectra of luminescence from the g 0g - state populated in a three-step three-color perturbation facilitated excitation scheme via the 0u - state. Energies of 41 rovibrational levels, molecular constants, and potential energy curve have been determined. Energy gaps between closest rovibrational levels of the 0u - and 0g + , 1u (bb) states are found to be large, ˜6 cm-1. However, interaction of all three 0g + , 1u, and 0u - (bb) states has been observed. It has been found that the 0u - and 1u electronic states are mixed by heterogeneous interactions, while their mixing with the 0g + one is due to hyperfine interactions predominantly. Admixture coefficients and electronic matrix elements of the coupling between the 0g + ˜1u, 0g + ˜ 0u - , and 0u - ˜1u states have been estimated.

  7. Application of Koopmans' theorem for density functional theory to full valence-band photoemission spectroscopy modeling.

    PubMed

    Li, Tsung-Lung; Lu, Wen-Cai

    2015-10-01

    In this work, Koopmans' theorem for Kohn-Sham density functional theory (KS-DFT) is applied to the photoemission spectra (PES) modeling over the entire valence-band. To examine the validity of this application, a PES modeling scheme is developed to facilitate a full valence-band comparison of theoretical PES spectra with experiments. The PES model incorporates the variations of electron ionization cross-sections over atomic orbitals and a linear dispersion of spectral broadening widths. KS-DFT simulations of pristine rubrene (5,6,11,12-tetraphenyltetracene) and potassium-rubrene complex are performed, and the simulation results are used as the input to the PES models. Two conclusions are reached. First, decompositions of the theoretical total spectra show that the dissociated electron of the potassium mainly remains on the backbone and has little effect on the electronic structures of phenyl side groups. This and other electronic-structure results deduced from the spectral decompositions have been qualitatively obtained with the anionic approximation to potassium-rubrene complexes. The qualitative validity of the anionic approximation is thus verified. Second, comparison of the theoretical PES with the experiments shows that the full-scale simulations combined with the PES modeling methods greatly enhance the agreement on spectral shapes over the anionic approximation. This agreement of the theoretical PES spectra with the experiments over the full valence-band can be regarded, to some extent, as a collective validation of the application of Koopmans' theorem for KS-DFT to valence-band PES, at least, for this hydrocarbon and its alkali-adsorbed complex. PMID:25974677

  8. Effect of Surface Defect States on Valence Band and Charge Separation and Transfer Efficiency

    NASA Astrophysics Data System (ADS)

    Xu, Juan; Teng, Yiran; Teng, Fei

    2016-09-01

    Both energy band and charge separation and transfer are the crucial affecting factor for a photochemical reaction. Herein, the BiOCl nanosheets without and with surface bismuth vacancy (BOC, V-BOC) are prepared by a simple hydrothermal method. It is found that the new surface defect states caused by bismuth vacancy have greatly up-shifted the valence band and efficiently enhanced the separation and transfer rates of photogenerated electron and hole. It is amazing that the photocatalytic activity of V-BOC is 13.6 times higher than that of BOC for the degradation methyl orange (MO). We can develop an efficient photocatalyst by the introduction of defects.

  9. Experimental determination of valence band maxima for SrTiO3,TiO2, and SrO and the associated valence band offsets with Si(001)

    SciTech Connect

    Chambers, Scott A.; Droubay, Timothy C.; Kaspar, Tiffany C.; Gutowski, Maciej S.

    2004-08-20

    We address the issue of accurate determination of the valence band maximum (VBM) for SrTiO3(001) single crystals and epitaxial films, as well as TiO2(001) anatase and SrO epitaxial films. These measurements are of critical importance in determining valence band offsets in heterojunctions of these oxides with Si. Three different methods are analyzed: (1) fitting a Gaussian broadened theoretical density of states to the x-ray photoelectron valence band spectrum; (2) finding the intersection of a regression line that spans the linear portion of the x-ray photoelectron valence band leading edge with the background between the valence band maximum and the Fermi level; and (3) determining the energy at which high-resolution ultraviolet photoemission intensity at the leading edge goes to zero. We find that method 1 yields physically unreasonable results when used in conjunction with density functional theory because the latter does not predict the detailed shape of the valence bands in these oxides with sufficient accuracy. In contrast, methods 2 and 3 give physically reasonable results that are in good mutual agreement. The difference in VBM between method 1 and methods 2 and 3 is 0.4–0.6 eV, depending on the oxide. Methods 2 and 3 yield the most reliable VBM, provided the experiments are carried out with adequate energy resolution.

  10. Experimental Determination of Valence Band Maxima for SrTiO3, TiO2, and SrO and the Associated Valence Band Offsets with Si(001)

    SciTech Connect

    Chambers, Scott A.; Droubay, Timothy C.; Kaspar, Tiffany C.; Gutowski, Maciej S.

    2004-08-20

    Abstract We address the issue of accurate determination of the energy at the top of the valence band for SrTiO₃(001) single crystals, as well as TiO₂(001) anatase and SrO epitaxial films. These measurements are of critical importance in determining valence band offsets for oxides in heterojunctions involving these materials. Three different methods are presented and compared: (1) fitting Gaussian broadened theoretical densities of states to x-ray excited valence band spectra, (2) finding the intersection of a regression line that spans the linear portion of the x-ray excited valence band leading edge with the background between the valence band maximum and the Fermi level, and, (3) determining the energy at which high-resolution ultraviolet photoemission intensity of the leading edge goes to zero. We find that method 1 is not reliable due to limitations in the accuracy of density functional theory when applied to these oxides. In contrast, methods 2 and 3 give physically reasonable results that are in good mutual agreement. The difference in VBM between method 1 and methods 2 & 3 is 0.4 – 0.6 eV, depending on the oxide. The true valence band maximum can be directly and accurately measured using methods 2 & 3 provided the experiment is carried out with adequate energy resolution. PACS numbers: 79.60.Jv a)Electronic mail: sa.chambers@pnl.gov

  11. Convergence of valence bands for high thermoelectric performance for p-type InN

    NASA Astrophysics Data System (ADS)

    Li, Hai-Zhu; Li, Ruo-Ping; Liu, Jun-Hui; Huang, Ming-Ju

    2015-12-01

    Band engineering to converge the bands to achieve high valley degeneracy is one of effective approaches for designing ideal thermoelectric materials. Convergence of many valleys in the valence band may lead to a high Seebeck coefficient, and induce promising thermoelectric performance of p-type InN. In the current work, we have systematically investigated the electronic structure and thermoelectric performance of wurtzite InN by using the density functional theory combined with semiclassical Boltzmann transport theory. Form the results, it can be found that intrinsic InN has a large Seebeck coefficient (254 μV/K) and the largest value of ZeT is 0.77. The transport properties of p-type InN are better than that of n-type one at the optimum carrier concentration, which mainly due to the large Seebeck coefficient for p-type InN, although the electrical conductivity of n-type InN is larger than that of p-type one. We found that the larger Seebeck coefficient for p-type InN may originate from the large valley degeneracy in the valence band. Moreover, the low minimum lattice thermal conductivity for InN is one key factor to become a good thermoelectric material. Therefore, p-type InN could be a potential material for further applications in the thermoelectric area.

  12. Band gap widening at random CIGS grain boundary detected by valence electron energy loss spectroscopy

    NASA Astrophysics Data System (ADS)

    Keller, Debora; Buecheler, Stephan; Reinhard, Patrick; Pianezzi, Fabian; Bissig, Benjamin; Carron, Romain; Hage, Fredrik; Ramasse, Quentin; Erni, Rolf; Tiwari, Ayodhya N.

    2016-10-01

    Cu(In,Ga) Se2 (CIGS) thin film solar cells have demonstrated very high efficiencies, but still the role of nanoscale inhomogeneities in CIGS and their impact on the solar cell performance are not yet clearly understood. Due to the polycrystalline structure of CIGS, grain boundaries are very common structural defects that are also accompanied by compositional variations. In this work, we apply valence electron energy loss spectroscopy in scanning transmission electron microscopy to study the local band gap energy at a grain boundary in the CIGS absorber layer. Based on this example, we demonstrate the capabilities of a 2nd generation monochromator that provides a very high energy resolution and allows for directly relating the chemical composition and the band gap energy across the grain boundary. A band gap widening of about 20 meV is observed at the grain boundary. Furthermore, the compositional analysis by core-loss EELS reveals an enrichment of In together with a Cu, Ga and Se depletion at the same area. The experimentally obtained results can therefore be well explained by the presence of a valence band barrier at the grain boundary.

  13. Band width and multiple-angle valence-state mapping of diamond

    SciTech Connect

    Jimenez, I.; Terminello, L.J.; Sutherland, D.G.J.

    1997-04-01

    The band width may be considered the single most important parameter characterizing the electronic structure of a solid. The ratio of band width and Coulomb repulsion determines how correlated or delocalized an electron system is. Some of the most interesting solids straddle the boundary between localized and delocalized, e.g. the high-temperature superconductors. The bulk of the band calculations available today is based on local density functional (DF) theory. Even though the Kohn-Sham eigenvalues from that theory do not represent the outcome of a band-mapping experiment, they are remarkably similar to the bands mapped via photoemission. Strictly speaking, one should use an excited state calculation that takes the solid`s many-body screening response to the hole created in photoemission into account. Diamond is a useful prototype semiconductor because of its low atomic number and large band width, which has made it a long-time favorite for testing band theory. Yet, the two experimental values of the band width of diamond have error bars of {+-}1 eV and differ by 3.2 eV. To obtain an accurate valence band width for diamond, the authors use a band-mapping method that collects momentum distributions instead of the usual energy distributions. This method has undergone extensive experimental and theoretical tests in determining the band width of lithium fluoride. An efficient, imaging photoelectron spectrometer is coupled with a state-of-the-art undulator beam line at the Advanced Light Source to allow collection of a large number of data sets. Since it takes only a few seconds to take a picture of the photoelectrons emitted into a 84{degrees} cone, the authors can use photon energies as high as 350 eV where the cross section for photoemission from the valence band is already quite low, but the emitted photoelectrons behave free-electron-like. This make its much easier to locate the origin of the inter-band transitions in momentum space.

  14. Valence-band electronic structure of silicon nitride studied with the use of soft-x-ray emission

    NASA Astrophysics Data System (ADS)

    Carson, R. D.; Schnatterly, S. E.

    1986-02-01

    We have studied the valence-band electronic structure of α-phase, β-phase, and amorphous silicon nitride samples, using Si L-x-ray emission. Our results are compared with a recent band-structure calculation and show that Si 3d states are necessary to properly describe the upper-valence-band and lower-conduction-band density of states. A prominent feature is seen above the valence band which is attributed to conduction-band states that are populated by the incident electron beam. By reducing the energy of the electron beam it is possible to enhance the surface emission relative to bulk emission, and such spectra are also presented and discussed.

  15. Valence-band electronic structure evolution of graphene oxide upon thermal annealing for optoelectronics

    DOE PAGES

    Yamaguchi, Hisato; Ogawa, Shuichi; Watanabe, Daiki; Hozumi, Hideaki; Gao, Yongqian; Eda, Goki; Mattevi, Cecilia; Fujita, Takeshi; Yoshigoe, Akitaka; Ishizuka, Shinji; et al

    2016-04-08

    We report valence band electronic structure evolution of graphene oxide (GO) upon its thermal reduction. Degree of oxygen functionalization was controlled by annealing temperatures, and an electronic structure evolution was monitored using real-time ultraviolet photoelectron spectroscopy. We observed a drastic increase in density of states around the Fermi level upon thermal annealing at ~600 °C. The result indicates that while there is an apparent band gap for GO prior to a thermal reduction, the gap closes after an annealing around that temperature. This trend of band gap closure was correlated with electrical, chemical, and structural properties to determine a setmore » of GO material properties that is optimal for optoelectronics. The results revealed that annealing at a temperature of ~500 °C leads to the desired properties, demonstrated by a uniform and an order of magnitude enhanced photocurrent map of an individual GO sheet compared to as-synthesized counterpart.« less

  16. Valence x-ray-emission bands of a-Si:H/a-SiNx:H superlattices

    NASA Astrophysics Data System (ADS)

    Nithianandam, Jeyasingh; Schnatterly, Stephen E.

    1990-11-01

    Si L2,3 x-ray-emission spectra from amorphous superlattices made with a-Si:H and a-SiNx:H are presented and interpreted using a two-phase linear superposition model for the valence-band region. The average thickness of buried interfaces in these superlattices was found to be 1.8 Å and the interfaces were shown to be of silicon-nitride character. A direct measurement of the fluorescence yield ratio in the soft-x-ray spectral range for any two materials is also presented.

  17. Experimental study of the valence band of Bi2Se3

    DOE PAGES

    Gao, Yi-Bin; He, Bin; Parker, David; Androulakis, Ioannis; Heremans, Joseph P.

    2014-09-26

    The valence band of Bi2Se3 is investigated with Shubnikov - de Haas measurements, galvanomagnetic and thermoelectric transport. At low hole concentration, the hole Fermi surface is closed and box-like, but at higher concentrations it develops tube-like extensions that are open. The experimentally determined density-of-states effective mass is lighter than density-functional theory calculations predict; while we cannot give a definitive explanation for this, we suspect that the theory may lack sufficient precision to compute room-temperature transport properties, such as the Seebeck coefficient, in solids in which there are Van der Waals interlayer bonds.

  18. Symmetry origins of the `caldera' valence band distortion in 2D semiconductors

    NASA Astrophysics Data System (ADS)

    Li, Pengke; Appelbaum, Ian; Physics Department Team

    The electronic structures of many two-dimensional van der Waals semiconductors exhibit various fascinating properties distinct from their three-dimensional bulk counterparts. Through an examination of their lattice symmetries, we identify several universal rules dictating their band dispersion in the monolayer limit, where in-plane mirror symmetry and quantum confinement play critical roles. Taking group-III metal monochalcogenides (such as GaSe) as an example, we reveal the origin of the unusual `caldera' shape of the valence band edge (otherwise inelegantly dubbed an `upside down Mexican hat'), which we show is surprisingly common among other 2D semiconductors (such as in phosphorene for k along its zigzag direction). Reference: arXiv:1508.06963

  19. Near valence-band electronic properties of semiconducting β -Ga2O3 (100) single crystals

    NASA Astrophysics Data System (ADS)

    Navarro-Quezada, A.; Alamé, S.; Esser, N.; Furthmüller, J.; Bechstedt, F.; Galazka, Z.; Skuridina, D.; Vogt, P.

    2015-11-01

    β -Ga2O3 is a transparent wide-band-gap semiconductor that has attracted considerable interest in recent years due to its suitable electrical conductivity and transparency in the ultraviolet spectral region. In this work we investigate the electronic properties of the near valence-band-edge region for semiconducting β -Ga2O3 (100) bulk single crystals using core-level photoelectron spectroscopy and ab initio theory within the framework of density functional theory and the GW approach. We find good agreement between the experimental results and the theoretical calculations. This is explained by the hybridization of the Ga 3 d and O 2 s states, similar as for In2O3 .

  20. Effect of Surface Defect States on Valence Band and Charge Separation and Transfer Efficiency.

    PubMed

    Xu, Juan; Teng, Yiran; Teng, Fei

    2016-01-01

    Both energy band and charge separation and transfer are the crucial affecting factor for a photochemical reaction. Herein, the BiOCl nanosheets without and with surface bismuth vacancy (BOC, V-BOC) are prepared by a simple hydrothermal method. It is found that the new surface defect states caused by bismuth vacancy have greatly up-shifted the valence band and efficiently enhanced the separation and transfer rates of photogenerated electron and hole. It is amazing that the photocatalytic activity of V-BOC is 13.6 times higher than that of BOC for the degradation methyl orange (MO). We can develop an efficient photocatalyst by the introduction of defects. PMID:27586149

  1. Effect of Surface Defect States on Valence Band and Charge Separation and Transfer Efficiency

    PubMed Central

    Xu, Juan; Teng, Yiran; Teng, Fei

    2016-01-01

    Both energy band and charge separation and transfer are the crucial affecting factor for a photochemical reaction. Herein, the BiOCl nanosheets without and with surface bismuth vacancy (BOC, V-BOC) are prepared by a simple hydrothermal method. It is found that the new surface defect states caused by bismuth vacancy have greatly up-shifted the valence band and efficiently enhanced the separation and transfer rates of photogenerated electron and hole. It is amazing that the photocatalytic activity of V-BOC is 13.6 times higher than that of BOC for the degradation methyl orange (MO). We can develop an efficient photocatalyst by the introduction of defects. PMID:27586149

  2. Electronic and thermoelectric properties of van der Waals materials with ring-shaped valence bands

    SciTech Connect

    Wickramaratne, Darshana E-mail: rlake@ece.ucr.edu; Lake, Roger K. E-mail: rlake@ece.ucr.edu; Zahid, Ferdows

    2015-08-21

    The valence band of a variety of few-layer, two-dimensional materials consist of a ring of states in the Brillouin zone. The energy-momentum relation has the form of a “Mexican hat” or a Rashba dispersion. The two-dimensional density of states is singular at or near the band edge, and the band-edge density of modes turns on nearly abruptly as a step function. The large band-edge density of modes enhances the Seebeck coefficient, the power factor, and the thermoelectric figure of merit ZT. Electronic and thermoelectric properties are determined from ab initio calculations for few-layer III–VI materials GaS, GaSe, InS, InSe, for Bi{sub 2}Se{sub 3}, for monolayer Bi, and for bilayer graphene as a function of vertical field. The effect of interlayer coupling on these properties in few-layer III–VI materials and Bi{sub 2}Se{sub 3} is described. Analytical models provide insight into the layer dependent trends that are relatively consistent for all of these few-layer materials. Vertically biased bilayer graphene could serve as an experimental test-bed for measuring these effects.

  3. Use of ESCA valence bands to infer structural information about the molybdenum phase in supported molybdenum catalysts

    SciTech Connect

    Fiedor, J.N.; Proctor, A.; Houalla, M.; Hercules, D.M. ); Sherwood, M.A. ); Mulcahy, F.M. )

    1992-12-24

    X-ray photoelectron spectroscopy (XPS, ESCA) valence band spectra were used to infer information about the molybdenum phase in standard Mo compounds such as sodium molybdate and ammonium heptamolybdate and in Mo/Al[sub 2]O[sub 3] catalysts prepared by equilibrium adsorption and incipient wetness impregnation methods. ESCA valence band measurements can distinguish between tetrahedrally coordinated Mo (sodium molybdate) and octahedrally coordinated Mo (ammonium molybdate). Mo ESCA valence band results show that Mo/Al[sub 2]O[sub 3] catalysts prepared by equilibrium adsorption at pH 2.2 and Mo/Al[sub 2]O[sub 3] catalysts prepared by incipient wetness impregnation contain primarily octahedral Mo. 31 refs., 7 figs.

  4. Site-specific intermolecular valence-band dispersion in α-phase crystalline films of cobalt phthalocyanine studied by angle-resolved photoemission spectroscopy

    SciTech Connect

    Yamane, Hiroyuki; Kosugi, Nobuhiro

    2014-12-14

    The valence band structure of α-phase crystalline films of cobalt phthalocyanine (CoPc) grown on Au(111) is investigated by using angle-resolved photoemission spectroscopy (ARPES) with synchrotron radiation. The photo-induced change in the ARPES peaks is noticed in shape and energy of the highest occupied molecular orbital (HOMO, C 2p) and HOMO-1 (Co 3d) of CoPc, and is misleading the interpretation of the electronic properties of CoPc films. From the damage-free normal-emission ARPES measurement, the clear valence-band dispersion has been first observed, showing that orbital-specific behaviors are attributable to the interplay of the intermolecular π-π and π-d interactions. The HOMO band dispersion of 0.1 eV gives the lower limit of the hole mobility for α-CoPc of 28.9 cm{sup 2} V{sup −1} s{sup −1} at 15 K. The non-dispersive character of the split HOMO-1 bands indicates that the localization of the spin state is a possible origin of the antiferromagnetism.

  5. The role of beryllium in the band structure of MgZnO: Lifting the valence band maximum

    NASA Astrophysics Data System (ADS)

    Chen, S. S.; Pan, X. H.; Chen, W.; Zhang, H. H.; Dai, W.; Ding, P.; Huang, J. Y.; Lu, B.; Ye, Z. Z.

    2014-09-01

    We investigate the effect of Be on the valence band maximum (VBM) of MgZnO by measuring the band offsets of MgxZn1-xO/BexMgyZn1-x-yO heterojunctions using X-ray photoelectron spectroscopy measurements. MgxZn1-xO and BexMgyZn1-x-yO films have been grown on c-plane sapphire substrates by plasma-assisted molecular beam epitaxy. The valence band offset ( Δ E V) of Mg0.15Zn0.85O ( E g = 3.62 eV)/Be0.005Mg0.19Zn0.805O ( E g = 3.73 eV) heterojunction is 0.01 eV and Be0.005Mg0.19Zn0.805O has a lower VBM. The increased Mg composition is the main factor for the reduction of VBM. The VBM of MgxZn1-xO is lower by 0.03 eV with the enlargement of E g from 3.62 eV to 3.73 eV by increasing Mg composition. Considering the effect of increased Mg composition, it is concluded that the little amount of Be makes the VBM go up by 0.02 eV when the E g of the alloy is 3.73 eV. The Δ E V of Mg0.11Zn0.89O ( E g = 3.56 eV)/Be0.007Mg0.12Zn0.873O ( E g = 3.56 eV) heterojunction is calculated to be 0.03 eV and Be0.007Mg0.12Zn0.873O has a higher VBM than Mg0.11Zn0.89O, which means that a little amount Be lifts the VBM by 0.03 eV when the E g of the alloy is 3.56 eV. The experimental measurements have offered a strong support for the theoretical research that alloying Be in MgxZn1-xO alloys is hopeful to form a higher VBM and to enhance the p-type dopability of MgZnO.

  6. Measurement of the valence band-offset in a PbSe/ZnO heterojunction by x-ray photoelectron spectroscopy

    SciTech Connect

    Li Lin; Qiu Jijun; Weng Binbin; Yuan Zijian; Shi Zhisheng; Li Xiaomin; Gan Xiaoyan; Sellers, Ian R.

    2012-12-24

    A heterojunction of PbSe/ZnO has been grown by molecular beam epitaxy. X-ray photoelectron spectroscopy was used to directly measure the valence-band offset (VBO) of the heterojunction. The VBO, {Delta}E{sub V}, was determined as 2.51 {+-} 0.05 eV using the Pb 4p{sup 3/2} and Zn 2p{sup 3/2} core levels as a reference. The conduction-band offset, {Delta}E{sub C}, was, therefore, determined to be 0.59 {+-} 0.05 eV based on the above {Delta}E{sub V} value. This analysis indicates that the PbSe/ZnO heterojunction forms a type I (Straddling Gap) heterostructure.

  7. Control of valence and conduction band energies in layered transition metal phosphates via surface functionalization.

    PubMed

    Lentz, Levi C; Kolb, Brian; Kolpak, Alexie M

    2016-05-18

    Layered transition metal phosphates and phosphites (TMPs) are a class of materials composed of layers of 2D sheets bound together via van der Waals interactions and/or hydrogen bonds. Explored primarily for use in proton transfer, their unique chemical tunability also makes TMPs of interest for forming large-scale hybrid materials. Further, unlike many layered materials, TMPs can readily be solution exfoliated to form single 2D sheets or bilayers, making them exciting candidates for a variety of applications. However, the electronic properties of TMPs have largely been unstudied to date. In this work, we use first-principles computations to investigate the atomic and electronic structure of TMPs with a variety of stoichiometries. We demonstrate that there exists a strong linear relationship between the band gap and the ionic radius of the transition metal cation in these materials, and show that this relationship, which opens opportunities for engineering new compositions with a wide range of band gaps, arises from constraints imposed by the phosphorus-oxygen bond geometry. In addition, we find that the energies of the valence and conduction band edges can be systematically tuned over a range of ∼3 eV via modification of the functional group extending from the phosphorus. Based on the Hammett constant of this functional group, we identify a simple, predictive relationship for the ionization potential and electron affinity of layered TMPs. Our results thus provide guidelines for systematic design of TMP-derived functional materials, which may enable new approaches for optimizing charge transfer in electronics, photovoltaics, electrocatalysts, and other applications. PMID:27157509

  8. Control of valence and conduction band energies in layered transition metal phosphates via surface functionalization.

    PubMed

    Lentz, Levi C; Kolb, Brian; Kolpak, Alexie M

    2016-05-18

    Layered transition metal phosphates and phosphites (TMPs) are a class of materials composed of layers of 2D sheets bound together via van der Waals interactions and/or hydrogen bonds. Explored primarily for use in proton transfer, their unique chemical tunability also makes TMPs of interest for forming large-scale hybrid materials. Further, unlike many layered materials, TMPs can readily be solution exfoliated to form single 2D sheets or bilayers, making them exciting candidates for a variety of applications. However, the electronic properties of TMPs have largely been unstudied to date. In this work, we use first-principles computations to investigate the atomic and electronic structure of TMPs with a variety of stoichiometries. We demonstrate that there exists a strong linear relationship between the band gap and the ionic radius of the transition metal cation in these materials, and show that this relationship, which opens opportunities for engineering new compositions with a wide range of band gaps, arises from constraints imposed by the phosphorus-oxygen bond geometry. In addition, we find that the energies of the valence and conduction band edges can be systematically tuned over a range of ∼3 eV via modification of the functional group extending from the phosphorus. Based on the Hammett constant of this functional group, we identify a simple, predictive relationship for the ionization potential and electron affinity of layered TMPs. Our results thus provide guidelines for systematic design of TMP-derived functional materials, which may enable new approaches for optimizing charge transfer in electronics, photovoltaics, electrocatalysts, and other applications.

  9. The role of beryllium in the band structure of MgZnO: Lifting the valence band maximum

    SciTech Connect

    Chen, S. S.; Pan, X. H. E-mail: yezz@zju.edu.cn; Chen, W.; Zhang, H. H.; Dai, W.; Ding, P.; Huang, J. Y.; Lu, B.; Ye, Z. Z. E-mail: yezz@zju.edu.cn

    2014-09-22

    We investigate the effect of Be on the valence band maximum (VBM) of MgZnO by measuring the band offsets of Mg{sub x}Zn{sub 1−x}O/Be{sub x}Mg{sub y}Zn{sub 1−x−y}O heterojunctions using X-ray photoelectron spectroscopy measurements. Mg{sub x}Zn{sub 1−x}O and Be{sub x}Mg{sub y}Zn{sub 1−x−y}O films have been grown on c-plane sapphire substrates by plasma-assisted molecular beam epitaxy. The valence band offset (ΔE{sub V}) of Mg{sub 0.15}Zn{sub 0.85}O (E{sub g} = 3.62 eV)/Be{sub 0.005}Mg{sub 0.19}Zn{sub 0.805}O (E{sub g} = 3.73 eV) heterojunction is 0.01 eV and Be{sub 0.005}Mg{sub 0.19}Zn{sub 0.805}O has a lower VBM. The increased Mg composition is the main factor for the reduction of VBM. The VBM of Mg{sub x}Zn{sub 1−x}O is lower by 0.03 eV with the enlargement of E{sub g} from 3.62 eV to 3.73 eV by increasing Mg composition. Considering the effect of increased Mg composition, it is concluded that the little amount of Be makes the VBM go up by 0.02 eV when the E{sub g} of the alloy is 3.73 eV. The ΔE{sub V} of Mg{sub 0.11}Zn{sub 0.89}O (E{sub g} = 3.56 eV)/Be{sub 0.007}Mg{sub 0.12}Zn{sub 0.873}O (E{sub g} = 3.56 eV) heterojunction is calculated to be 0.03 eV and Be{sub 0.007}Mg{sub 0.12}Zn{sub 0.873}O has a higher VBM than Mg{sub 0.11}Zn{sub 0.89}O, which means that a little amount Be lifts the VBM by 0.03 eV when the E{sub g} of the alloy is 3.56 eV. The experimental measurements have offered a strong support for the theoretical research that alloying Be in Mg{sub x}Zn{sub 1−x}O alloys is hopeful to form a higher VBM and to enhance the p-type dopability of MgZnO.

  10. A low-temperature study of manganese-induced ferromagnetism and valence band convergence in tin telluride

    NASA Astrophysics Data System (ADS)

    Chi, Hang; Tan, Gangjian; Kanatzidis, Mercouri G.; Li, Qiang; Uher, Ctirad

    2016-05-01

    SnTe is renowned for its promise in advancing energy-related technologies based on thermoelectricity and for its topological crystalline insulator character. Here, we demonstrate that each Mn atom introduces ˜4 μB (Bohr magneton) of magnetic moment to Sn1-xMnxTe. The Curie temperature TC reaches ˜14 K for x = 0.12, as observed in the field dependent hysteresis of magnetization and the anomalous Hall effect. In accordance with a modified two-band electronic Kane model, the light L-valence-band and the heavy Σ-valence-band gradually converge in energy with increasing Mn concentration, leading to a decreasing ordinary Hall coefficient RH and a favorably enhanced Seebeck coefficient S at the same time. With the thermal conductivity κ lowered chiefly via point defects associated with the incorporation of Mn, the strategy of Mn doping also bodes well for efficient thermoelectric applications at elevated temperatures.

  11. Valence and Conduction Band Densities of States of Metal Halide Perovskites: A Combined Experimental–Theoretical Study

    PubMed Central

    2016-01-01

    We report valence and conduction band densities of states measured via ultraviolet and inverse photoemission spectroscopies on three metal halide perovskites, specifically methylammonium lead iodide and bromide and cesium lead bromide (MAPbI3, MAPbBr3, CsPbBr3), grown at two different institutions on different substrates. These are compared with theoretical densities of states (DOS) calculated via density functional theory. The qualitative agreement achieved between experiment and theory leads to the identification of valence and conduction band spectral features, and allows a precise determination of the position of the band edges, ionization energy and electron affinity of the materials. The comparison reveals an unusually low DOS at the valence band maximum (VBM) of these compounds, which confirms and generalizes previous predictions of strong band dispersion and low DOS at the MAPbI3 VBM. This low DOS calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites. PMID:27364125

  12. Valence and Conduction Band Densities of States of Metal Halide Perovskites: A Combined Experimental-Theoretical Study.

    PubMed

    Endres, James; Egger, David A; Kulbak, Michael; Kerner, Ross A; Zhao, Lianfeng; Silver, Scott H; Hodes, Gary; Rand, Barry P; Cahen, David; Kronik, Leeor; Kahn, Antoine

    2016-07-21

    We report valence and conduction band densities of states measured via ultraviolet and inverse photoemission spectroscopies on three metal halide perovskites, specifically methylammonium lead iodide and bromide and cesium lead bromide (MAPbI3, MAPbBr3, CsPbBr3), grown at two different institutions on different substrates. These are compared with theoretical densities of states (DOS) calculated via density functional theory. The qualitative agreement achieved between experiment and theory leads to the identification of valence and conduction band spectral features, and allows a precise determination of the position of the band edges, ionization energy and electron affinity of the materials. The comparison reveals an unusually low DOS at the valence band maximum (VBM) of these compounds, which confirms and generalizes previous predictions of strong band dispersion and low DOS at the MAPbI3 VBM. This low DOS calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites. PMID:27364125

  13. Internal-strain effect on the valence band of strained silicon and its correlation with the bond angles

    SciTech Connect

    Inaoka, Takeshi Yanagisawa, Susumu; Kadekawa, Yukihiro

    2014-02-14

    By means of the first-principles density-functional theory, we investigate the effect of relative atom displacement in the crystal unit cell, namely, internal strain on the valence-band dispersion of strained silicon, and find close correlation of this effect with variation in the specific bond angles due to internal strain. We consider the [111] ([110]) band dispersion for (111) ((110)) biaxial tensility and [111] ([110]) uniaxial compression, because remarkably small values of hole effective mass m* can be obtained in this dispersion. Under the practical condition of no normal stress, biaxial tensility (uniaxial compression) involves additional normal compression (tensility) and internal strain. With an increase in the internal-strain parameter, the energy separation between the highest and second-highest valence bands becomes strikingly larger, and the highest band with conspicuously small m* extends remarkably down to a lower energy region, until it intersects or becomes admixed with the second band. This is closely correlated with the change in the specific bond angles, and this change can reasonably explain the above enlargement of the band separation.

  14. Valence band gaps and plasma energies for galena, sphalerite, and chalcopyrite natural minerals using differential optical reflectance spectroscopy

    NASA Astrophysics Data System (ADS)

    Todoran, R.; Todoran, D.; Szakacs, Zs.

    2015-12-01

    The paper presents the determinations of the valence band gaps and plasma energies of the galena, sphalerite and chalcopyrite natural minerals. The work was carried out using differential optical reflectance spectroscopy of the clean mineral surfaces. The determination of the optical properties such as refractive index, real part of the complex dielectric constant and the location of certain van Hove singularities, was carried out using the Kramers-Kronig formalism.

  15. Anomalous temperature dependence in valence band spectra: A resonant photoemission study of layered perovskite Sr{sub 2}CoO{sub 4}

    SciTech Connect

    Pandey, Pankaj K.; Choudhary, R. J. Phase, D. M.

    2014-05-05

    Valence band spectra (VBS) and its modification across Curie temperature (T{sub C}) of Sr{sub 2}CoO{sub 4} thin film are studied using resonant photoemission spectroscopy. It is found that VBS mainly consists of hybridized states of Co-3d t{sub 2g}e{sub g} and O-2p; however, Co-3d e{sub g} states show its prominence only in the ferromagnetic temperature regime. Below T{sub C}, spectral weight transfer takes place anomalously from high binding energy (B.E.) region to low B.E. region, signifying the enhanced intermediate or low spin state Co{sup 4+} ions. It is suggested that spin-lattice coupling and many-body effects in Sr{sub 2}CoO{sub 4} derived from the strong electron correlations lead to such temperature dependence of VBS.

  16. Direct determination of the band offset in atomic layer deposited ZnO/hydrogenated amorphous silicon heterojunctions from X-ray photoelectron spectroscopy valence band spectra

    SciTech Connect

    Korte, L. Rößler, R.; Pettenkofer, C.

    2014-05-28

    The chemical composition and band alignment at the heterointerface between atomic layer deposition-grown zinc oxide (ZnO) and hydrogenated amorphous silicon (a-Si:H) is investigated using monochromatized X-ray photoelectron spectroscopy. A new approach for obtaining the valence band offset ΔE{sub V} is developed, which consists in fitting the valence band (VB) spectrum obtained for a-Si:H with a thin ZnO overlayer as the sum of experimentally obtained VB spectra of a bulk a-Si:H film and a thick ZnO film. This approach allows obtaining ΔE{sub V} = 2.71 ± 0.15 eV with a minimum of assumptions, and also yields information on the change in band bending of both substrate and ZnO film. The band offset results are compared to values obtained using the usual approach of comparing valence band edge-to-core level energy differences, ΔE{sub B,CL} − ΔE{sub B,VB}. Furthermore, a theoretical value for the VB offset is calculated from the concept of charge neutrality level line-up, using literature data for the charge neutrality levels and the experimentally determined ZnO/a-Si:H interface dipole. The thus obtained value of ΔE{sub V}{sup CNL} = 2.65 ± 0.3 eV agrees well with the experimental ΔE{sub V}.

  17. Valence Band Modification and High Thermoelectric Performance in SnTe Heavily Alloyed with MnTe.

    PubMed

    Tan, Gangjian; Shi, Fengyuan; Hao, Shiqiang; Chi, Hang; Bailey, Trevor P; Zhao, Li-Dong; Uher, Ctirad; Wolverton, Chris; Dravid, Vinayak P; Kanatzidis, Mercouri G

    2015-09-01

    We demonstrate a high solubility limit of >9 mol% for MnTe alloying in SnTe. The electrical conductivity of SnTe decreases gradually while the Seebeck coefficient increases remarkably with increasing MnTe content, leading to enhanced power factors. The room-temperature Seebeck coefficients of Mn-doped SnTe are significantly higher than those predicted by theoretical Pisarenko plots for pure SnTe, indicating a modified band structure. The high-temperature Hall data of Sn1-xMnxTe show strong temperature dependence, suggestive of a two-valence-band conduction behavior. Moreover, the peak temperature of the Hall plot of Sn1-xMnxTe shifts toward lower temperature as MnTe content is increased, which is clear evidence of decreased energy separation (band convergence) between the two valence bands. The first-principles electronic structure calculations based on density functional theory also support this point. The higher doping fraction (>9%) of Mn in comparison with ∼3% for Cd and Hg in SnTe gives rise to a much better valence band convergence that is responsible for the observed highest Seebeck coefficient of ∼230 μV/K at 900 K. The high doping fraction of Mn in SnTe also creates stronger point defect scattering, which when combined with ubiquitous endotaxial MnTe nanostructures when the solubility of Mn is exceeded scatters a wide spectrum of phonons for a low lattice thermal conductivity of 0.9 W m(-1) K(-1) at 800 K. The synergistic role that Mn plays in regulating the electron and phonon transport of SnTe yields a high thermoelectric figure of merit of 1.3 at 900 K. PMID:26308902

  18. Valence Band Modification and High Thermoelectric Performance in SnTe Heavily Alloyed with MnTe.

    PubMed

    Tan, Gangjian; Shi, Fengyuan; Hao, Shiqiang; Chi, Hang; Bailey, Trevor P; Zhao, Li-Dong; Uher, Ctirad; Wolverton, Chris; Dravid, Vinayak P; Kanatzidis, Mercouri G

    2015-09-01

    We demonstrate a high solubility limit of >9 mol% for MnTe alloying in SnTe. The electrical conductivity of SnTe decreases gradually while the Seebeck coefficient increases remarkably with increasing MnTe content, leading to enhanced power factors. The room-temperature Seebeck coefficients of Mn-doped SnTe are significantly higher than those predicted by theoretical Pisarenko plots for pure SnTe, indicating a modified band structure. The high-temperature Hall data of Sn1-xMnxTe show strong temperature dependence, suggestive of a two-valence-band conduction behavior. Moreover, the peak temperature of the Hall plot of Sn1-xMnxTe shifts toward lower temperature as MnTe content is increased, which is clear evidence of decreased energy separation (band convergence) between the two valence bands. The first-principles electronic structure calculations based on density functional theory also support this point. The higher doping fraction (>9%) of Mn in comparison with ∼3% for Cd and Hg in SnTe gives rise to a much better valence band convergence that is responsible for the observed highest Seebeck coefficient of ∼230 μV/K at 900 K. The high doping fraction of Mn in SnTe also creates stronger point defect scattering, which when combined with ubiquitous endotaxial MnTe nanostructures when the solubility of Mn is exceeded scatters a wide spectrum of phonons for a low lattice thermal conductivity of 0.9 W m(-1) K(-1) at 800 K. The synergistic role that Mn plays in regulating the electron and phonon transport of SnTe yields a high thermoelectric figure of merit of 1.3 at 900 K.

  19. Valence state, hybridization and electronic band structure in the charge ordered AlV2O4.

    PubMed

    Kalavathi, S; Amirthapandian, S; Chandra, Sharat; Sahu, P Ch; Sahu, H K

    2014-01-01

    The valence state, hybridization and electronic band structure of charge ordered AlV2O4 are investigated by measuring the electron energy loss spectra (EELS) and performing band structure calculations using the WIEN2k code. White line ratio and O K edges of V2O5, VO2, V2O3 and AlV2O4, obtained using electron energy loss spectroscopy, are analysed specifically to probe systematically the VO6 octahedra in all of them. The systematic decrease of the L2 intensity and the O K edge intensity from V(5+) in V2O5 to AlV2O4 indicates a progressive increase in the occupancy of the hybridized states, which is corroborated by the absence of a transition from O 1s to hybridized 2t(2g). Band structure calculations on the parent charge frustrated cubic phase and the charge ordered rhombohedral phase clearly document a band gap in the charge ordered state. From the structural information obtained after convergence and the spectroscopic information from EELS, it appears that partial orbital occupancy may lead to a deviation from an integral valence state on all the vanadium in this exotic charge ordered spinel system.

  20. Valence state, hybridization and electronic band structure in the charge ordered AlV2O4.

    PubMed

    Kalavathi, S; Amirthapandian, S; Chandra, Sharat; Sahu, P Ch; Sahu, H K

    2014-01-01

    The valence state, hybridization and electronic band structure of charge ordered AlV2O4 are investigated by measuring the electron energy loss spectra (EELS) and performing band structure calculations using the WIEN2k code. White line ratio and O K edges of V2O5, VO2, V2O3 and AlV2O4, obtained using electron energy loss spectroscopy, are analysed specifically to probe systematically the VO6 octahedra in all of them. The systematic decrease of the L2 intensity and the O K edge intensity from V(5+) in V2O5 to AlV2O4 indicates a progressive increase in the occupancy of the hybridized states, which is corroborated by the absence of a transition from O 1s to hybridized 2t(2g). Band structure calculations on the parent charge frustrated cubic phase and the charge ordered rhombohedral phase clearly document a band gap in the charge ordered state. From the structural information obtained after convergence and the spectroscopic information from EELS, it appears that partial orbital occupancy may lead to a deviation from an integral valence state on all the vanadium in this exotic charge ordered spinel system. PMID:24285259

  1. A low-temperature study of manganese-induced ferromagnetism and valence band convergence in tin telluride

    DOE PAGES

    Chi, Hang; Tan, Gangjian; Kanatzidis, Mercouri G.; Li, Qiang; Uher, Ctirad

    2016-05-02

    Here, SnTe is renowned for its promise in advancing energy-related technologies based on thermoelectricity and for its topological crystalline insulator character. Here, we demonstrate that each Mn atom introduces ~ 4 μB (Bohr magneton) of magnetic moment to Sn1-xMnxTe. The Curie temperature TC reaches ~ 14 K for x = 0.12, as observed in the field dependent hysteresis of magnetization and the anomalous Hall effect. In accordance with a modified two-band electronic Kane model, the light L-valence-band and the heavy Σ-valence-band gradually converge in energy with increasing Mn concentration, leading to a decreasing ordinary Hall coefficient RH and a favorablymore » enhanced Seebeck coefficient S at the same time. With the thermal conductivity κ lowered chiefly via point defects associated with the incorporation of Mn, the strategy of Mn doping also bodes well for efficient thermoelectric applications at elevated temperatures.« less

  2. Experimental valence-band study of Ti(NiCu) alloys with different compositions and crystal structures

    NASA Astrophysics Data System (ADS)

    Senkovskiy, B. V.; Usachev, D. Yu.; Fedorov, A. V.; Shelyakov, A. V.; Adamchuk, V. K.

    2012-08-01

    The density of valence-band electronic states of Ti(NiCu) alloys with different crystal structures and elemental compositions has been studied by X-ray photoelectron spectroscopy. It has been established that the change in the crystal state initiated by a martensitic transformation or a transition from the amorphous state to the crystal state does not affect the valence-band electronic state density distribution of the Ti50Ni50 and Ti50Ni25Cu25 alloys. It has been shown that a change in the elemental composition leads to a noticeable redistribution of the electronic density in alloys of the Ti50Ni50 - x Cu x system ( x = 0, 10, 15, 25, 30, 38, 50 at. %). As the copper concentration in the Ti(NiCu) alloys increases, the contribution of the Ni d states in the vicinity of the Fermi level decreases, with the d band of nickel shifting toward higher binding energies, and that of copper, toward lower binding energies.

  3. Effects of ion aggregation on the intervalence transfer band of the mixed-valence biferrocenium cation in solution

    SciTech Connect

    Lowery, M.D.; Hammack, W.S.; Drickamer, H.G.; Hendrickson, D.N.

    1987-12-23

    The concentration dependence of the energy (E/sup op/) of the intervalence transfer (IT) electronic absorption band of mixed-valence biferrocenium triiodide dissolved in either nitrobenzene or dichloromethane is examined. In nitrobenzene, E/sup op/ increases rapidly from approx. 5.57 to approx. 6.05 x 10/sup 3/ cm/sup -1/ in the 0.24-0.4 mM range, whereupon further increases in the concentration of biferrocenium triiodide lead to E/sup op/ increasing more gradually to a value approx. 6.3 x 10/sup 3/ cm/sup -1/ at 24 mM. On the other hand, the full width at half maximum (..delta.. anti v/sub 1/2) and the transition moment of the IT band decrease with increasing concentration for biferrocenium triiodide in nitrobenzene. E/sup op/ increases, ..delta.. anti v/sub 1/2 remains constant, and the transition moment of the IT band increases with increasing concentration for biferrocenium triiodide in dichloromethane in the more limited range of 0.30-0.95 mM. These concentration dependencies of the IT band for biferrocenium triiodide are attributable to variable degrees of ion aggregation in solution. The concentration dependencies of the electrical conductivity of solutions of biferrocenium triiodide in either nitrobenzene or dichloromethane substantiate this proposal. IT band contours obtained at different concentrations are fit to the PKS vibronic model to yield parameters that characterize the electronic and vibronic coupling within the mixed-valence biferrocenium cation.

  4. Elucidation of the highest valence band and lowest conduction band shifts using XPS for ZnO and Zn0.99Cu0.01O band gap changes

    NASA Astrophysics Data System (ADS)

    Kamarulzaman, N.; Kasim, M. F.; Chayed, N. F.

    ZnO and Zn0.99Cu0.01O nanostructures were prepared by a simple sol-gel method. The band gaps of the materials were systematically studied based on the dependence of the dimensions of the nanostructures as well as the presence of a dopant material, Cu. ZnO and Zn0.99Cu0.01O nanostructures were found to exhibit band gap widening whilst substitution of Cu in the lattice of ZnO caused its band gap to narrow with respect to the pure ZnO materials. In order to understand the phenomenon of band gap change, structural, spectroscopic, particle size and morphological studies were done. The band gap change occurring when the materials were in the nanostructured phase was proven to be mainly due to the downward shift of the valence band. Interestingly, when the band gaps of the pure ZnO and Cu doped ZnO were compared, the band gap changes were due to different shifts of the valence bands.

  5. Impact of [110]/(001) uniaxial stress on valence band structure and hole effective mass of silicon

    NASA Astrophysics Data System (ADS)

    Jianli, Ma; Heming, Zhang; Jianjun, Song; Guanyu, Wang; Xiaoyan, Wang; Xiaobo, Xu

    2011-02-01

    The valence band structure and hole effective mass of silicon under a uniaxial stress in (001) surface along the [110] direction were detailedly investigated in the framework of the k · p theory. The results demonstrated that the splitting energy between the top band and the second band for uniaxial compressive stress is bigger than that of the tensile one at the same stress magnitude, and of all common used crystallographic direction, such as [110], [001], [1¯10] and [100], the effective mass for the top band along [110] crystallographic direction is lower under uniaxial compressive stress compared with other stresses and crystallographic directions configurations. In view of suppressing the scattering and reducing the effective mass, the [110] crystallographic direction is most favorable to be used as transport direction of the charge carrier to enhancement mobility when a uniaxial compressive stress along [110] direction is applied. The obtained results can provide a theory reference for the design and the selective of optimum stress and crystallorgraphic direction configuration of uniaxial strained silicon devices.

  6. Thermoelectric Enhancement in PbTe with K or Na codoping from tuning the interaction of the light- and heavy-hole valence bands

    SciTech Connect

    Androulakis, John; Todorov, Iliya; Chung, Duck Young; Ballikaya, Sedat; Wang, Guoyu Y; Uher, Ctirad; Kanatzidis, Mercouri G.

    2010-09-16

    The effect of K and K-Na substitution for Pb atoms in the rocksalt lattice of PbTe was investigated to test a hypothesis for development of resonant states in the valence band that may enhance the thermoelectric power. We combined high-temperature Hall-effect, electrical conductivity, and thermal conductivity measurements to show that K-Na codoping do not form resonance states but can control the energy difference of the maxima of the two primary valence subbands in PbTe. This leads to an enhanced interband interaction with rising temperature and a significant rise in the thermoelectric figure of merit of p -type PbTe. The experimental data can be explained by a combination of a single- and two-band models for the valence band of PbTe depending on hole density that varies in the range of 1–15x1019 cm-3 .

  7. Thermoelectric enhancement in PbTe with K or Na codoping from tuning the interaction of the light- and heavy-hole valence bands.

    SciTech Connect

    Androulakis, J.; Todorov, I.; Chung, D.-Y.; Ballikaya, S.; Wang, G.; Uher, C.; Kanatzidis, M.; Materials Science Division; Northwestern Univ.; Univ. of Michigan at Ann Arbor; Univ. of Istanbul

    2010-09-15

    The effect of K and K-Na substitution for Pb atoms in the rocksalt lattice of PbTe was investigated to test a hypothesis for development of resonant states in the valence band that may enhance the thermoelectric power. We combined high-temperature Hall-effect, electrical conductivity, and thermal conductivity measurements to show that K-Na codoping do not form resonance states but can control the energy difference of the maxima of the two primary valence subbands in PbTe. This leads to an enhanced interband interaction with rising temperature and a significant rise in the thermoelectric figure of merit of p-type PbTe. The experimental data can be explained by a combination of a single- and two-band models for the valence band of PbTe depending on hole density that varies in the range of 1-15 x 10{sup 19} cm{sup -3}.

  8. Deduction of the chemical state and the electronic structure of Nd{sub 2}Fe{sub 14}B compound from X-ray photoelectron spectroscopy core-level and valence-band spectra

    SciTech Connect

    Wang, Jing; Liang, Le; Zhang, Lanting E-mail: lmsun@sjtu.edu.cn; Sun, Limin E-mail: lmsun@sjtu.edu.cn; Hirano, Shinichi

    2014-10-28

    Characterization of chemical state and electronic structure of the technologically important Nd{sub 2}Fe{sub 14}B compound is attractive for understanding the physical nature of its excellent magnetic properties. X-ray photoelectron spectroscopy (XPS) study of such rare-earth compound is important and also challenging due to the easy oxidation of surface and small photoelectron cross-sections of rare-earth 4f electrons and B 2p electrons, etc. Here, we reported an investigation based on XPS spectra of Nd{sub 2}Fe{sub 14}B compound as a function of Ar ion sputtering time. The chemical state of Fe and that of B in Nd{sub 2}Fe{sub 14}B compound can be clearly determined to be 0 and −3, respectively. The Nd in Nd{sub 2}Fe{sub 14}B compound is found to have the chemical state of close to +3 instead of +3 as compared with the Nd in Nd{sub 2}O{sub 3}. In addition, by comparing the valence-band spectrum of Nd{sub 2}Fe{sub 14}B compound to that of the pure Fe, the contributions from Nd, Fe, and B to the valence-band structure of Nd{sub 2}Fe{sub 14}B compound is made more clear. The B 2p states and B 2s states are identified to be at ∼11.2 eV and ∼24.6 eV, respectively, which is reported for the first time. The contribution from Nd 4f states can be identified both in XPS core-level spectrum and XPS valence-band spectrum. Although Nd 4f states partially hybridize with Fe 3d states, Nd 4f states are mainly localized in Nd{sub 2}Fe{sub 14}B compound.

  9. Determination of the valence-band offset of CdS/CIS solar cell devices by target factor analysis

    SciTech Connect

    Niles, D.W.; Contreras, M.; Ramanathan, K.; Noufi, R.

    1996-05-01

    X-ray photoemission spectroscopy (XPS) is used to determine and compare the valence-band offsets ({Delta}E{sub v}) for CdS grown by chemical bath deposition on single-crystal and thin-film CuInSe{sub 2} (CIS). The thin-film CIS device was suitable for photovoltaic energy production. By sputtering through the CdS/CIS interface and reducing the depth profile with target factor analysis, the magnitude of {Delta}E{sub v} was determined to be {Delta}E{sub v} = 1.06 {+-} 0.15 eV for both the single-crystal and thin-film interfaces. This determination of {Delta}E{sub v} is about 0.25 eV larger than many previously reported estimations CdS grown by physical vapor deposition on CIS and helps explain the record performance of CdS/CIS photovoltaic devices.

  10. Experimental Observation and Theoretical Description of the Pure Fano Effect in the Valence-Band Photoemission of Ferromagnets

    SciTech Connect

    Minar, J.; Ebert, H.; De Nadaie, C.; Brookes, N.B.; Venturini, F.; Ghiringhelli, G.; Chioncel, L.; Katsnelson, M. I.; Lichtenstein, A. I.

    2005-10-14

    The pure Fano effect in angle-integrated valence-band photoemission of ferromagnets has been observed for the first time. A contribution of the intrinsic spin polarization to the spin polarization of the photoelectrons has been avoided by an appropriate choice of the experimental parameters. The theoretical description of the resulting spectra reveals a complete analogy to the Fano effect observed before for paramagnetic transition metals. While the theoretical photocurrent and spin-difference spectra are found in good quantitative agreement with experiment in the case of Fe and Co, only a qualitative agreement could be achieved in the case of Ni by calculations on the basis of plain local spin-density approximation. Agreement with experimental data could be improved in this case in a very substantial way by a treatment of correlation effects on the basis of dynamical mean field theory.

  11. Fano effect in the angle-integrated valence band photoemission of the noble metals Cu, Ag, and Au

    SciTech Connect

    De Nadaie, C.; Brookes, N.B.; Minar, J.; Ebert, H.; Ghiringhelli, G.; Tagliaferri, A.

    2004-10-01

    Results of a combined experimental and theoretical investigation on the Fano-effect in the angle-integrated valence band photoemission of the noble metals are presented. In line with the fact that the Fano-effect is caused by the spin-orbit-coupling, the observed spin polarization of the photocurrent was found to be the more pronounced the higher the atomic number of the element investigated. The ratio of the normalized spin difference curves, however, agreed only for Cu and Ag with the ratio of the corresponding spin-orbit coupling strength parameters. The deviation from this expected behavior in the case of Au could be explained by the properties of individual d-p- and d-f-contributions to the total spin difference curves, that were found to be quite different for Au compared to Cu and Ag.

  12. The valence band structure of Ag{sub x}Rh{sub 1–x} alloy nanoparticles

    SciTech Connect

    Yang, Anli; Sakata, Osami; Kusada, Kohei; Kobayashi, Hirokazu; Yayama, Tomoe; Ishimoto, Takayoshi; Yoshikawa, Hideki; Koyama, Michihisa; and others

    2014-10-13

    The valence band (VB) structures of face-centered-cubic Ag-Rh alloy nanoparticles (NPs), which are known to have excellent hydrogen-storage properties, were investigated using bulk-sensitive hard x-ray photoelectron spectroscopy. The observed VB spectra profiles of the Ag-Rh alloy NPs do not resemble simple linear combinations of the VB spectra of Ag and Rh NPs. The observed VB hybridization was qualitatively reproduced via a first-principles calculation. The electronic structure of the Ag{sub 0.5}Rh{sub 0.5} alloy NPs near the Fermi edge was strikingly similar to that of Pd NPs, whose superior hydrogen-storage properties are well known.

  13. Valence band structure of PDMS surface and a blend with MWCNTs: A UPS and MIES study of an insulating polymer

    NASA Astrophysics Data System (ADS)

    Schmerl, Natalya M.; Khodakov, Dmitriy A.; Stapleton, Andrew J.; Ellis, Amanda V.; Andersson, Gunther G.

    2015-10-01

    The use of polydimethylsiloxane (PDMS) is increasing with new technologies working toward compact, flexible and transparent devices for use in medical and microfluidic systems. Electronic characterization of PDMS and other insulating materials is difficult due to charging, yet necessary for many applications where the interfacial structure is vital to device function or further modification. The outermost layer in particular is of importance as this is the area where chemical reactions such as surface functionalization will occur. Here, we investigate the valence band structure of the outermost layer and near surface area of PDMS through the use of metastable induced photoelectron spectroscopy (MIES) paired with ultraviolet photoelectron spectroscopy (UPS). The chemical composition of the samples under investigation were measured via X-ray photoelectron spectroscopy (XPS), and the vertical distribution of the polymer was shown with neutral impact collision ion scattering spectroscopy (NICISS). Three separate methods for charge compensation are used for the samples, and their effectiveness is compared.

  14. Valence band offset of β-Ga2O3/wurtzite GaN heterostructure measured by X-ray photoelectron spectroscopy

    PubMed Central

    2012-01-01

    A sample of the β-Ga2O3/wurtzite GaN heterostructure has been grown by dry thermal oxidation of GaN on a sapphire substrate. X-ray diffraction measurements show that the β-Ga2O3 layer was formed epitaxially on GaN. The valence band offset of the β-Ga2O3/wurtzite GaN heterostructure is measured by X-ray photoelectron spectroscopy. It is demonstrated that the valence band of the β-Ga2O3/GaN structure is 1.40 ± 0.08 eV. PMID:23046910

  15. Hot photoluminescence and valence band warping in GaAs and InP crytals

    NASA Astrophysics Data System (ADS)

    Alekseev, M. A.; Karlik, I. Ya.; Merkulov, I. A.; Mirlin, D. N.; Sapega, V. F.

    1988-03-01

    The investigations of hot photoluminescence are shown to be a powerful technique for determination of band parameters (Luttinger parameters) of A 3B 5 compounds. The experiment and calculations are carried out for GaAs and InP crystals.

  16. Theory of Auger-electron and appearance-potential spectroscopy for interacting valence-band electrons

    NASA Astrophysics Data System (ADS)

    Nolting, W.; Geipel, G.; Ertl, K.

    1991-12-01

    A theory of Auger-electron spectroscopy (AES) and appearance-potential spectroscopy (APS) is presented for interacting electrons in a nondegenerate energy band, described within the framework of the Hubbard model. Both types of spectroscopy are based on the same two-particle spectral density. A diagrammatic vertex-correction method (Matsubara formalism) is used to express this function in terms of the one-particle spectral density. The latter is approximately determined for arbitrary temperature T, arbitrary coupling strength U/W (U, the intra-atomic Coulomb matrix element; W, the width of the ``free'' Bloch band), and arbitrary band occupations n (0<=n<=2 average number of band electrons per site) by a self-consistent moment method. In weakly coupled systems the electron correlations give rise to certain deformations of the quasiparticle density of states (QDOS) in relation to the Bloch density of states (BDOS), where, however, spontaneous magnetic order is excluded, irrespective of the band filling n. The AE (AP) spectra consist of only one structure a few eV wide (``bandlike'') which is strongly n dependent, but only slightly T dependent, being rather well approximated by a simple self-convolution of the occupied (unoccupied) QDOS. For strongly correlated electrons the Bloch band splits into two quasiparticle subbands. This leads for n<1 to one line in the AE spectrum and three lines in the AP spectrum, and vice versa for n>1. For sufficiently strong correlations U/W additional satellites appear that refer to situations where the two excited quasiparticles (quasiholes) propagate as tightly bound pairs through the lattice without being scattered by other charge carriers. As soon as the satellite splits off from the bandlike part of the spectrum, it takes almost the full spectral weight, conveying the impression of an ``atomiclike'' AE (AP) line shape. The satellite has almost exactly the structure of the free BDOS. If the particle density n as well as the hole

  17. AgI alloying in SnTe boosts the thermoelectric performance via simultaneous valence band convergence and carrier concentration optimization

    NASA Astrophysics Data System (ADS)

    Banik, Ananya; Biswas, Kanishka

    2016-10-01

    SnTe, a Pb-free analogue of PbTe, was earlier assumed to be a poor thermoelectric material due to excess p-type carrier concentration and large energy separation between light and heavy hole valence bands. Here, we report the enhancement of the thermoelectric performance of p-type SnTe by Ag and I co-doping. AgI (1-6 mol%) alloying in SnTe modulates its electronic structure by increasing the band gap of SnTe, which results in decrease in the energy separation between its light and heavy hole valence bands, thereby giving rise to valence band convergence. Additionally, iodine doping in the Te sublattice of SnTe decreases the excess p-type carrier concentration. Due to significant decrease in hole concentration and reduction of the energy separation between light and heavy hole valence bands, significant enhancement in Seebeck coefficient was achieved at the temperature range of 600-900 K for Sn1-xAgxTe1-xIx samples. A maximum thermoelectric figure of merit, zT, of ~1.05 was achieved at 860 K in high quality crystalline ingot of p-type Sn0.95Ag0.05Te0.95I0.05.

  18. Coupled valence band dispersions and the quantum defect of excitons in Cu2O

    NASA Astrophysics Data System (ADS)

    Schöne, Florian; Krüger, Sjard-Ole; Grünwald, Peter; Aßmann, Marc; Heckötter, Julian; Thewes, Johannes; Stolz, Heinrich; Fröhlich, Dietmar; Bayer, Manfred; Scheel, Stefan

    2016-07-01

    Recent high-resolution absorption spectroscopy on highly excited excitons in cuprous oxide (Kazimierczuk et al 2014 Nature 514 343-347) have revealed significant deviations of their spectrum from the ideal hydrogen-like series. In atomic physics, the influence of the ionic core and the resulting modifications of the Coulomb interaction are accounted for by the introduction of a quantum defect. Here we translate this concept to the realm of semiconductor physics and show how the complex band dispersion of a crystal is mirrored in a set of empirical parameters similar to the quantum defect in atoms. Experimental data collected from high-resolution absorption spectroscopy in electric fields allow us to compare results for multiple angular momentum states of the yellow and even the green exciton series of {{Cu}}2{{O}}. The agreement between theory and experiment validates our assignment of the quantum defect to the nonparabolicity of the band dispersion.

  19. Magnetic-field-induced nonparabolicity of exciton dispersion in semiconductors with a nondegenerate valence band

    SciTech Connect

    Loginov, D. K. Chegodaev, A. D.

    2011-09-15

    The nonparabolicity of exciton dispersion due to the mixing of the ground and excited states of an exciton in an external magnetic field perpendicular to the direction of its motion is considered. A model describing this effect is proposed and the nonparabolicity for an exciton in a CdTe crystal is calculated. The magnetic-field induced exciton nonparabolicity is compared with the effect caused by the nonparabolicity of the electron energy dispersion in the conduction band.

  20. Generalized valence bond description of the ground states (X(1)Σg(+)) of homonuclear pnictogen diatomic molecules: N2, P2, and As2.

    PubMed

    Xu, Lu T; Dunning, Thom H

    2015-06-01

    The ground state, X1Σg+, of N2 is a textbook example of a molecule with a triple bond consisting of one σ and two π bonds. This assignment, which is usually rationalized using molecular orbital (MO) theory, implicitly assumes that the spins of the three pairs of electrons involved in the bonds are singlet-coupled (perfect pairing). However, for a six-electron singlet state, there are five distinct ways to couple the electron spins. The generalized valence bond (GVB) wave function lifts this restriction, including all of the five spin functions for the six electrons involved in the bond. For N2, we find that the perfect pairing spin function is indeed dominant at Re but that it becomes progressively less so from N2 to P2 and As2. Although the perfect pairing spin function is still the most important spin function in P2, the importance of a quasi-atomic spin function, which singlet couples the spins of the electrons in the σ orbitals while high spin coupling those of the electrons in the π orbitals on each center, has significantly increased relative to N2 and, in As2, the perfect pairing and quasi-atomic spin couplings are on essentially the same footing. This change in the spin coupling of the electrons in the bonding orbitals down the periodic table may contribute to the rather dramatic decrease in the strengths of the Pn2 bonds from N2 to As2 as well as in the increase in their chemical reactivity and should be taken into account in more detailed analyses of the bond energies in these species. We also compare the spin coupling in N2 with that in C2, where the quasi-atomic spin coupling dominants around Re. PMID:26575549

  1. Interpretation of valence band photoemission spectra at organic-metal interfaces

    NASA Astrophysics Data System (ADS)

    Giovanelli, L.; Bocquet, F. C.; Amsalem, P.; Lee, H.-L.; Abel, M.; Clair, S.; Koudia, M.; Faury, T.; Petaccia, L.; Topwal, D.; Salomon, E.; Angot, T.; Cafolla, A. A.; Koch, N.; Porte, L.; Goldoni, A.; Themlin, J.-M.

    2013-01-01

    Adsorption of organic molecules on well-oriented single-crystal coinage metal surfaces fundamentally affects the energy distribution curve of ultraviolet photoelectron spectroscopy spectra. New features not present in the spectrum of the pristine metal can be assigned as “interface states” having some degree of molecule-substrate hybridization. Here it is shown that interface states having molecular orbital character can easily be identified at low binding energy as isolated features above the featureless substrate sp plateau. On the other hand, much care must be taken in assigning adsorbate-induced features when these lie within the d-band spectral region of the substrate. In fact, features often interpreted as characteristic of the molecule-substrate interaction may actually arise from substrate photoelectrons scattered by the adsorbates. This phenomenon is illustrated through a series of examples of noble-metal single-crystal surfaces covered by monolayers of large π-conjugated organic molecules.

  2. Precise tuning of the Curie temperature of (Ga,Mn)As-based magnetic semiconductors by hole compensation: Support for valence-band ferromagnetism

    NASA Astrophysics Data System (ADS)

    Zhou, Shengqiang; Li, Lin; Yuan, Ye; Rushforth, A. W.; Chen, Lin; Wang, Yutian; Böttger, R.; Heller, R.; Zhao, Jianhua; Edmonds, K. W.; Campion, R. P.; Gallagher, B. L.; Timm, C.; Helm, M.

    2016-08-01

    For the prototype diluted ferromagnetic semiconductor (Ga,Mn)As, there is a fundamental concern about the electronic states near the Fermi level, i.e., whether the Fermi level resides in a well-separated impurity band derived from Mn doping (impurity-band model) or in the valence band that is already merged with the Mn-derived impurity band (valence-band model). We investigate this question by carefully shifting the Fermi level by means of carrier compensation. We use helium-ion implantation, a standard industry technology, to precisely compensate the hole doping of GaAs-based diluted ferromagnetic semiconductors while keeping the Mn concentration constant. We monitor the change of Curie temperature (TC) and conductivity. For a broad range of samples including (Ga,Mn)As and (Ga,Mn)(As,P) with various Mn and P concentrations, we observe a smooth decrease of TC with carrier compensation over a wide temperature range while the conduction is changed from metallic to insulating. The existence of TC below 10 K is also confirmed in heavily compensated samples. Our experimental results are naturally explained within the valence-band picture.

  3. Ionization equilibrium at the transition from valence-band to acceptor-band migration of holes in boron-doped diamond

    NASA Astrophysics Data System (ADS)

    Poklonski, N. A.; Vyrko, S. A.; Poklonskaya, O. N.; Kovalev, A. I.; Zabrodskii, A. G.

    2016-06-01

    A quasi-classical model of ionization equilibrium in the p-type diamond between hydrogen-like acceptors (boron atoms which substitute carbon atoms in the crystal lattice) and holes in the valence band (v-band) is proposed. The model is applicable on the insulator side of the insulator-metal concentration phase transition (Mott transition) in p-Dia:B crystals. The densities of the spatial distributions of impurity atoms (acceptors and donors) and of holes in the crystal are considered to be Poissonian, and the fluctuations of their electrostatic potential energy are considered to be Gaussian. The model accounts for the decrease in thermal ionization energy of boron atoms with increasing concentration, as well as for electrostatic fluctuations due to the Coulomb interaction limited to two nearest point charges (impurity ions and holes). The mobility edge of holes in the v-band is assumed to be equal to the sum of the threshold energy for diffusion percolation and the exchange energy of the holes. On the basis of the virial theorem, the temperature Tj is determined, in the vicinity of which the dc band-like conductivity of holes in the v-band is approximately equal to the hopping conductivity of holes via the boron atoms. For compensation ratio (hydrogen-like donor to acceptor concentration ratio) K ≈ 0.15 and temperature Tj, the concentration of "free" holes in the v-band and their jumping (turbulent) drift mobility are calculated. Dependence of the differential energy of thermal ionization of boron atoms (at the temperature 3Tj/2) as a function of their concentration N is calculated. The estimates of the extrapolated into the temperature region close to Tj hopping drift mobility of holes hopping from the boron atoms in the charge states (0) to the boron atoms in the charge states (-1) are given. Calculations based on the model show good agreement with electrical conductivity and Hall effect measurements for p-type diamond with boron atom concentrations in the

  4. Valence band structure and magnetic properties of Co-doped Fe3O4(100) films

    NASA Astrophysics Data System (ADS)

    Ran, F. Y.; Tsunemaru, Y.; Hasegawa, T.; Takeichi, Y.; Harasawa, A.; Yaji, K.; Kim, S.; Kakizaki, A.

    2011-06-01

    Structural and magnetic properties, and the valence band structure of pure and Co-doped (up to 33%) Fe3O4(100) films were investigated. Reconstruction of the Fe3O4(100) surface is found to be blocked by Co doping. Doped Co ions in Fe3O4 are in a charge state of 2 + and substitute the Fe2+ in the B site of Fe3O4. All the films exhibit room temperature ferromagnetism. Co doping changes the coercivity and reduces saturation magnetization. The density of states near the Fermi level is reduced by Co doping due to the decrease of Fe2+ in the B site, which might responsible for the decrease in conductivity and magnetoresistance of Co-doped Fe3O4. The Verwey transition in the range of 100-120 K is observed for the pure Fe3O4 film, while no transition could be detected for Co-doped Fe3O4 films.

  5. Exciton binding energies and the valence-band offset in mixed type-I--type-II strained-layer superlattices

    SciTech Connect

    Peyla, P.; Merle d'Aubigne, Y.; Wasiela, A.; Romestain, R.; Mariette, H. ); Sturge, M.D. ); Magnea, N.; Tuffigo, H. )

    1992-07-15

    Strained CdTe-Cd{sub 1{minus}{ital x}}Zn{sub {ital x}}Te superlattices are of mixed type: electrons and heavy holes are confined to the CdTe layers (type I) while light holes are confined to the Cd{sub 1{minus}{ital x}}Zn{sub {ital x}}Te layers (type II). In this paper we calculate the exciton binding energy (EBE) as a function of superlattice period for both type-I (spatially direct) and type-II (spatially indirect) excitons. For the heavy-hole (type-I) exciton the binding energy is larger than the bulk value, and varies only slowly with the period down to small periods, where the exciton acquires a three-dimensional character and our calculation breaks down. For the light-hole (type-II) exciton the binding energy at large period is much smaller, due to the spatial separation of electron and hole. As the period decreases, the binding energy increases steadily to reach its bulk value for vanishingly small period. Given the EBE's, we can fit the already published data on the exciton transition energies with a single adjustable parameter, the average valence-band offset'' (averaged over the heavy and light holes). This is the algebraic sum of the chemical-offset and the hydrostatic-strain contribution, and is found to be (2{plus minus}4)% of the difference in band gap between the barrier and well. This value lies in the range predicted theoretically.

  6. Duplication and deletion of chromosome band 2(p21p22) resulting from a familial interstitial insertion (2;11)(p21;p15)

    SciTech Connect

    Sawyer, J.R.; Jones, E.; Hawks, F.F.; Quirk, J.G. Jr.; Cunniff, C.

    1994-02-15

    Routine amniocentesis for advanced maternal age led to the prenatal diagnosis of a fetus with a karyotype of a 46,XX,del(2)(p21p22). At delivery the baby had holopresencephaly as the major clinical finding, which has been associated with a deletion of band 2p21 in several other case reports. Chromosome studies of the parents showed a normal 46,XY karyotype in the father, and a balanced interstitial insertion 46,XX dir ins (11;2)(p15.1;p21p22) in the mother. Subsequent chromosome studies of other relatives documented a 23-year-old half-brother of the proposita with a partial trisomy for the segment deleted in the proposita. The half-brother showed the derivative chromosome 11 from the mother, resulting in a 46,XY,der(11)dup(2)(p21p22) karyotype. Major clinical findings include short stature, mild development delay, and behavior abnormalities. A half-sister of the proposita is also a balanced carrier of the dir ins (11;2)(p15.1;p21p22.2). The association of the deletion chromosome band 2p21 and the clinical finding of holoprosencephaly is further supported by the findings in this family. 9 refs., 5 figs.

  7. Valence band offsets of Sc x Ga1‑x N/AlN and Sc x Ga1‑x N/GaN heterojunctions

    NASA Astrophysics Data System (ADS)

    Tsui, H. C. L.; Goff, L. E.; Palgrave, R. G.; Beere, H. E.; Farrer, I.; Ritchie, D. A.; Moram, M. A.

    2016-07-01

    The valence band offsets of Sc x Ga1‑x N/AlN heterojunctions were measured by x-ray photoelectron spectroscopy (XPS) and were found to increase from 0.42 eV to 0.95 eV as the Sc content x increased from 0 to 0.15. The increase in valence band offset with increasing x is attributed to the corresponding increase in spontaneous polarization of the wurtzite structure. The Sc x Ga1‑x N/AlN heterojunction is type I, similar to other III-nitride-based heterojunctions. The data also indicate that a type II staggered heterojunction, which can enhance spatial charge separation, could be formed if Sc x Ga1‑x N is grown on GaN.

  8. Influence of leaching on surface composition, microstructure, and valence band of single grain icosahedral Al-Cu-Fe quasicrystal

    SciTech Connect

    Lowe, M.; McGrath, R.; Sharma, H. R.; Yadav, T. P.; Fournée, V.; Ledieu, J.

    2015-03-07

    The use of quasicrystals as precursors to catalysts for the steam reforming of methanol is potentially one of the most important applications of these new materials. To develop application as a technology requires a detailed understanding of the microscopic behavior of the catalyst. Here, we report the effect of leaching treatments on the surface microstructure, chemical composition, and valence band of the icosahedral (i-) Al-Cu-Fe quasicrystal in an attempt to prepare a model catalyst. The high symmetry fivefold surface of a single grain i-Al-Cu-Fe quasicrystal was leached with NaOH solution for varying times, and the resulting surface was characterized by x-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The leaching treatments preferentially remove Al producing a capping layer consisting of Fe and Cu oxides. The subsurface layer contains elemental Fe and Cu in addition to the oxides. The quasicrystalline bulk structure beneath remains unchanged. The subsurface gradually becomes Fe{sub 3}O{sub 4} rich with increasing leaching time. The surface after leaching exhibits micron sized dodecahedral cavities due to preferential leaching along the fivefold axis. Nanoparticles of the transition metals and their oxides are precipitated on the surface after leaching. The size of the nanoparticles is estimated by high resolution transmission microscopy to be 5-20 nm, which is in agreement with the AFM results. Selected area electron diffraction (SAED) confirms the crystalline nature of the nanoparticles. SAED further reveals the formation of an interface between the high atomic density lattice planes of nanoparticles and the quasicrystal. These results provide an important insight into the preparation of model catalysts of nanoparticles for steam reforming of methanol.

  9. Influence of leaching on surface composition, microstructure, and valence band of single grain icosahedral Al-Cu-Fe quasicrystal

    NASA Astrophysics Data System (ADS)

    Lowe, M.; Yadav, T. P.; Fournée, V.; Ledieu, J.; McGrath, R.; Sharma, H. R.

    2015-03-01

    The use of quasicrystals as precursors to catalysts for the steam reforming of methanol is potentially one of the most important applications of these new materials. To develop application as a technology requires a detailed understanding of the microscopic behavior of the catalyst. Here, we report the effect of leaching treatments on the surface microstructure, chemical composition, and valence band of the icosahedral (i-) Al-Cu-Fe quasicrystal in an attempt to prepare a model catalyst. The high symmetry fivefold surface of a single grain i-Al-Cu-Fe quasicrystal was leached with NaOH solution for varying times, and the resulting surface was characterized by x-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The leaching treatments preferentially remove Al producing a capping layer consisting of Fe and Cu oxides. The subsurface layer contains elemental Fe and Cu in addition to the oxides. The quasicrystalline bulk structure beneath remains unchanged. The subsurface gradually becomes Fe3O4 rich with increasing leaching time. The surface after leaching exhibits micron sized dodecahedral cavities due to preferential leaching along the fivefold axis. Nanoparticles of the transition metals and their oxides are precipitated on the surface after leaching. The size of the nanoparticles is estimated by high resolution transmission microscopy to be 5-20 nm, which is in agreement with the AFM results. Selected area electron diffraction (SAED) confirms the crystalline nature of the nanoparticles. SAED further reveals the formation of an interface between the high atomic density lattice planes of nanoparticles and the quasicrystal. These results provide an important insight into the preparation of model catalysts of nanoparticles for steam reforming of methanol.

  10. Interaction of Cr(3+) with valence and conduction bands in the long persistent phosphor ZnGa2O4:Cr(3+), studied by ENDOR spectroscopy.

    PubMed

    Binet, Laurent; Sharma, Suchinder K; Gourier, Didier

    2016-09-28

    Cr(3+)-doped zinc gallate ZnGa2O4 is a red-near infrared (IR) long persistent phosphor that can be excited by orange-red light, in the transparency window of living tissues. With this property, persistent luminescence nanoparticles were recently used for in vivo optical imaging of tumors in mice. In order to understand the origin of the excitability of persistent luminescence by visible light in this material, a Q-band ENDOR investigation of (71/69)Ga and (53)Cr nuclei was performed in ZnGa2O4:Cr(3+) to get information on the interaction of Cr(3+) with valence and conduction bands. The positive electron spin density at Ga nuclei revealed a dominant interaction of the (4)A2 ground state of Cr(3+) with the valence band, and a weaker interaction with the conduction band. The latter may occur only in the excited (2)E and (4)T2 states of Cr(3+). It is proposed that when these two interactions are present, pairs of electrons and holes can be generated from excited Cr(3+) in distorted sites undergoing local electric field produced by neighboring defects with opposite charges. PMID:27460505

  11. Interaction of Cr3+ with valence and conduction bands in the long persistent phosphor ZnGa2O4:Cr3+, studied by ENDOR spectroscopy

    NASA Astrophysics Data System (ADS)

    Binet, Laurent; Sharma, Suchinder K.; Gourier, Didier

    2016-09-01

    Cr3+-doped zinc gallate ZnGa2O4 is a red-near infrared (IR) long persistent phosphor that can be excited by orange-red light, in the transparency window of living tissues. With this property, persistent luminescence nanoparticles were recently used for in vivo optical imaging of tumors in mice. In order to understand the origin of the excitability of persistent luminescence by visible light in this material, a Q-band ENDOR investigation of 71/69Ga and 53Cr nuclei was performed in ZnGa2O4:Cr3+ to get information on the interaction of Cr3+ with valence and conduction bands. The positive electron spin density at Ga nuclei revealed a dominant interaction of the 4A2 ground state of Cr3+ with the valence band, and a weaker interaction with the conduction band. The latter may occur only in the excited 2E and 4T2 states of Cr3+. It is proposed that when these two interactions are present, pairs of electrons and holes can be generated from excited Cr3+ in distorted sites undergoing local electric field produced by neighboring defects with opposite charges.

  12. Interaction of Cr(3+) with valence and conduction bands in the long persistent phosphor ZnGa2O4:Cr(3+), studied by ENDOR spectroscopy.

    PubMed

    Binet, Laurent; Sharma, Suchinder K; Gourier, Didier

    2016-09-28

    Cr(3+)-doped zinc gallate ZnGa2O4 is a red-near infrared (IR) long persistent phosphor that can be excited by orange-red light, in the transparency window of living tissues. With this property, persistent luminescence nanoparticles were recently used for in vivo optical imaging of tumors in mice. In order to understand the origin of the excitability of persistent luminescence by visible light in this material, a Q-band ENDOR investigation of (71/69)Ga and (53)Cr nuclei was performed in ZnGa2O4:Cr(3+) to get information on the interaction of Cr(3+) with valence and conduction bands. The positive electron spin density at Ga nuclei revealed a dominant interaction of the (4)A2 ground state of Cr(3+) with the valence band, and a weaker interaction with the conduction band. The latter may occur only in the excited (2)E and (4)T2 states of Cr(3+). It is proposed that when these two interactions are present, pairs of electrons and holes can be generated from excited Cr(3+) in distorted sites undergoing local electric field produced by neighboring defects with opposite charges.

  13. M-banding characterization of a 16p11.2p13.1 tandem duplication in a child with autism, neurodevelopmental delay and dysmorphism.

    PubMed

    Behjati, Farkhondeh; Shafaghati, Yousef; Firouzabadi, Saghar Ghasemi; Kahrizi, Kimia; Bagherizadeh, Iman; Najmabadi, Hossein; Bint, Susan; Ogilvie, Caroline

    2008-01-01

    We describe a partial duplication of the chromosome 16 short arm [46,XY,dup(16)(p11.2p13.1)] in an Iranian girl with autism, neurodevelopmental delay, mental retardation, very poor memory, and dysmorphism including sparse hair, upslanting palpebral fissures, long philtrum, micrognathia, hypotonia, small feet and hands, syndactyly of the fingers, and hypoplastic thumbs. The patient now four years old, has a normal twin sister, and the parents are unrelated. The abnormal 16p was originally detected by banding cytogenetic techniques, and was characterized by multicolour banding fluorescence in situ hybridization (MCB). The MCB pattern on the derivative chromosome 16 indicated a direct duplication of the region 16p11.2 to 16p13.1. PMID:18674645

  14. Size and alloying induced shift in core and valence bands of Pd-Ag and Pd-Cu nanoparticles

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Govind

    2014-03-28

    In this report, X-ray photoelectron spectroscopy studies have been carried out on Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles having identical sizes corresponding to mobility equivalent diameters of 60, 40, and 20 nm. The nanoparticles were prepared by the gas phase synthesis method. The effect of size on valence and core levels in metal and alloy nanoparticles has been studied by comparing the values to those with the 60 nm nanoparticles. The effect of alloying has been investigated by comparing the valence and core level binding energies of Pd-Cu and Pd-Ag alloy nanoparticles with the corresponding values for Pd, Ag, and Cu nanoparticles of identical sizes. These effects have been explained in terms of size induced lattice contractions, alloying induced charge transfer, and hybridization effects. The observation of alloying and size induced binding energy shifts in bimetallic nanoparticles is important from the point of view of hydrogen reactivity.

  15. Spectroscopy of neutron-rich {sup 168,170}Dy: Yrast band evolution close to the N{sub p}N{sub n} valence maximum

    SciTech Connect

    Soederstroem, P.-A.; Nyberg, J.; Regan, P. H.; Ashley, S. F.; Catford, W. N.; Gelletly, W.; Jones, G. A.; Liu, Z.; Pietri, S.; Podolyak, Zs.; Steer, S. J.; Thompson, N. J.; Williams, S. J.; Algora, A.; Angelis, G. de; Corradi, L.; Fioretto, E.; Gottardo, A.; Grodner, E.; He, C. Y.

    2010-03-15

    The yrast sequence of the neutron-rich dysprosium isotope {sup 168}Dy has been studied using multinucleon transfer reactions following collisions between a 460-MeV {sup 82}Se beam and an {sup 170}Er target. The reaction products were identified using the PRISMA magnetic spectrometer and the gamma rays detected using the CLARA HPGe-detector array. The 2{sup +} and 4{sup +} members of the previously measured ground-state rotational band of {sup 168}Dy have been confirmed and the yrast band extended up to 10{sup +}. A tentative candidate for the 4{sup +}->2{sup +} transition in {sup 170}Dy was also identified. The data on these nuclei and on the lighter even-even dysprosium isotopes are interpreted in terms of total Routhian surface calculations and the evolution of collectivity in the vicinity of the proton-neutron valence product maximum is discussed.

  16. Phosphorus K β X-Ray Emission Spectra and Valence-Band Structures of Transition-Metal Phosphides and GaAs 1-xPx

    NASA Astrophysics Data System (ADS)

    Sugiura, Chikara

    1996-07-01

    The P Kβ emission spectra in fluorescence from ZrP, NbP, MoP,HfP, TaP, WP, AgP2, CdP2, Mn3P2, Cd3P2 and GaAs1-xPxfor 0.2 ≤ x ≤ 1 are measured with a high-resolutiontwo-crystal vacuum spectrometer equipped with Ge(111) crystals. Theinfluence of metal atoms appears distinctly in the P Kβemission spectra of transition-metal phosphides. The effect ofarsenic atoms appears slightly in the P Kβ emission spectraof GaAs1-xPx. The P Kβ emission spectra of AgP2,CdP2, Cd3P2 and GaAs0.6 P0.4 are compared withavailable P L2,3 emission and XPS valence-band spectra ona common energy scale. It is shown that the P 3p electronsinteract fairly with the metal d electrons in the upper partof the valence band for MP ( M = Zr, Nb, Mo, Hf, Ta, W) and Mn3P2;considerable p-d, s mixing occurs in the middle part for AgP2and in the lower part for CdP2 and Cd3P2; and the Ga 3dstates mix fairly with the P 3s states in GaAs0.6P0.4.

  17. Neutral-Type One-Dimensional Mixed-Valence Halogen-Bridged Platinum Chain Complexes with Large Charge-Transfer Band Gaps.

    PubMed

    Otake, Ken-ichi; Otsubo, Kazuya; Sugimoto, Kunihisa; Fujiwara, Akihiko; Kitagawa, Hiroshi

    2016-03-01

    One-dimensional (1D) electronic systems have attracted significant attention for a long time because of their various physical properties. Among 1D electronic systems, 1D halogen-bridged mixed-valence transition-metal complexes (the so-called MX chains) have been thoroughly studied owing to designable structures and electronic states. Here, we report the syntheses, structures, and electronic properties of three kinds of novel neutral MX-chain complexes. The crystal structures consist of 1D chains of Pt-X repeating units with (1R,2R)-(-)-diaminocychlohexane and CN(-) in-plane ligands. Because of the absence of a counteranion, the neutral MX chains have short interchain distances, so that strong interchain electronic interaction is expected. Resonance Raman spectra and diffuse-reflectance UV-vis spectra indicate that their electronic states are mixed-valence states (charge-density-wave state: Pt(2+)···X-Pt(4+)-X···Pt(2+)···X-Pt(4+)-X···). In addition, the relationship between the intervalence charge-transfer (IVCT) band gap and the degree of distortion of the 1D chain shows that the neutral MX chains have a larger IVCT band gap than that of cationic MX-chain complexes. These results provide new insight into the physical and electronic properties of 1D chain compounds. PMID:26901774

  18. The observation of valence band change on resistive switching of epitaxial Pr0.7Ca0.3MnO3 film using removable liquid electrode

    NASA Astrophysics Data System (ADS)

    Lee, Hong-Sub; Park, Hyung-Ho

    2015-12-01

    The resistive switching (RS) phenomenon in transition metal oxides (TMOs) has received a great deal of attention for non-volatile memory applications. Various RS mechanisms have been suggested as to explain the observed RS characteristics. Many reports suggest that changes of interface and the role of oxygen vacancies originate in RS phenomena; therefore, in this study, we use a liquid drop of mercury as the top electrode (TE), epitaxial Pr0.7Ca0.3MnO3 (PCMO) (110) film of the perovskite manganite family for RS material, and an Nb-doped (0.7 at. %) SrTiO3 (100) single crystal as the substrate to observe changes in the interface between the TE and TMOs. The use of removable liquid electrode Hg drop as TE not only enables observation of the RS characteristic as a bipolar RS curve (counterclockwise) but also facilitates analysis of the valence band of the PCMO surface after resistive switching via photoelectron spectroscopy. The observed I-V behaviors of the low and high resistance states (HRS) are explained with an electrochemical migration model in PCMO film where accumulated oxygen vacancies at the interface between the Hg TE and PCMO (110) surface induce the HRS. The interpreted RS mechanism is directly confirmed via valence band spectrum analysis.

  19. Symmetry properties of n-doped (Cd,Mn)Te quantum well photoluminescence spectra: An exemplary evidence for anisotropy-induced valence-band mixing

    NASA Astrophysics Data System (ADS)

    Koudinov, A. V.; Kehl, C.; Astakhov, G.; Geurts, J.; Wojtowicz, T.; Karczewski, G.

    2016-05-01

    The symmetry properties of photoluminescence spectra of an n-doped (001)-Cd0.99Mn0.01Te quantum well provide a simple and intuitive demonstration of the valence-band mixing induced by spontaneous in-plane anisotropy of the sample. The spectra were taken with linear-polarization resolution in an in-plane external magnetic field. They consisted of several features which are characteristic for a two-dimensional electron gas. Because the quantum well layer contained "magnetic" ions of Mn, the spectra showed pronounced polarization-dependent modifications induced by the magnetic field. With the field applied, a 90° rotation of the sample about the surface normal axis resulted in a clearly different spectrum, meaning that the nominally equivalent [110 ] and [1 1 ¯ 0 ] in-plane directions in the sample are not equivalent in fact. But, remarkably, the additional 90° rotations of both the polarizer and the analyzer restored the initial spectrum. This combined invariance regarding simultaneous 90° rotation of the sample and reversal of the polarization configuration was known earlier for spin-flip Raman spectra only. Our present observations are interpreted in terms of an intermixing of valence subbands leading to a pseudoisotropic g-factor of the ground-state holes.

  20. Electronic Structure and Phase Transition in Ferroelectic Sn2P2S6 Crystal

    PubMed Central

    Glukhov, Konstantin; Fedyo, Kristina; Banys, Juras; Vysochanskii, Yulian

    2012-01-01

    An analysis of the P2S6 cluster electronic structure and its comparison with the crystal valence band in the paraelectric and ferroelectric phases has been done by first-principles calculations for Sn2P2S6 ferroelectrics. The origin of ferroelectricity has been outlined. It was established that the spontaneous polarization follows from the stereochemical activity of the electron lone pair of tin cations, which is determined by hybridization with P2S6 molecular orbitals. The chemical bonds covalence increase and rearrangement are related to the valence band changes at transition from the paraelectric phase to the ferroelectric phase. PMID:23203069

  1. Valence band offset in heterojunctions between crystalline silicon and amorphous silicon (sub)oxides (a-SiO{sub x}:H, 0 < x < 2)

    SciTech Connect

    Liebhaber, M.; Mews, M.; Schulze, T. F.; Korte, L. Rech, B.; Lips, K.

    2015-01-19

    The heterojunction between amorphous silicon (sub)oxides (a-SiO{sub x}:H, 0 < x < 2) and crystalline silicon (c-Si) is investigated. We combine chemical vapor deposition with in-system photoelectron spectroscopy in order to determine the valence band offset ΔE{sub V} and the interface defect density, being technologically important junction parameters. ΔE{sub V} increases from ≈0.3 eV for the a-Si:H/c-Si interface to >4 eV for the a-SiO{sub 2}/c-Si interface, while the electronic quality of the heterointerface deteriorates. High-bandgap a-SiO{sub x}:H is therefore unsuitable for the hole contact in heterojunction solar cells, due to electronic transport hindrance resulting from the large ΔE{sub V}. Our method is readily applicable to other heterojunctions.

  2. On the combined use of GW approximation and cumulant expansion in the calculations of quasiparticle spectra: The paradigm of Si valence bands

    NASA Astrophysics Data System (ADS)

    Gumhalter, Branko; Kovač, Vjekoslav; Caruso, Fabio; Lambert, Henry; Giustino, Feliciano

    2016-07-01

    Since the earliest implementations of the various GW approximations and cumulant expansion in the calculations of quasiparticle propagators and spectra, several attempts have been made to combine the advantageous properties and results of these two theoretical approaches. While the GW-plus-cumulant approach has proven successful in interpreting photoemission spectroscopy data in solids, the formal connection between the two methods has not been investigated in detail. By introducing a general bijective integral representation of the cumulants, we can rigorously identify at which point these two approximations can be connected for the paradigmatic model of quasiparticle interaction with the dielectric response of the system that has been extensively exploited in recent interpretations of the satellite structures in photoelectron spectra. We establish a protocol for consistent practical implementation of the thus established GW +cumulant scheme and illustrate it by comprehensive state-of-the-art first-principles calculations of intrinsic angle-resolved photoemission spectra from Si valence bands.

  3. Impact of cation-based localized electronic states on the conduction and valence band structure of Al{sub 1−x}In{sub x}N alloys

    SciTech Connect

    Schulz, S.; Caro, M. A.; O'Reilly, E. P.

    2014-04-28

    We demonstrate that cation-related localized states strongly perturb the band structure of Al{sub 1−x}In{sub x}N leading to a strong band gap bowing at low In content. Our first-principles calculations show that In-related localized states are formed both in the conduction and the valence band in Al{sub 1−x}In{sub x}N for low In composition, x, and that these localized states dominate the evolution of the band structure with increasing x. Therefore, the commonly used assumption of a single composition-independent bowing parameter breaks down when describing the evolution both of the conduction and of the valence band edge in Al{sub 1−x}In{sub x}N.

  4. Evaluation of the band alignment and valence plasmonic features of a DIBS grown Ga-doped Mg0.05Zn0.95O/CIGSe heterojunction by photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Awasthi, Vishnu; Pandey, Sushil Kumar; Kumar, Shailendra; Mukherjee, C.; Gupta, Mukul; Mukherjee, Shaibal

    2015-12-01

    The bandgap alignment of a Ga-doped MgZnO (GMZO)/CIGSe heterojunction exposed to short duration Ar+  ion beam sputtering has been investigated by ultraviolet photoelectron spectroscopy measurement. The offset values at the valence and conduction band of the GMZO/CIGSe hetrojunction are calculated to be 2.69 and  -0.63 eV, respectively. Moreover, the valence band onsets of GMZO and CIGSe thin films before and after few minutes Ar+ ion sputtering have been investigated. The presented study demonstrates the photoelectron-induced generation of resonant valence bulk and surface plasmonic features of various metal and metal oxide nanoclusters embedded within a GMZO matrix. The presence of such nanoclusters is proven to be beneficial in realizing cost-effective, ultra-thin, and high-performance photovoltaics based on the heterojunction.

  5. Evaluation of valence band top and electron affinity of SiO2 and Si-based semiconductors using X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Fujimura, Nobuyuki; Ohta, Akio; Makihara, Katsunori; Miyazaki, Seiichi

    2016-08-01

    An evaluation method for the energy level of the valence band (VB) top from the vacuum level (VL) for metals, dielectrics, and semiconductors from the results of X-ray photoelectron spectroscopy (XPS) is presented for the accurate determination of the energy band diagram for materials of interest. In this method, the VB top can be determined by the energy difference between the onset of VB signals and the cut-off energy for secondary photoelectrons by considering the X-ray excitation energy (hν). The energy level of the VB top for three kinds of Si-based materials (H-terminated Si, wet-cleaned 4H-SiC, and thermally grown SiO2) has been investigated by XPS under monochromatized Al Kα radiation (hν = 1486.6 eV). We have also demonstrated the determination of the electron affinity for the samples by this measurement technique in combination with the measured and reported energy bandgaps (E g).

  6. Study of valence-band intersublevel transitions in InAs/GaAs quantum dots-in-well infrared photodetectors

    SciTech Connect

    Lao, Yan-Feng; Wolde, Seyoum; Unil Perera, A. G.; Zhang, Y. H.; Wang, T. M.; Kim, J. O.; Schuler-Sandy, Ted; Tian, Zhao-Bing; Krishna, S. S.

    2014-04-28

    The n-type quantum dot (QD) and dots-in-well (DWELL) infrared photodetectors, in general, display bias-dependent multiple-band response as a result of optical transitions between different quantum levels. Here, we present a unique characteristic of the p-type hole response, a well-preserved spectral profile, due to the much reduced tunneling probability of holes compared to electrons. This feature remains in a DWELL detector, with the dominant transition contributing to the response occurring between the QD ground state and the quantum-well states. The bias-independent response will benefit applications where single-color detection is desired and also allows achieving optimum performance by optimizing the bias.

  7. Valence and conduction band alignment at ScN interfaces with 3C-SiC (111) and 2H-GaN (0001)

    SciTech Connect

    King, Sean W.; Nemanich, Robert J.; Davis, Robert F.

    2014-08-25

    In order to understand and predict the behavior of future scandium nitride (ScN) semiconductor heterostructure devices, we have utilized in situ x-ray and ultra-violet photoelectron spectroscopy to determine the valence band offset (VBO) present at ScN/3C-SiC (111) and 2H-GaN (0001)/ScN (111) interfaces formed by ammonia gas source molecular beam epitaxy. The ScN/3C-SiC (111) VBO was dependent on the ScN growth temperature and resistivity. VBOs of 0.4 ± 0.1 and 0.1 ± 0.1 eV were, respectively, determined for ScN grown at 925 °C (low resistivity) and 800 °C (high resistivity). Using the band-gaps of 1.6 ± 0.2 and 1.4 ± 0.2 eV previously determined by reflection electron energy loss spectroscopy for the 925 and 800 °C ScN films, the respective conduction band offsets (CBO) for these interfaces were 0.4 ± 0.2 and 0.9 ± 0.2 eV. For a GaN (0001) interface with 925 °C ScN (111), the VBO and CBO were similarly determined to be 0.9 ± 0.1 and 0.9 ± 0.2 eV, respectively.

  8. Valence band study of Sm0.1Ca0.9 - xSrxMnO3 using high resolution photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Dalai, Manas Kumar; Sekhar, Biju Raja; Biswas, Deepnarayan; Thakur, Sangeeta; Maiti, Kalobaran; Chiang, Tai-Chang; Martin, Christine

    2014-03-01

    We have studied the valence band electronic structure of Sm0.1Ca0.9- xSrxMnO3 (x = 0, 0.1, 0.3 and 0.6) at various temperatures using high resolution photoemission spectroscopy (HRPES). The data were taken using a Scienta R4000 energy analyser and the resolution was set at 5 meV. The doping dependent studies of Sm0.1Ca0.9-x SrxMnO3 at 50 K, 100 K and 295 K are quite interesting. The density of eg states near the Fermi level decreases with Sr substitution at the Ca site at 50 K. Also the similar trend has been observed at 100 K. At 295 K the changes in the eg states is quite different than the earlier temperatures where the intensity remains the same for x = 0, 0.1 and 0.3 and then decreases for x = 0.6. These changes in the density of states near the Fermi level will be explained by taking into account the structural, electrical and magnetic properties associated with this system. Permanent affiliation of Manas Kumar Dalai ; CSIR-National Physical Laboratory, New Delhi-110012, India. MKD acknowledges the Indo-US Science and Technology Forum (IUSSTF) for the fellowship.

  9. Valence band offset at Al{sub 2}O{sub 3}/In{sub 0.17}Al{sub 0.83}N interface formed by atomic layer deposition

    SciTech Connect

    Akazawa, M.; Nakano, T.

    2012-09-17

    The valence band offset, {Delta}E{sub V}, at an Al{sub 2}O{sub 3}/In{sub 0.17}Al{sub 0.83}N interface formed by atomic layer deposition was measured by x-ray photoelectron spectroscopy. The conventional method of using the core level separation, {Delta}E{sub CL}, between O 1s and In 4d resulted in {Delta}E{sub V} = 1.3 eV, which was apparently consistent with the direct observation of the valence band edge varying the photoelectron exit angle, {theta}. However, {Delta}E{sub CL} and full width at half maximum of core-level spectra were dependent on {theta}, which indicated significant potential gradients in Al{sub 2}O{sub 3} and InAlN layers. An actual {Delta}E{sub V} of 1.2 eV was obtained considering the potential gradients.

  10. Valence and conduction band offsets at low-k a-SiO{sub x}C{sub y}:H/a-SiC{sub x}N{sub y}:H interfaces

    SciTech Connect

    King, Sean W. Brockman, Justin; French, Marc; Jaehnig, Milt; Kuhn, Markus; French, Benjamin

    2014-09-21

    In order to understand the fundamental electrical leakage and reliability failure mechanisms in nano-electronic low-k dielectric/metal interconnect structures, we have utilized x-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy to determine the valence and conduction band offsets present at interfaces between non-porous and porous low-k a-SiO{sub x}C{sub y}:H interlayer dielectrics and a-SiC{sub x}N{sub y}:H metal capping layers. The valence band offset for such interfaces was determined to be 2.7±0.2 eV and weakly dependent on the a-SiOC:H porosity. The corresponding conduction band offset was determined to be 2.1±0.2 eV. The large band offsets indicate that intra metal layer leakage is likely dominated by defects and trap states in the a-SiOC:H and a-SiCN:H dielectrics.

  11. Communication: First observation of ground state I({sup 2}P{sub 3/2}) atoms from the CH{sub 3}I photodissociation in the B-band

    SciTech Connect

    Gonzalez, M. G.; Rodriguez, J. D.; Rubio-Lago, L.; Banares, L.

    2011-07-14

    The photodissociation of CH{sub 3}I in the second absorption band (the B-band) has been studied at the wavelength 199.11 nm, coincident with the 3{sub 0}{sup 1} {sup 3}R{sub 1}(E)(leftarrow)X(tilde sign)({sup 1}A{sub 1}) CH{sub 3}I vibronic transition, using a combination of slice imaging and resonance enhanced multiphoton ionization detection of the CH{sub 3} fragment. The kinetic energy and angular distributions of the recoiling CH{sub 3} fragment confirm a major predissociation dynamics channel as a result of the interaction between the bound {sup 3}R{sub 1} Rydberg state and the repulsive {sup 3}A{sub 1}(E) state - ascribed to the A-band - yielding CH{sub 3} fragments in correlation with spin-orbit excited I*({sup 2}P{sub 1/2}) atoms. In addition, first evidence of a non-negligible population of ground state I({sup 2}P{sub 3/2}) atoms in the CH{sub 3} fragment slice images, suggests a secondary predissociation mechanism via interaction between the {sup 3}R{sub 1} Rydberg state and the repulsive A-band {sup 1}Q{sub 1} state.

  12. Experimental study of the valence band of Bi2Se3

    SciTech Connect

    Gao, Yi-Bin; He, Bin; Parker, David; Androulakis, Ioannis; Heremans, Joseph P.

    2014-09-26

    The valence band of Bi2Se3 is investigated with Shubnikov - de Haas measurements, galvanomagnetic and thermoelectric transport. At low hole concentration, the hole Fermi surface is closed and box-like, but at higher concentrations it develops tube-like extensions that are open. The experimentally determined density-of-states effective mass is lighter than density-functional theory calculations predict; while we cannot give a definitive explanation for this, we suspect that the theory may lack sufficient precision to compute room-temperature transport properties, such as the Seebeck coefficient, in solids in which there are Van der Waals interlayer bonds.

  13. The role of the hybridization between Mn 3d and O 2p orbitals in the existence of the Griffiths phase in La0.85Ca0.15MnO3.

    PubMed

    Zhang, Hong-guang; Shi, Jiang-jian; Li, Yong-tao; Dong, Xue-guang; Ge, Xiao-peng; Liu, Hao; Hou, Qing-teng; Li, Qi; Tang, Yan-kun

    2014-04-01

    Favourable conditions for the existence of the Griffiths phase in the La0.85Ca0.15MnO3 compound are experimentally investigated in terms of electronic and lattice structure by temperature-dependent x-ray absorption spectroscopy, valence band photoemission spectroscopy, and x-ray diffraction experiments. The chemical shifts of Mn L-edge and O K-edge x-ray absorption lines in the Griffiths phase are understood to be related to the hybridization between Mn 3d and O 2p states instead of the variation of Mn valence states. Valence band spectra also indicate that the hybridization of O 2p with Mn 3d is enhanced in the Griffiths phase. From a 2D diluted Ising ferromagnet model, this hybridization between Mn 3d and O 2p orbitals surely enhances the Griffiths phase feature. PMID:24637382

  14. Thermal stability of the HfO2/SiO2 interface for sub-0.1 μm complementary metal-oxide-semiconductor gate oxide stacks: A valence band and quantitative core-level study by soft x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Barrett, N.; Renault, O.; Damlencourt, J.-F.; Martin, F.

    2004-12-01

    Synchrotron-radiation photoelectron spectroscopy is used to study the valence-band structure and the core-level photoemission spectra of HfO2 ultrathin films grown onto SiO2/Si substrates by atomic layer deposition (ALD). We determine the band offsets (valence and conduction) of HfO2 to Si as a function of postdeposition annealing treatments (under an inert N2 atmosphere or in situ in ultrahigh vacuum) and find a significant evolution, the conduction-band offset remaining larger than 1.5eV. The Si2p and the Hf4f core-level spectra give detailed information on the composition and the spatial extent of the interfacial Hf silicate layer formed between the SiO2 bottom oxide and the HfO2 ALD thin film. By a quantitative treatment of the Si2p core-level intensities, we examine the thermal stability of the interface silicate after postdeposition annealing under N2 and in situ annealing in ultrahigh vacuum (UHV), both at 800°C. The as-deposited layer gives rise to a HfO2/Hf0.35Si0.65O2/SiO2 stack with corresponding thicknesses of 0.74/0.51/0.73nm. After postdeposition annealing at 800°C in a N2 atmosphere, this becomes a HfO2/Hf0.31Si0.69O2/SiO2 stack with corresponding thicknesses of 0.71:0.58:0.91nm. In situ annealing in UHV, on the other hand, gives a HfO2/Hf0.35Si0.65O2/SiO2 stack with corresponding thicknesses of 0.65:0.70:0.76nm. The former favors an extension of both the silicate and the SiO2 interface layers, whereas the latter develops only the silicate layer.

  15. The observation of valence band change on resistive switching of epitaxial Pr{sub 0.7}Ca{sub 0.3}MnO{sub 3} film using removable liquid electrode

    SciTech Connect

    Lee, Hong-Sub; Park, Hyung-Ho

    2015-12-07

    The resistive switching (RS) phenomenon in transition metal oxides (TMOs) has received a great deal of attention for non-volatile memory applications. Various RS mechanisms have been suggested as to explain the observed RS characteristics. Many reports suggest that changes of interface and the role of oxygen vacancies originate in RS phenomena; therefore, in this study, we use a liquid drop of mercury as the top electrode (TE), epitaxial Pr{sub 0.7}Ca{sub 0.3}MnO{sub 3} (PCMO) (110) film of the perovskite manganite family for RS material, and an Nb-doped (0.7 at. %) SrTiO{sub 3} (100) single crystal as the substrate to observe changes in the interface between the TE and TMOs. The use of removable liquid electrode Hg drop as TE not only enables observation of the RS characteristic as a bipolar RS curve (counterclockwise) but also facilitates analysis of the valence band of the PCMO surface after resistive switching via photoelectron spectroscopy. The observed I-V behaviors of the low and high resistance states (HRS) are explained with an electrochemical migration model in PCMO film where accumulated oxygen vacancies at the interface between the Hg TE and PCMO (110) surface induce the HRS. The interpreted RS mechanism is directly confirmed via valence band spectrum analysis.

  16. Chemical bonding and charge redistribution - Valence band and core level correlations for the Ni/Si, Pd/Si, and Pt/Si systems

    NASA Technical Reports Server (NTRS)

    Grunthaner, P. J.; Grunthaner, F. J.; Madhukar, A.

    1982-01-01

    Via a systematic study of the correlation between the core and valence level X-ray photoemission spectra, the nature of the chemical bonding and charge redistribution for bulk transition metal silicides has been examined. Particular emphasis is placed on Pt2Si and PtSi. It is observed that the strength of the metal (d)-silicon (p) interaction increases in the order Ni2Si, Pd2Si, Pt2Si. It is also observed that both the metal and silicon core lines shift to higher binding energy as the silicides are formed. The notion of charge redistribution for metallic bonds is invoked to explain these data.

  17. Band alignment of Ga2O3/Si heterojunction interface measured by X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Zhengwei; Nishihagi, Kazuo; Wang, Xu; Saito, Katsuhiko; Tanaka, Tooru; Nishio, Mitsuhiro; Arita, Makoto; Guo, Qixin

    2016-09-01

    Ga2O3 thin films were deposited on (111) Si substrate by pulsed laser deposition method. X-ray photoelectron spectroscopy has been used to determine the valence band offset at Ga2O3/Si heterojunction interface. We measured the binding energies of Si 2p and Ga 2p3/2 core levels and the valence band maxima energies. The valence band offset is determined to be 3.5 ± 0.1 eV. As a consequence a type Ι heterojunction with a conduction band offset of 0.2 ± 0.1 eV is found. The determination of the band alignment of Ga2O3/Si heterojunction facilitates the design of optical and electronic devices based on the Ga2O3/Si structure.

  18. Levels of valence.

    PubMed

    Shuman, Vera; Sander, David; Scherer, Klaus R

    2013-01-01

    The distinction between the positive and the negative is fundamental in our emotional life. In appraisal theories, in particular in the component process model of emotion (Scherer, 1984, 2010), qualitatively different types of valence are proposed based on appraisals of (un)pleasantness, goal obstructiveness/conduciveness, low or high power, self-(in)congruence, and moral badness/goodness. This multifaceted conceptualization of valence is highly compatible with the frequent observation of mixed feelings in real life. However, it seems to contradict the one-dimensional conceptualization of valence often encountered in psychological theories, and the notion of valence as a common currency used to explain choice behavior. Here, we propose a framework to integrate the seemingly disparate conceptualizations of multifaceted valence and one-dimensional valence by suggesting that valence should be conceived at different levels, micro and macro. Micro-valences correspond to qualitatively different types of evaluations, potentially resulting in mixed feelings, whereas one-dimensional macro-valence corresponds to an integrative "common currency" to compare alternatives for choices. We propose that conceptualizing levels of valence may focus research attention on the mechanisms that relate valence at one level (micro) to valence at another level (macro), leading to new hypotheses, and addressing various concerns that have been raised about the valence concept, such as the valence-emotion relation. PMID:23717292

  19. Levels of Valence

    PubMed Central

    Shuman, Vera; Sander, David; Scherer, Klaus R.

    2013-01-01

    The distinction between the positive and the negative is fundamental in our emotional life. In appraisal theories, in particular in the component process model of emotion (Scherer, 1984, 2010), qualitatively different types of valence are proposed based on appraisals of (un)pleasantness, goal obstructiveness/conduciveness, low or high power, self-(in)congruence, and moral badness/goodness. This multifaceted conceptualization of valence is highly compatible with the frequent observation of mixed feelings in real life. However, it seems to contradict the one-dimensional conceptualization of valence often encountered in psychological theories, and the notion of valence as a common currency used to explain choice behavior. Here, we propose a framework to integrate the seemingly disparate conceptualizations of multifaceted valence and one-dimensional valence by suggesting that valence should be conceived at different levels, micro and macro. Micro-valences correspond to qualitatively different types of evaluations, potentially resulting in mixed feelings, whereas one-dimensional macro-valence corresponds to an integrative “common currency” to compare alternatives for choices. We propose that conceptualizing levels of valence may focus research attention on the mechanisms that relate valence at one level (micro) to valence at another level (macro), leading to new hypotheses, and addressing various concerns that have been raised about the valence concept, such as the valence-emotion relation. PMID:23717292

  20. Dynamics of Impurity and Valence Bands in Ga1-xMnxAs Within the Dynamical Mean-Field Approximation

    SciTech Connect

    Majidi, M. A.; Moreno, Juana; Jarrell, Mark; Fishman, Randy Scott; Aryanpour, K. A.

    2006-08-01

    We calculate the density-of-states and the spectral function of Ga1−xMnxAs within the dynamical mean-field approximation. Our model includes the competing effects of the strong spin-orbit coupling on the J=3/2 GaAs hole bands and the exchange interaction between the magnetic ions and the itinerant holes. We study the quasiparticle and impurity bands in the paramagnetic and ferromagnetic phases for different values of impurity-hole coupling Jc at a Mn doping of x=0.05. By analyzing the anisotropic angular distribution of the impurity band carriers at T=0, we conclude that the carrier polarization is optimal when the carriers move along the direction parallel to the average magnetization.

  1. Energy Correlation among Three Photoelectrons Emitted in Core-Valence-Valence Triple Photoionization of Ne

    SciTech Connect

    Hikosaka, Y.; Soejima, K.; Lablanquie, P.; Penent, F.; Palaudoux, J.; Andric, L.; Shigemasa, E.; Suzuki, I. H.; Nakano, M.; Ito, K.

    2011-09-09

    The direct observation of triple photoionization involving one inner shell and two valence electrons is reported. The energy distribution of the three photoelectrons emitted from Ne is obtained using a very efficient multielectron coincidence method using the magnetic bottle electron spectroscopic technique. A predominance of the direct path to triple photoionization for the formation of Ne{sup 3+} in the 1s2s{sup 2}2p{sup 4} configuration is observed. It is demonstrated that the energy distribution evolves with photon energy and indicates a significant difference with triple photoionization involving only valence electrons.

  2. Gas-to-cluster effects in S 2p-excited SF{sub 6}

    SciTech Connect

    Flesch, Roman; Serdaroglu, Ertugrul; Ruehl, Eckart; Brykalova, Xenia O.; Kan, Elena I.; Klyushina, Ekaterina S.; Krivosenko, Yuri S.; Pavlychev, Andrey A.

    2013-04-14

    High resolution X-ray spectroscopic studies on free SF{sub 6} molecules and SF{sub 6} clusters near the S 2p ionization thresholds are reported. Spectral changes occurring in clusters for the intense molecular-like S 2p{sub 1/2,3/2}{yields} 6a{sub 1g}-, 2t{sub 2g}-, and 4e{sub g}-resonances are examined in detail. Neither gas-to-cluster spectral shifts nor changes in peak shape are observed for the pre-edge 6a{sub 1g}-band. Significant changes in band shape and distinct gas-to-cluster shifts occur in the S 2p{sub 1/2,3/2}{yields} 2t{sub 2g}- and 4e{sub g}-transitions. These are found in the S 2p-ionization continua. The quasiatomic approach is used to assign the experimental results. It is shown that a convolution of asymmetric and symmetric contributions from Lorentzian and Gaussian line shapes allows us to model the spectral distribution of oscillator strength for the S 2p{sub 1/2,3/2}{yields} 2t{sub 2g}-, and 4e{sub g}-transitions. The asymmetry is due to trapping of the photoelectron within the finite size potential barrier. The Lorentzian contribution is found to be dominating in the line shape of the S 2p{yields} 2t{sub 2g}- and 4e{sub g}-bands. The spectroscopic parameters of the spin-orbit components of both the 2t{sub 2g}- and 4e{sub g}-bands are extracted and their gas-to-cluster changes are analyzed. The photoelectron trapping times in free and clustered SF{sub 6} molecules are determined. Specifically, it is shown that spectral changes in clusters reflected in core-to-valence-transitions are due to a superposition of the singly scattered photoelectron waves at the neighboring molecules with the primary and multiply scattered waves within the molecular cage.

  3. Photoionization studies of the 2p resonances of atomic calcium

    NASA Astrophysics Data System (ADS)

    Obst, B.; Hansen, J. E.; Sonntag, B.; Wernet, Ph.; Zimmermann, P.

    2002-06-01

    The Ca 2p resonances at 345-355 eV were studied by photoion and photoelectron spectroscopy using monochromatized synchrotron radiation and atomic-beam technique. The analysis of the excitation and decay of these resonances shows strong configuration mixing between the different subshells of the valence electrons 4s, 3d, and 4p. In the case of the 2p-13/2 resonance structure at 348 eV there are two excited states with nearly equal contributions from the configuration 2p53d4s2 and 2p53d24s, which gives rise to strong variations of the resonantly enhanced 3p4(3d,4s)3 photoelectron lines when scanning the photon energy across the resonance.

  4. Band structure in 113Sn

    NASA Astrophysics Data System (ADS)

    Banerjee, P.; Ganguly, S.; Pradhan, M. K.; Sharma, H. P.; Muralithar, S.; Singh, R. P.; Bhowmik, R. K.

    2016-07-01

    The structure of collective bands in 113Sn, populated in the reaction 100Mo(19F,p 5 n ) at a beam energy of 105 MeV, has been studied. A new positive-parity sequence of eight states extending up to 7764.9 keV and spin (39 /2+) has been observed. The band is explained as arising from the coupling of the odd valence neutron in the g7 /2 or the d5 /2 orbital to the deformed 2p-2h proton configuration of the neighboring even-A Sn isotope. Lifetimes of six states up to an excitation energy of 9934.9 keV and spin 47 /2-belonging to a Δ I =2 intruder band have been measured for the first time, including an upper limit for the last state, from Doppler-shift-attenuation data. A moderate average quadrupole deformation β2=0.22 ±0.02 is deduced from these results for the five states up to spin 43 /2- . The transition quadrupole moments decrease with increase in rotational frequency, indicating a reduction of collectivity with spin, a feature common for terminating bands. The behavior of the kinematic and dynamic moments of inertia as a function of rotational frequency has been studied and total Routhian surface calculations have been performed in an attempt to obtain an insight into the nature of the states near termination.

  5. Quantitative study of band structure in BaTiO3 particles with vacant ionic sites

    NASA Astrophysics Data System (ADS)

    Oshime, Norihiro; Kano, Jun; Ikeda, Naoshi; Teranishi, Takashi; Fujii, Tatsuo; Ueda, Takeji; Ohkubo, Tomoko

    2016-10-01

    Levels of the conduction band minimum and the valence band maximum in ion-deficient BaTiO3 particles were investigated with optical band gap and ionization energy measurements. Though it is known that the quantification of the band structure in an insulator is difficult, due to the poor electrical conductivity of BaTiO3, systematic variation in the band energy levels was found that correlated with the introduction of vacancies. Photoelectron yield spectroscopy provided direct observation of the occupancy level of electrons, which is altered by the presence of oxygen and barium vacancies. In addition, the conduction band deviation from the vacuum level was determined by optical reflectance spectroscopy. Our results show that: (1) Introduction of oxygen vacancies forms a donor level below the conduction band. (2) The conduction band is shifted to a lower level by a larger number of oxygen vacancies, while the valence band also shifts to a lower level, due to the reduction in the density of O 2p orbitals. (3) Introduction of barium vacancies widens the band gap. Since barium vacancies can induce a small number of oxygen vacancies with accompanying charge compensation, this behavior suppresses any large formation of donor levels in the gap states, indicating that cation vacancies can control the number of both donor and acceptor levels.

  6. Optical study of archetypical valence-fluctuating Eu systems.

    PubMed

    Guritanu, V; Seiro, S; Sichelschmidt, J; Caroca-Canales, N; Iizuka, T; Kimura, S; Geibel, C; Steglich, F

    2012-12-14

    We have investigated the optical conductivity of the prominent valence-fluctuating compounds EuIr(2)Si(2) and EuNi(2)P(2) in the infrared energy range to get new insights into the electronic properties of valence-fluctuating systems. For both compounds, we observe upon cooling the formation of a renormalized Drude response, a partial suppression of the optical conductivity below 100 meV, and the appearance of a midinfrared peak at 0.15 eV for EuIr(2)Si(2) and 0.13 eV for EuNi(2)P(2). Most remarkably, our results show a strong similarity with the optical spectra reported for many Ce- or Yb-based heavy-fermion metals and intermediate valence systems, although the phase diagrams and the temperature dependence of the valence differ strongly between Eu systems and Ce- or Yb-based systems. This suggests that the hybridization between 4f and conduction electrons, which is responsible for the properties of Ce and Yb systems, plays an important role in valence-fluctuating Eu systems.

  7. Structural evolution and valence electron-state change during ultra thin silicon-oxide growth

    NASA Astrophysics Data System (ADS)

    Shimizu, A.; Abe, S.; Nakayama, H.; Nishino, T.; Iida, S.

    2000-06-01

    We have studied valence electron-state changes of Si during initial oxidation of Si(111) clean surface, HF-treated Si(001) and Si(111) surfaces by Auger valence electron spectroscopy (AVES). The results showed that the valence electron-state changes during initial oxidation were sensitively reflected in Si[2s,2p,V] (V=3s,3p) AVES spectra and that they depended on both initial surface treatment and surface orientation. The local valence electron-states, local density of states in other words, showed the characteristic-structure evolution depending on the initial surface treatment and surface orientation.

  8. Optical properties of mixed-valence platinum halides

    NASA Astrophysics Data System (ADS)

    Albin, Michael; Patterson, Howard H.

    1980-08-01

    Temperature dependent absorption spectra are reported for PtX 2-4 -PtX 2-6 doped in Cs 2ZrX 6 (X = Cl, Br). Intense, broad bands have been assigned as mixed-valence (MV) transitions. Vibronic structure has been observed for the MV bromide system. Our results are discussed in terms of a model proposed by Hush.

  9. Racah materials: role of atomic multiplets in intermediate valence systems

    PubMed Central

    Shick, A. B.; Havela, L.; Lichtenstein, A. I.; Katsnelson, M. I.

    2015-01-01

    We address the long-standing mystery of the nonmagnetic insulating state of the intermediate valence compound SmB6. Within a combination of the local density approximation (LDA) and an exact diagonalization (ED) of an effective discrete Anderson impurity model, the intermediate valence ground state with the f-shell occupation 〈n4f〉 = 5.6 is found for the Sm atom in SmB6. This ground state is a singlet, and the first excited triplet state ~3 meV higher in the energy. SmB6 is a narrow band insulator already in LDA, with the direct band gap of ~10 meV. The electron correlations increase the band gap which now becomes indirect. Thus, the many-body effects are relevant to form the indirect band gap, crucial for the idea of “topological Kondo insulator" in SmB6. Also, an actinide analog PuB6 is considered, and the intermediate valence singlet ground state is found for the Pu atom. We propose that [Sm, Pu]B6 belong to a new class of the intermediate valence materials with the multi-orbital “Kondo-like" singlet ground-state. Crucial role of complex spin-orbital f  n–f  n+1 multiplet structure differently hybridized with ligand states in such Racah materials is discussed. PMID:26490021

  10. Racah materials: role of atomic multiplets in intermediate valence systems.

    PubMed

    Shick, A B; Havela, L; Lichtenstein, A I; Katsnelson, M I

    2015-10-22

    We address the long-standing mystery of the nonmagnetic insulating state of the intermediate valence compound SmB6. Within a combination of the local density approximation (LDA) and an exact diagonalization (ED) of an effective discrete Anderson impurity model, the intermediate valence ground state with the f-shell occupation 〈n4f〉 = 5.6 is found for the Sm atom in SmB6. This ground state is a singlet, and the first excited triplet state ~3 meV higher in the energy. SmB6 is a narrow band insulator already in LDA, with the direct band gap of ~10 meV. The electron correlations increase the band gap which now becomes indirect. Thus, the many-body effects are relevant to form the indirect band gap, crucial for the idea of "topological Kondo insulator" in SmB6. Also, an actinide analog PuB6 is considered, and the intermediate valence singlet ground state is found for the Pu atom. We propose that [Sm, Pu]B6 belong to a new class of the intermediate valence materials with the multi-orbital "Kondo-like" singlet ground-state. Crucial role of complex spin-orbital f(  n)-f ( n+1) multiplet structure differently hybridized with ligand states in such Racah materials is discussed.

  11. Multiple valence superatoms.

    PubMed

    Reveles, J U; Khanna, S N; Roach, P J; Castleman, A W

    2006-12-01

    We recently demonstrated that, in gas phase clusters containing aluminum and iodine atoms, an Al(13) cluster behaves like a halogen atom, whereas an Al(14) cluster exhibits properties analogous to an alkaline earth atom. These observations, together with our findings that Al(13)(-) is inert like a rare gas atom, have reinforced the idea that chosen clusters can exhibit chemical behaviors reminiscent of atoms in the periodic table, offering the exciting prospect of a new dimension of the periodic table formed by cluster elements, called superatoms. As the behavior of clusters can be controlled by size and composition, the superatoms offer the potential to create unique compounds with tailored properties. In this article, we provide evidence of an additional class of superatoms, namely Al(7)(-), that exhibit multiple valences, like some of the elements in the periodic table, and hence have the potential to form stable compounds when combined with other atoms. These findings support the contention that there should be no limitation in finding clusters, which mimic virtually all members of the periodic table.

  12. Multiple valence superatoms

    PubMed Central

    Reveles, J. U.; Khanna, S. N.; Roach, P. J.; Castleman, A. W.

    2006-01-01

    We recently demonstrated that, in gas phase clusters containing aluminum and iodine atoms, an Al13 cluster behaves like a halogen atom, whereas an Al14 cluster exhibits properties analogous to an alkaline earth atom. These observations, together with our findings that Al13− is inert like a rare gas atom, have reinforced the idea that chosen clusters can exhibit chemical behaviors reminiscent of atoms in the periodic table, offering the exciting prospect of a new dimension of the periodic table formed by cluster elements, called superatoms. As the behavior of clusters can be controlled by size and composition, the superatoms offer the potential to create unique compounds with tailored properties. In this article, we provide evidence of an additional class of superatoms, namely Al7−, that exhibit multiple valences, like some of the elements in the periodic table, and hence have the potential to form stable compounds when combined with other atoms. These findings support the contention that there should be no limitation in finding clusters, which mimic virtually all members of the periodic table. PMID:17121987

  13. Inorganic electron transfer: sharpening a fuzzy border in mixed valency and extending mixed valency across supramolecular systems.

    PubMed

    Kubiak, Clifford P

    2013-05-20

    This article describes research from our laboratory on the chemistry and spectroscopic properties of inorganic mixed-valence complexes. After a brief review of the seminal work of Taube, Creutz, Day, Robin, Hush, and others in the 1960s and the confounding efforts to identify the borderline between class II and III mixed-valence systems in the 1990s and early 2000s, we describe our first experiments to observe and analyze the coalescence of ν(CO) band shapes in the 1D IR spectra of mixed-valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}(-), where L = a pyridyl ligand and BL = pyrazine or 4,4'-bipyridine, to estimate rate constants of intramolecular electron transfer (ET). The strong involvement of the bridging ligands in mixed-valence complexes of this type was first identified in the appearance of totally symmetric vibrational modes of pyrazine bridging ligands in the IR because of strong vibronic coupling within a three-state metal cluster-bridge-metal cluster model. Application of the Brunschwig-Creutz-Sutin semiclassical three-state model of mixed valency accounts well for the appearance of two intervalence charge-transfer bands that are observed in the near-IR region of the electronic absorption spectra of these mixed-valence ions. The direct spectroscopic observation of "mixed-valence isomers", the two alternate charge distributions of a mixed-valence ion, are described. The equilibrium constants of mixed-valence isomers provide quantitative thermodynamic estimates of the electronic coupling, H(ab). The extent of delocalization in many of the mixed-valent bridged dimers of triruthenium clusters produces unusual behavior, especially rate constants for ET that are independent of normal solvent reorganization energies but do depend on solvent dynamical dipolar reorientation times. The strong dependence of rates on solvent dynamics is also found to produce a non-Arrhenius dependence of ET rate constants on temperature, faster rates in frozen solutions

  14. Micro-Valences: Perceiving Affective Valence in Everyday Objects

    PubMed Central

    Lebrecht, Sophie; Bar, Moshe; Barrett, Lisa Feldman; Tarr, Michael J.

    2012-01-01

    Perceiving the affective valence of objects influences how we think about and react to the world around us. Conversely, the speed and quality with which we visually recognize objects in a visual scene can vary dramatically depending on that scene’s affective content. Although typical visual scenes contain mostly “everyday” objects, the affect perception in visual objects has been studied using somewhat atypical stimuli with strong affective valences (e.g., guns or roses). Here we explore whether affective valence must be strong or overt to exert an effect on our visual perception. We conclude that everyday objects carry subtle affective valences – “micro-valences” – which are intrinsic to their perceptual representation. PMID:22529828

  15. Band offsets in YSZ/InGaZnO4 heterostructure system.

    PubMed

    Kim, J K; Kim, K W; Douglas, E A; Gila, B P; Craciun, V; Lambers, E S; Norton, D P; Ren, F; Pearton, S J; Cho, Hyun

    2014-05-01

    The energy discontinuity in the valence band (deltaE(v)) of Y2O3-stabilized ZrO2 (YSZ)/InGaZnO4 (IGZO) heterostructures was obtained from X-ray photoelectron spectroscopy (XPS) measurements. The YSZ exhibited a bandgap of 4.4 eV from absorption measurements. A value of deltaE(v) = 0.57 +/- 0.12 eV was obtained by using Ga 2P3/2, Zn 2p3/2 and In 3d5/2 energy levels as references. This implies a conduction band offset (deltaE(c)) of 0.63 eV in YSZ/InGaZnO4 heterostructures and a nested interface band alignment.

  16. {alpha}- and {beta}-La{sub 4}Ti{sub 9}Si{sub 4}O{sub 30}. Synthesis and structure of the second member (m = 2) of novel layered oxosilicates containing (110) rutile sheets. Electrical property and band structure characterization of the mixed-valence titanium(III/IV) oxosilicate series, La{sub 4}Ti(Si{sub 2}O{sub 7}){sub 2}(TiO{sub 2}){sub 4m} (m = 1, 2)

    SciTech Connect

    Wang, S.; Hwu, S.J.; Paradis, J.A.; Whangbo, M.H.

    1995-05-24

    Detailed description is presented of molten salt synthesis, single crystal structures, and a comparison is offered of the {alpha}- and {beta}-La{sub 4}Ti{sub 9}Si{sub 4}O{sub 30} phases. The electrical property and band struture of this mixed-valence titanium (III/IV) oxosilicate series, La{sub 4}Ti(Si{sub 2}O{sub 7}){sub 2}(TiO{sub 2}){sub 4m} (m = 1,2), are discussed in terms of electronic interactions in a confined space with respect to the (110) rutile sheets. The results from the extended Hueckel tight binding calculations and the bond valence sum analysis are contrasted with regard to charge distribution. 33 refs., 9 figs., 3 tabs.

  17. Attosecond photoionization dynamics with stimulated core-valence transitions

    NASA Astrophysics Data System (ADS)

    You, Jhih-An; Rohringer, Nina; Dahlström, Jan Marcus

    2016-03-01

    We investigate ionization of neon atoms by an isolated attosecond pump pulse in the presence of two coherent extreme ultraviolet or x-ray probe fields. The probe fields are tuned to a core-valence transition in the residual ion and induce spectral shearing of the photoelectron distributions. We show that the photoelectron-ion coincidence signal contains an interference pattern that depends on the temporal structure of the attosecond pump pulse and the stimulated core-valence transition. Many-body perturbation theory is used to compute "atomic response times" for the processes and we find strikingly different behavior for stimulation to the outer-core hole (2 p ↔2 s ) and stimulation to the inner-core hole (2 p ↔1 s ). The response time of the inner-core transition is found to be comparable to that of state-of-the-art laser-based characterization techniques for attosecond pulses.

  18. Conduction-band electronic states of YbInCu{sub 4} studied by photoemission and soft x-ray absorption spectroscopies

    SciTech Connect

    Utsumi, Yuki; Kurihara, Hidenao; Maso, Hiroyuki; Tobimatsu, Komei; Sato, Hitoshi; Shimada, Kenya; Namatame, Hirofumi; Hiraoka, Koichi; Kojima, Kenichi; Ohkochi, Takuo; Fujimori, Shin-ichi; Takeda, Yukiharu; Saitoh, Yuji; Mimura, Kojiro; Ueda, Shigenori; Yamashita, Yoshiyuki; Yoshikawa, Hideki; Kobayashi, Keisuke; Oguchi, Tamio; Taniguchi, Masaki

    2011-09-15

    We have studied conduction-band (CB) electronic states of a typical valence-transition compound YbInCu{sub 4} by means of temperature-dependent hard x-ray photoemission spectroscopy (HX-PES) of the Cu 2p{sub 3/2} and In 3d{sub 5/2} core states taken at h{nu}=5.95 keV, soft x-ray absorption spectroscopy (XAS) of the Cu 2p{sub 3/2} core absorption region around h{nu}{approx}935 eV, and soft x-ray photoemission spectroscopy (SX-PES) of the valence band at the Cu 2p{sub 3/2} absorption edge of h{nu}=933.0 eV. With decreasing temperature below the valence transition at T{sub V}=42 K, we have found that (1) the Cu 2p{sub 3/2} and In 3d{sub 5/2} peaks in the HX-PES spectra exhibit the energy shift toward the lower binding-energy side by {approx}40 and {approx}30 meV, respectively, (2) an energy position of the Cu 2p{sub 3/2} main absorption peak in the XAS spectrum is shifted toward higher photon-energy side by {approx}100 meV, with an appearance of a shoulder structure below the Cu 2p{sub 3/2} main absorption peak, and (3) an intensity of the Cu L{sub 3}VV Auger spectrum is abruptly enhanced. These experimental results suggest that the Fermi level of the CB-derived density of states is shifted toward the lower binding-energy side. We have described the valence transition in YbInCu{sub 4} in terms of the charge transfer from the CB to Yb 4f states.

  19. A Multidimensional Measure of Work Valences

    ERIC Educational Resources Information Center

    Porfeli, Erik J.; Lee, Bora; Weigold, Ingrid K.

    2012-01-01

    Work valence is derived from expectancy-valence theory and the literature on children's vocational development and is presumed to be a general appraisal of work that emerges during the childhood period. Work valence serves to promote and inhibit the motivation and tasks associated with vocational development. A measure of work valence, composed of…

  20. 2p2 Team News

    NASA Astrophysics Data System (ADS)

    Jones, H.

    2000-06-01

    The 2p2 Team continued towards the implementation at the 2.2-m of the same BOB (Broker for Observation Blocks) observing interface as seen at other ESO telescopes. This requires an interface to be written between the existing BOB software and the non-VLT compatible control software for the Wide-Field Imager (WFI) and 2.2-m. Cristian Urrutia, Tatiana Paz and Eduardo Robledo are heading its development. With this software in place, observers can use the VLT Phase 2 Proposal Preparation System (P2PP) for definition of their exposures, whether they are for Visitor or Service Mode.

  1. Band alignment at a MgO/GaSb heterointerface using x-ray photoelectron spectroscopy measurements

    NASA Astrophysics Data System (ADS)

    Li, Ruxue; Wei, Zhipeng; Liu, Xue; Li, Yongfeng; Fang, Xuan; Tang, Jilong; Fang, Dan; Gao, Xian; Wang, Dengkui; Hao, Yongqin; Yao, Bin; Ma, Xiaohui; Wang, Xiaohua

    2016-07-01

    The valence band offset (ΔE V) of a MgO/GaSb heterostructure was determined using x-ray photoelectron spectroscopy measurements. A ΔE V value of 2.84 ± 0.10 eV was calculated by using Ga 3d3/2 and Mg 2p1/2 binding energies as references. Taking the empirical band gaps of 7.83 eV and 0.73 eV for MgO and GaSb thin films into consideration, respectively, we obtained the type-I band alignment of a MgO/GaSb heterostructure with a conduction band offset (ΔE c) of 4.26 ± 0.10 eV, suggesting a nested interface band alignment.

  2. Study on the energy band structure and photoelectrochemical performances of spinel Li{sub 4}Ti{sub 5}O{sub 12}

    SciTech Connect

    Ge, Hao; Tian, Hui; Song, Hua; Liu, Daliang; Wu, Shuyao; Shi, Xicheng; Gao, Xiaoqiang; Lv, Li; Song, Xi-Ming

    2015-01-15

    Highlights: • Spinel Li{sub 4}Ti{sub 5}O{sub 12} possesses more positive potential of valence band and wider band gap than TiO{sub 2}. • Spinel Li{sub 4}Ti{sub 5}O{sub 12} displays typical n-type semiconductor characteristic and excellent UV-excitateded photocatalysis activity. • Our preliminary study will open new perspectives in investigation of other lithium-based compounds for new photocatalysts. - Abstract: Energy band structure, photoelectrochemical performances and photocatalysis activity of spinel Li{sub 4}Ti{sub 5}O{sub 12} are investigated for the first time in this paper. Li{sub 4}Ti{sub 5}O{sub 12} possesses more positive valence band potential and wider band gap than TiO{sub 2} due to its valence band consisting of Li{sub 1s} and Ti{sub 3d} orbitals mixed with O{sub 2p}. Li{sub 4}Ti{sub 5}O{sub 12} shows typical photocatalysis material characteristics and excellent photocatlytic activity under UV irradiation.

  3. Valence band of LiNi{sub {ital x}}Mn{sub 2{minus}{ital x}}O{sub 4} and its effects on the voltage profiles of LiNi{sub {ital x}}Mn{sub 2{minus}{ital x}}O{sub 4}/Li electrochemical cells

    SciTech Connect

    Gao, Y.; Myrtle, K.; Zhang, M. |; Reimers, J.N.; Dahn, J.R.

    1996-12-01

    A high-voltage plateau at 4.7 V in LiNi{sub {ital x}}Mn{sub 2{minus}{ital x}}O{sub 4}/Li electrochemical cells appears with the introduction of Ni into the LiMn{sub 2}O{sub 4} spinel. The capacity of the 4.7-V plateau increases linearly at the expense of the 4.1-V plateau as {ital x} increases. Using ultraviolet photoelectron spectroscopy, we have studied the top of the valence band of LiNi{sub {ital x}}Mn{sub 2{minus}{ital x}}O{sub 4} for a series of samples with 0.0{le}{ital x}{le}0.5. A component attributed to Ni 3{ital d} electrons was found at about 0.5-eV higher binding energy than the Mn 3{ital d} {ital e}{sub {ital g}} electrons. We propose that the increased voltage of the 4.7-V plateau is due to the increased energy required to remove electrons from Ni 3{ital d} levels compared to Mn 3{ital d} {ital e}{sub {ital g}} levels. {copyright} {ital 1996 The American Physical Society.}

  4. Valence holes observed in nanodiamonds dispersed in water.

    PubMed

    Petit, Tristan; Pflüger, Mika; Tolksdorf, Daniel; Xiao, Jie; Aziz, Emad F

    2015-02-21

    Colloidal dispersion is essential for most nanodiamond applications, but its influence on nanodiamond electronic properties remains unknown. Here we have probed the electronic structure of oxidized detonation nanodiamonds dispersed in water by using soft X-ray absorption and emission spectroscopies at the carbon and oxygen K edges. Upon dispersion in water, the π* transitions from sp(2)-hybridized carbon disappear, and holes in the valence band are observed.

  5. Valency configuration of transition metal impurities in ZnO

    SciTech Connect

    Petit, Leon; Schulthess, Thomas C; Svane, Axel; Temmerman, Walter M; Szotek, Zdzislawa; Janotti, Anderson

    2006-01-01

    We use the self-interaction corrected local spin-density approximation to investigate the ground state valency configuration of transition metal (TM=Mn, Co) impurities in n- and p-type ZnO. We find that in pure Zn{sub 1-x}TM{sub x}O, the localized TM{sup 2+} configuration is energetically favored over the itinerant d-electron configuration of the local spin density (LSD) picture. Our calculations indicate furthermore that the (+/0) donor level is situated in the ZnO gap. Consequently, for n-type conditions, with the Fermi energy {epsilon}F close to the conduction band minimum, TM remains in the 2+ charge state, while for p-type conditions, with {epsilon}F close to the valence band maximum, the 3+ charge state is energetically preferred. In the latter scenario, modeled here by co-doping with N, the additional delocalized d-electron charge transfers into the entire states at the top of the valence band, and hole carriers will only exist, if the N concentration exceeds the TM impurity concentration.

  6. Silicene Nano-Ribbons: Strong Resistance Towards Oxidation due to sp2 Hybridization of the Si Valence Orbitals

    NASA Astrophysics Data System (ADS)

    Le Lay, Guy; de Padova, Paola; Quaresima, Claudio; Olivieri, Bruno; Perfetti, Paolo

    2011-03-01

    We have synthesized for the first time silicene, that is, a new silicon allotrope analogous to graphene recently theoretically predicted, in the form of a massively parallel array of quantized zigzag nano-ribbons with a common ``magic'' width of 1.6 nm. They display characteristic linear band dispersions similar to the Dirac cones of graphene, in correspondence with their hexagonal arrangement seen in STM imaging. Here we show, through the angle-dependence of REEL spectra taken at the Si L2 , 3 edge, the typical signatures of 2p --> π * and 2p --> σ * transitions associated with sp 2 hybridization of the Si valence orbitals. We further show through high-resolution synchrotron radiation Si 2p core-level spectroscopy measurements that the afore mentioned silicene grating is very resistant toward oxidation. Typically, the oxygen uptake starts at about 104 higher doses than on the clean Si(111)7x7 surface. Indeed, this striking behavior is directly related to the sp 2 bonding, an additional confirmation of the silicene (i.e., graphene-like) nature of the nano-ribbons.

  7. Aesthetic valence of visual illusions

    PubMed Central

    Stevanov, Jasmina; Marković, Slobodan; Kitaoka, Akiyoshi

    2012-01-01

    Visual illusions constitute an interesting perceptual phenomenon, but they also have an aesthetic and affective dimension. We hypothesized that the illusive nature itself causes the increased aesthetic and affective valence of illusions compared with their non-illusory counterparts. We created pairs of stimuli. One qualified as a standard visual illusion whereas the other one did not, although they were matched in as many perceptual dimensions as possible. The phenomenal quality of being an illusion had significant effects on “Aesthetic Experience” (fascinating, irresistible, exceptional, etc), “Evaluation” (pleasant, cheerful, clear, bright, etc), “Arousal” (interesting, imaginative, complex, diverse, etc), and “Regularity” (balanced, coherent, clear, realistic, etc). A subsequent multiple regression analysis suggested that Arousal was a better predictor of Aesthetic Experience than Evaluation. The findings of this study demonstrate that illusion is a phenomenal quality of the percept which has measurable aesthetic and affective valence. PMID:23145272

  8. Comparison of the electronic band structures of LiCaAlF6 and LiSrAlF6 ultraviolet laser host media from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Viet Luong, Mui; Cadatal-Raduban, Marilou; Empizo, Melvin John F.; Arita, Ren; Minami, Yuki; Shimizu, Toshihiko; Sarukura, Nobuhiko; Azechi, Hiroshi; Pham, Minh Hong; Nguyen, Hung Dai; Kawazoe, Yoshiyuki

    2015-12-01

    We report the electronic structures and density of states (DOS) of perfect LiCAF and LiSAF crystals calculated from density functional theory (DFT) with local density approximation (LDA) using optimized lattice constants. DOS calculations reveal that the valence band is mainly derived from F 2p, thereby resulting to a very narrow valence band manifold. Meanwhile, the conduction band is mainly derived from Ca 4s or Sr 5s resulting to Sr having a broader band dispersion compared to Ca. Both fluoride compounds have indirect band gaps with LiCAF having a band gap of 8.02 eV and LiSAF a band gap of 7.92 eV. This is, to the best of our knowledge, the first report on the electronic structure of LiSAF calculated using DFT with LDA. Our results suggest that when doped with Ce3+, the shorter 5d-conduction band distance in Ce:LiSAF combined with the difficulty of growing high-purity crystals lead to the more pronounced excited state absorption (ESA) and solarization effect experimentally observed in Ce:LiSAF, limiting its potential as a laser material compared with Ce:LiCAF.

  9. The electronic structures of vanadate salts: Cation substitution as a tool for band gap manipulation

    NASA Astrophysics Data System (ADS)

    Dolgos, Michelle R.; Paraskos, Alexandra M.; Stoltzfus, Matthew W.; Yarnell, Samantha C.; Woodward, Patrick M.

    2009-07-01

    The electronic structures of six ternary metal oxides containing isolated vanadate ions, Ba 3(VO 4) 2, Pb 3(VO 4) 2, YVO 4, BiVO 4, CeVO 4 and Ag 3VO 4 were studied using diffuse reflectance spectroscopy and electronic structure calculations. While the electronic structure near the Fermi level originates largely from the molecular orbitals of the vanadate ion, both experiment and theory show that the cation can strongly influence these electronic states. The observation that Ba 3(VO 4) 2 and YVO 4 have similar band gaps, both 3.8 eV, shows that cations with a noble gas configuration have little impact on the electronic structure. Band structure calculations support this hypothesis. In Pb 3(VO 4) 2 and BiVO 4 the band gap is reduced by 0.9-1.0 eV through interactions of (a) the filled cation 6 s orbitals with nonbonding O 2 p states at the top of the valence band, and (b) overlap of empty 6 p orbitals with antibonding V 3 d-O 2 p states at the bottom of the conduction band. In Ag 3VO 4 mixing between filled Ag 4 d and O 2 p states destabilizes states at the top of the valence band leading to a large decrease in the band gap ( Eg=2.2 eV). In CeVO 4 excitations from partially filled 4 f orbitals into the conduction band lower the effective band gap to 1.8 eV. In the Ce 1-xBi xVO 4 (0≤ x≤0.5) and Ce 1-xY xVO 4 ( x=0.1, 0.2) solid solutions the band gap narrows slightly when Bi 3+ or Y 3+ are introduced. The nonlinear response of the band gap to changes in composition is a result of the localized nature of the Ce 4 f orbitals.

  10. Black Phosphorus Transistors with Near Band Edge Contact Schottky Barrier.

    PubMed

    Ling, Zhi-Peng; Sakar, Soumya; Mathew, Sinu; Zhu, Jun-Tao; Gopinadhan, K; Venkatesan, T; Ang, Kah-Wee

    2015-01-01

    Black phosphorus (BP) is a new class of 2D material which holds promise for next generation transistor applications owing to its intrinsically superior carrier mobility properties. Among other issues, achieving good ohmic contacts with low source-drain parasitic resistance in BP field-effect transistors (FET) remains a challenge. For the first time, we report a new contact technology that employs the use of high work function nickel (Ni) and thermal anneal to produce a metal alloy that effectively reduces the contact Schottky barrier height (ΦB) in a BP FET. When annealed at 300 °C, the Ni electrode was found to react with the underlying BP crystal and resulted in the formation of nickel-phosphide (Ni2P) alloy. This serves to de-pin the metal Fermi level close to the valence band edge and realizes a record low hole ΦB of merely ~12 meV. The ΦB at the valence band has also been shown to be thickness-dependent, wherein increasing BP multi-layers results in a smaller ΦB due to bandgap energy shrinkage. The integration of hafnium-dioxide high-k gate dielectric additionally enables a significantly improved subthreshold swing (SS ~ 200 mV/dec), surpassing previously reported BP FETs with conventional SiO2 gate dielectric (SS > 1 V/dec). PMID:26667402

  11. Black Phosphorus Transistors with Near Band Edge Contact Schottky Barrier

    PubMed Central

    Ling, Zhi-Peng; Sakar, Soumya; Mathew, Sinu; Zhu, Jun-Tao; Gopinadhan, K.; Venkatesan, T.; Ang, Kah-Wee

    2015-01-01

    Black phosphorus (BP) is a new class of 2D material which holds promise for next generation transistor applications owing to its intrinsically superior carrier mobility properties. Among other issues, achieving good ohmic contacts with low source-drain parasitic resistance in BP field-effect transistors (FET) remains a challenge. For the first time, we report a new contact technology that employs the use of high work function nickel (Ni) and thermal anneal to produce a metal alloy that effectively reduces the contact Schottky barrier height (ΦB) in a BP FET. When annealed at 300 °C, the Ni electrode was found to react with the underlying BP crystal and resulted in the formation of nickel-phosphide (Ni2P) alloy. This serves to de-pin the metal Fermi level close to the valence band edge and realizes a record low hole ΦB of merely ~12 meV. The ΦB at the valence band has also been shown to be thickness-dependent, wherein increasing BP multi-layers results in a smaller ΦB due to bandgap energy shrinkage. The integration of hafnium-dioxide high-k gate dielectric additionally enables a significantly improved subthreshold swing (SS ~ 200 mV/dec), surpassing previously reported BP FETs with conventional SiO2 gate dielectric (SS > 1 V/dec). PMID:26667402

  12. The electronic properties of mixed valence hydrated europium chloride thin film.

    PubMed

    Silly, M G; Charra, F; Lux, F; Lemercier, G; Sirotti, F

    2015-07-28

    We investigate the electronic properties of a model mixed-valence hydrated chloride europium salt by means of high resolution photoemission spectroscopy (HRPES) and resonant photoemission spectroscopy (RESPES) at the Eu 3d → 4f and 4d → 4f transitions. From the HRPES spectra, we have determined that the two europium oxidation states are homogeneously distributed in the bulk and that the hydrated salt film is exempt from surface mixed valence transition. From the RESPES spectra, the well separated resonant contributions characteristic of divalent and trivalent europium species (4f(6) and 4f(7) final states, respectively) are accurately extracted and quantitatively determined from the resonant features measured at the two edges. The partial absorption yield spectra, obtained by integrating the photoemission intensity in the valence-band region, can be well reproduced by atomic multiplet calculation at the M(4,5) (3d-4f) absorption edge and by an asymmetric Fano-like shape profile at the N(4,5) (4d-4f) absorption edge. The ratio of Eu(2+) and Eu(3+) species measured at the two absorption edges matches with the composition of the mixed valence europium salt as determined chemically. We have demonstrated that the observed spectroscopic features of the mixed valence salt are attributed to the mixed-valence ground state rather than surface valence transition. HRPES and RESPES spectra provide reference spectra for the study of europium salts and their derivatives. PMID:26105214

  13. The electronic properties of mixed valence hydrated europium chloride thin film.

    PubMed

    Silly, M G; Charra, F; Lux, F; Lemercier, G; Sirotti, F

    2015-07-28

    We investigate the electronic properties of a model mixed-valence hydrated chloride europium salt by means of high resolution photoemission spectroscopy (HRPES) and resonant photoemission spectroscopy (RESPES) at the Eu 3d → 4f and 4d → 4f transitions. From the HRPES spectra, we have determined that the two europium oxidation states are homogeneously distributed in the bulk and that the hydrated salt film is exempt from surface mixed valence transition. From the RESPES spectra, the well separated resonant contributions characteristic of divalent and trivalent europium species (4f(6) and 4f(7) final states, respectively) are accurately extracted and quantitatively determined from the resonant features measured at the two edges. The partial absorption yield spectra, obtained by integrating the photoemission intensity in the valence-band region, can be well reproduced by atomic multiplet calculation at the M(4,5) (3d-4f) absorption edge and by an asymmetric Fano-like shape profile at the N(4,5) (4d-4f) absorption edge. The ratio of Eu(2+) and Eu(3+) species measured at the two absorption edges matches with the composition of the mixed valence europium salt as determined chemically. We have demonstrated that the observed spectroscopic features of the mixed valence salt are attributed to the mixed-valence ground state rather than surface valence transition. HRPES and RESPES spectra provide reference spectra for the study of europium salts and their derivatives.

  14. The Valence Bond Interpretation of Molecular Geometry.

    ERIC Educational Resources Information Center

    Smith, Derek W.

    1980-01-01

    Presents ways in which the valence bond (VB) theory describes the bonding and geometry of molecules, following directly from earlier principles laid down by Pauling and others. Two other theories (molecular orbital approach and valence shell electron pair repulsion) are discussed and compared to VB. (CS)

  15. Valence-Bond Theory and Chemical Structure.

    ERIC Educational Resources Information Center

    Klein, Douglas J.; Trinajstic, Nenad

    1990-01-01

    Discussed is the importance of valence bond theory on the quantum-mechanical theory of chemical structure and the nature of the chemical bond. Described briefly are early VB theory, development of VB theory, modern versions, solid-state applications, models, treatment in textbooks, and flaws in criticisms of valence bond theory. (KR)

  16. Band offsets between amorphous LaAlO3 and In0.53Ga0.47As

    NASA Astrophysics Data System (ADS)

    Goel, N.; Tsai, W.; Garner, C. M.; Sun, Y.; Pianetta, P.; Warusawithana, M.; Schlom, D. G.; Wen, H.; Gaspe, C.; Keay, J. C.; Santos, M. B.; Goncharova, L. V.; Garfunkel, E.; Gustafsson, T.

    2007-09-01

    The band offsets between an amorphous LaAlO3 dielectric prepared by molecular-beam deposition and a n-type In0.53Ga0.47As (001) layer have been measured using synchrotron radiation photoemission spectroscopy. The valence and conduction band offsets at the postdeposition annealed LaAlO3/InGaAs interface are 3.1±0.1 and 2.35±0.2eV, respectively. The band gap of LaAlO3, as determined by Al 2p and O 1s core level energy loss spectra, is 6.2±0.1eV. Within the resolution of the medium energy ion scattering technique, no interfacial oxide layer is seen between the InGaAs and the 3.6nm thick amorphous LaAlO3.

  17. Avoided valence transition in a plutonium superconductor.

    PubMed

    Ramshaw, B J; Shekhter, Arkady; McDonald, Ross D; Betts, Jon B; Mitchell, J N; Tobash, P H; Mielke, C H; Bauer, E D; Migliori, Albert

    2015-03-17

    The d and f electrons in correlated metals are often neither fully localized around their host nuclei nor fully itinerant. This localized/itinerant duality underlies the correlated electronic states of the high-Tc cuprate superconductors and the heavy-fermion intermetallics and is nowhere more apparent than in the 5f valence electrons of plutonium. Here, we report the full set of symmetry-resolved elastic moduli of PuCoGa5--the highest Tc superconductor of the heavy fermions (Tc = 18.5 K)--and find that the bulk modulus softens anomalously over a wide range in temperature above Tc. The elastic symmetry channel in which this softening occurs is characteristic of a valence instability--therefore, we identify the elastic softening with fluctuations of the plutonium 5f mixed-valence state. These valence fluctuations disappear when the superconducting gap opens at Tc, suggesting that electrons near the Fermi surface play an essential role in the mixed-valence physics of this system and that PuCoGa5 avoids a valence transition by entering the superconducting state. The lack of magnetism in PuCoGa5 has made it difficult to reconcile with most other heavy-fermion superconductors, where superconductivity is generally believed to be mediated by magnetic fluctuations. Our observations suggest that valence fluctuations play a critical role in the unusually high Tc of PuCoGa5.

  18. Avoided valence transition in a plutonium superconductor

    PubMed Central

    Ramshaw, B. J.; Shekhter, Arkady; McDonald, Ross D.; Betts, Jon B.; Mitchell, J. N.; Tobash, P. H.; Mielke, C. H.; Bauer, E. D.; Migliori, Albert

    2015-01-01

    The d and f electrons in correlated metals are often neither fully localized around their host nuclei nor fully itinerant. This localized/itinerant duality underlies the correlated electronic states of the high-Tc cuprate superconductors and the heavy-fermion intermetallics and is nowhere more apparent than in the 5f valence electrons of plutonium. Here, we report the full set of symmetry-resolved elastic moduli of PuCoGa5—the highest Tc superconductor of the heavy fermions (Tc = 18.5 K)—and find that the bulk modulus softens anomalously over a wide range in temperature above Tc. The elastic symmetry channel in which this softening occurs is characteristic of a valence instability—therefore, we identify the elastic softening with fluctuations of the plutonium 5f mixed-valence state. These valence fluctuations disappear when the superconducting gap opens at Tc, suggesting that electrons near the Fermi surface play an essential role in the mixed-valence physics of this system and that PuCoGa5 avoids a valence transition by entering the superconducting state. The lack of magnetism in PuCoGa5 has made it difficult to reconcile with most other heavy-fermion superconductors, where superconductivity is generally believed to be mediated by magnetic fluctuations. Our observations suggest that valence fluctuations play a critical role in the unusually high Tc of PuCoGa5. PMID:25737548

  19. Generalized resonating valence bond description of cyclobutadiene

    SciTech Connect

    Voter, A.F.; Goddard, W.A. III

    1986-05-28

    The low-lying electronic states of square and rectangular cyclobutadiene (CBD) are calculated by using the generalized resonating valence bond (GRVB) method and compared with the results from Hartree-Fock and configuration interaction wavefunctions. We find that simple valence bond concepts correctly predict the sequence of excited states (including ground-state singlet) and the distortion to a rectangular geometry for the ground state. Contrary to common expectation, we find that the singlet ground state of square CBD has 22 kcal of resonance energy (relative to a single valence bond structure). Thus, CBD is not antiresonant, though it is much less stable than normal conjugated systems.

  20. High quality HfO{sub 2}/p-GaSb(001) metal-oxide-semiconductor capacitors with 0.8 nm equivalent oxide thickness

    SciTech Connect

    Barth, Michael; Datta, Suman; Bruce Rayner, G.; McDonnell, Stephen; Wallace, Robert M.; Bennett, Brian R.; Engel-Herbert, Roman

    2014-12-01

    We investigate in-situ cleaning of GaSb surfaces and its effect on the electrical performance of p-type GaSb metal-oxide-semiconductor capacitor (MOSCAP) using a remote hydrogen plasma. Ultrathin HfO{sub 2} films grown by atomic layer deposition were used as a high permittivity gate dielectric. Compared to conventional ex-situ chemical cleaning methods, the in-situ GaSb surface treatment resulted in a drastic improvement in the impedance characteristics of the MOSCAPs, directly evidencing a much lower interface trap density and enhanced Fermi level movement efficiency. We demonstrate that by using a combination of ex-situ and in-situ surface cleaning steps, aggressively scaled HfO{sub 2}/p-GaSb MOSCAP structures with a low equivalent oxide thickness of 0.8 nm and efficient gate modulation of the surface potential are achieved, allowing to push the Fermi level far away from the valence band edge high up into the band gap of GaSb.

  1. Band alignment of HfO{sub 2}/In{sub 0.18}Al{sub 0.82}N determined by angle-resolved x-ray photoelectron spectroscopy

    SciTech Connect

    Owen, Man Hon Samuel E-mail: yeo@ieee.org; Bhuiyan, Maruf Amin; Yeo, Yee-Chia E-mail: yeo@ieee.org; Zhang, Zheng; Pan, Ji Sheng; Tok, Eng Soon

    2014-07-21

    The band-alignment of atomic layer deposited (ALD)-HfO{sub 2}/In{sub 0.18}Al{sub 0.82}N was studied by high resolution angle-resolved X-ray photoelectron spectroscopy measurements. The band bending near the HfO{sub 2}/In{sub 0.18}Al{sub 0.82}N interface was investigated, and the potential variation across the interface was taken into account in the band alignment calculation. It is observed that the binding energies for N 1s and Al 2p in In{sub 0.18}Al{sub 0.82}N decreases and the corresponding extracted valence band offsets increases with increasing θ (i.e., closer to the HfO{sub 2}/In{sub 0.18}Al{sub 0.82}N interface), as a result of an upward energy band bending towards the HfO{sub 2}/In{sub 0.18}Al{sub 0.82}N interface. The resultant valence band offset and the conduction band offset for the ALD-HfO{sub 2}/In{sub 0.18}Al{sub 0.82}N interface calculated was found to be 0.69 eV and 1.01 eV, respectively.

  2. Action versus valence in decision making

    PubMed Central

    Guitart-Masip, Marc; Duzel, Emrah; Dolan, Ray; Dayan, Peter

    2014-01-01

    The selection of actions, and the vigor with which they are executed, are influenced by the affective valence of predicted outcomes. This interaction between action and valence significantly influences appropriate and inappropriate choices and is implicated in the expression of psychiatric and neurological abnormalities, including impulsivity and addiction. We review a series of recent human behavioral, neuroimaging, and pharmacological studies whose key design feature is an orthogonal manipulation of action and valence. These studies find that the interaction between the two is subject to the critical influence of dopamine. They also challenge existing views that neural representations in the striatum focus on valence, showing instead a dominance of the anticipation of action. PMID:24581556

  3. Photoionization of iodine atoms: Rydberg series which converge to the I{sup +}({sup 1}S{sub 0})<-I({sup 2}P{sub 3/2}) threshold

    SciTech Connect

    Eypper, Marie; Innocenti, Fabrizio; Morris, Alan; Dyke, John M.; Stranges, Stefano; West, John B.; King, George C.

    2010-06-28

    Relative partial photoionization cross sections and angular distribution parameters {beta} have been measured for the first and fourth (5p){sup -1} photoelectron (PE) bands of atomic iodine by performing angle-resolved constant-ionic-state (CIS) measurements on these PE bands between the {sup 1}D{sub 2} and {sup 1}S{sub 0} (5p){sup -1} ionic thresholds in the photon energy region of 12.9-14.1 eV. Rydberg series arising from the 5p{yields}ns and 5p{yields}nd excitations are observed in both the first PE band, I{sup +}({sup 3}P{sub 2})<-I({sup 2}P{sub 3/2}), and the fourth PE band, I{sup +}({sup 1}D{sub 2})<-I({sup 2}P{sub 3/2}), CIS spectra. For each Rydberg state, the resonance energy, quantum defect, linewidth, line shape, and photoelectron angular distribution parameter {beta} have been determined. For the {beta}-plots for each PE band, only resonances corresponding to 5p{yields}nd excitations are observed; no resonances were seen at photon energies corresponding to the 5p{yields}ns resonances in the CIS spectra. The {beta}-plots are interpreted in terms of the parity unfavored channel with j{sub t}=4 being the major contributor at the 5p{yields}nd resonance positions, where j{sub t} is the quantum number for angular momentum transferred between the molecule, and the ion and photoelectron. Comparison of the results obtained with those published for bromine shows reasonably good agreement for the CIS spectra but poor agreement for the {beta}-plots. It appears that parity unfavored channels are playing a greater role in the valence (np){sup -1} ionization of atomic iodine than in the corresponding ionization of atomic bromine.

  4. 2p radioactivity studied by tracking technique

    SciTech Connect

    Mukha, Ivan

    2010-06-01

    The recent advance in experimental studies of short-lived exotic nuclei beyond the proton drip line is presented. In particular, in-flight decays of proton-unbound nuclei with picosecond lifetimes can be probed by a novel technique which tracks all decay products precisely, and the decay vertices as well as the angular correlations of the fragments are deduced from the measured trajectories. The corresponding pioneering experiment which identified a previously-unknown isotope {sup 19}Mg and its two-proton (2p) radioactivity as well as studied the reference 2p decay of the known isotope {sup 16}Ne is described. Systematic studies of other 2p precursors beyond the proton drip line are foreseen with this powerful technique whose sensitivity is larger by factor of 30 in comparison with a conventional invariant-mass method. The 2p radioactivity candidates {sup 30}Ar, {sup 34}Ca and {sup 26}S are discussed. Information about the respective one-proton unbound nuclei can be obtained with this technique by evaluating proton-heavy-fragment correlations. Systematic studies of nuclei beyond the proton drip line, e.g., the well-known proton resonances above the 'waiting points' in the astrophysical rp-process, {sup 69}Br and {sup 73}Br are feasible.

  5. Surface band structure of Si(111)2×1

    NASA Astrophysics Data System (ADS)

    Chen, B.; Haneman, D.

    1995-02-01

    The surface band structures of the three-bond scission (TBS) model and the Pandey-chain (PC) model have been computed using an ab initio Hartree-Fock program crystal 92. In the case of the bulk energy bands, the method gives the correct shapes and structure but overestimates the valence-band dispersion by about 50%. For the TBS model, the calculated valence-band dispersion came out about 50% wider than measured experimentally. This would suggest that the model is consistent with optical data. In the case of the PC model, the valence-band dispersion was qualitatively similar to those of previous calculations, but the width discrepancy was large. The method overestimates the surface band gap for both TBS and PC models. The significance is discussed.

  6. Symmetry of valence states of Heusler compounds explored by linear dichroism in hard-x-ray photoelectron spectroscopy.

    PubMed

    Ouardi, Siham; Fecher, Gerhard H; Kozina, Xeniya; Stryganyuk, Gregory; Balke, Benjamin; Felser, Claudia; Ikenaga, Eiji; Sugiyama, Takeharu; Kawamura, Naomi; Suzuki, Motohiro; Kobayashi, Keisuke

    2011-07-15

    This study reports on the linear dichroism in angular-resolved photoemission from the valence band of the Heusler compounds NiTi0.9Sc0.1Sn and NiMnSb. High-resolution photoelectron spectroscopy was performed with an excitation energy of hν = 7.938  keV. The linear polarization of the photons was changed using an in-vacuum diamond phase retarder. The valence band spectra exhibit the typical structure expected from first-principles calculations of the electronic structure of these compounds. Noticeable linear dichroism is found in the valence band of both materials, and this allows for a symmetry analysis of the contributing states. The differences in the spectra are found to be caused by symmetry-dependent angular asymmetry parameters, and these occur even in polycrystalline samples without preferential crystallographic orientation.

  7. Local atomic configuration and Auger Valence Electron Spectra in BiSrCaCuO single crystals

    SciTech Connect

    Fujiwara, Y.; Hirata, S.; Nishikubo, M.; Kobayashi, T. ); Nakayama, H.; Fujita, H. . Faculty of Engineering)

    1991-03-01

    This paper reports on Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub y} (2212) and Ca-doped Bi{sub 2}Sr{sub 2}CuO{sub y} (2201) single crystals systematically investigated by Auger Valence Electron Spectroscopy (AVES). In AVES measurements on two kinds of crystals, a drastic difference was observed in the spectral shape of Ca(2p,3p,3p), reflecting a difference in spin-orbit splitting induced by local atomic configuration in the vicinity of Ca atoms. Furthermore, Ca(2p,3p,4s) spectrum appeared in both the crystals, which indicates that the real valency of Ca atoms is deviated from + 2 in the crystals. These results suggest that AVES is a promising probe for characterizing local atomic configuration and valence electron states of the constituent elements.

  8. Role of Interlayer Coupling on the Evolution of Band Edges in Few-Layer Phosphorene.

    PubMed

    Wang, V; Liu, Y C; Kawazoe, Y; Geng, W T

    2015-12-17

    Using first-principles calculations, we have investigated the evolution of band edges in few-layer phosphorene as a function of the number of P layers. Our results predict that monolayer phosphorene is an indirect band gap semiconductor and its valence band edge is extremely sensitive to strain. Its band gap could undergo an indirect-to-direct transition under a lattice expansion as small as 1% along the zigzag direction. A semiempirical interlayer coupling model is proposed, which can reproduce the evolution of valence band edges obtained by first-principles calculations well. We conclude that the interlayer coupling plays a dominant role in the evolution of the band edges via decreasing both band gap and carrier effective masses with the increase of phosphorene thickness. Scrutiny of the orbital-decomposed band structure provides a better understanding of the upward shift of the valence band maximum, surpassing that of the conduction band minimum.

  9. Subliminal Affect Valence Words Change Conscious Mood Potency but Not Valence: Is This Evidence for Unconscious Valence Affect?

    PubMed Central

    Shevrin, Howard; Panksepp, Jaak; Brakel, Linda A. W.; Snodgrass, Michael

    2012-01-01

    Whether or not affect can be unconscious remains controversial. Research claiming to demonstrate unconscious affect fails to establish clearly unconscious stimulus conditions. The few investigations that have established unconscious conditions fail to rule out conscious affect changes. We report two studies in which unconscious stimulus conditions were met and conscious mood changes measured. The subliminal stimuli were positive and negative affect words presented at the objective detection threshold; conscious mood changes were measured with standard manikin valence, potency, and arousal scales. We found and replicated that unconscious emotional stimuli produced conscious mood changes on the potency scale but not on the valence scale. Were positive and negative affects aroused unconsciously, but reflected consciously in potency changes? Or were the valence words unconscious cognitive causes of conscious mood changes being activated without unconscious affect? A thought experiment is offered as a way to resolve this dilemma. PMID:24961258

  10. The valence electronic structure and conformational flexibility of epichlorohydrin.

    PubMed

    Stranges, S; Alagia, M; Decleva, P; Stener, M; Fronzoni, G; Toffoli, D; Speranza, M; Catone, D; Turchini, S; Prosperi, T; Zema, N; Contini, G; Keheyan, Y

    2011-07-21

    The electronic structure of epichlorohydrin is investigated in the whole valence region by a combined experimental and theoretical study. The issue of controversial assignments of the molecular electronic structure is here addressed. Photoelectron spectra (PES) and Threshold Photoelectron spectra (TPES) of room temperature molecules in the gas phase are recorded. Geometries and energies of the stable conformers due to internal rotation of the C-C-C-Cl dihedral angle, gauche-II (g-II), gauche-I (g-I), and cis, are calculated, and the effect of the conformational flexibility on the photoionization energetics is studied by DFT and 2h-1p Configuration Interaction (CI) methods. Strong breakdown of the Koopmans Theorem (KT) is obtained for the four outermost ionizations, which are further investigated by higher level ab initio calculations. The full assignment of the spectrum is put on a firm basis by the combination of experimental and theoretical results. The orbital composition from correlated calculations is found closer to the DFT orbitals, which are then used to analyze the electronic structure of the molecule. The Highest Occupied Molecular Orbital (HOMO) and HOMO--2 are n(O)/n(Cl) mixed orbitals. The nature of each valence MO is generally preserved in all the conformers, although the magnitude of the n(O)/n(Cl) mixing in HOMO and HOMO--2 varies to some extent with the C-C-C-Cl dihedral angle. The low energy part of the HOMO PE band is predicted to be substantially affected by the conformational flexibility, as experimentally observed in the spectra. The rest of the spectrum is described in terms of the dominant conformer g-II, and a good agreement between experiment and theory is found. The inner-valence PE spectrum is characterized by satellite structures, due to electron correlation effects, which are interpreted by means of 2h-1p CI calculations.

  11. Data Sharing in P2P Systems

    NASA Astrophysics Data System (ADS)

    Hayek, Rabab; Raschia, Guillaume; Valduriez, Patrick; Mouaddib, Noureddine

    In this chapter, we survey P2P data sharing systems. All along, we focus on the evolution from simple file-sharing systems, with limited functionalities, to Peer Data Management Systems (PDMS) that support advanced applications with more sophisticated data management techniques. Advanced P2P applications are dealing with semantically rich data (e.g., XML documents, relational tables), using a high-level SQL-like query language. We start our survey with an overview over the existing P2P network architectures, and the associated routing protocols. Then, we discuss data indexing techniques based on their distribution degree and the semantics they can capture from the underlying data. We also discuss schema management techniques which allow integrating heterogeneous data. We conclude by discussing the techniques proposed for processing complex queries (e.g., range and join queries). Complex query facilities are necessary for advanced applications which require a high level of search expressiveness. This last part shows the lack of querying techniques that allow for an approximate query answering.

  12. Molybdenum Valence in Basaltic Silicate Melts

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Pando, K.

    2010-01-01

    The moderately siderophile element molybdenum has been used as an indicator in planetary differentiation processes, and is particularly relevant to core formation [for example, 1-6]. However, models that apply experimental data to an equilibrium differentiation scenario infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Partitioning behavior of molybdenum, a multivalent element with a transition near the J02 of interest for core formation (IW-2) will be sensitive to changes in JO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo6+ can be either octahedrally or tetrahedrally coordinated. Here we present first XANES measurements of Mo valence in basaltic run products at a range of P, T, and JO2 and further quantify the valence transition of Mo.

  13. Evidence for Valence Alternation in Amorphous Selenium

    NASA Astrophysics Data System (ADS)

    Xiaodong, Zhang; Drabold, D. A.

    1998-05-01

    A molecular-dynamics simulation has been carried out for amorphous selenium. The simulation used 64 atoms as well as 216 atoms in a constant volume simple cubic cell. The pair correlation function g(r) and structure factors S(Q) were computed and compared with experimental and previous theoretical data. The coordination number is exactly 2 in both 64 atoms and 216 atoms model. In 64 atoms model, only 1 intimate valence alternation pair (IVAP) type defect was produced. The majority defect types are IVAP and valence alternation pair (VAP) in 216 atoms model. The electronic density function of state and the localization of the electronic state also manisfest some characternistic of VAP defect type. The results give a theoretical evidence for valence alternation in a-Se.

  14. Band gap engineering via electrostatic chemical strain in cation ordered LaSrAlO4

    NASA Astrophysics Data System (ADS)

    Balachandran, Prasanna V.; Rondinelli, James M.

    2014-03-01

    In this work, we employ density functional theory to examine a novel design route that employs A-site cation ordering to engineer the band gaps of (A,A')BO4 Ruddlesden-Popper (RP) oxides. Using LaSrAlO4 as a model material, we show that the band gap is highly sensitive to the A-site cation ordering ranging from 3-4.5 eV. When the [AlO2]-1 layers are interleaved between two chemically equivalent [LaO]1+ or [SrO]0+ layers, we obtain the smallest band gap with a reduction of ~1 eV determined from the Heyd, Scuseria, and Ernzerhof (HSE) hybrid exchange-correlation functional. We relate the observed band gap reduction to the local bond distortions arising from electrostatic chemical strain induced changes to the O 2 p and La 5 d states in the valence and conduction bands, respectively. The project was supported by The Defense Advanced Research Projects Agency (grant no. N66001-12-4224). The views, opinions, and/or findings reported here are solely those of the authors and do not represent official views of DARPA or DOD.

  15. Electronic states of BP, BP +, BP -, B 2P 2, B2P2- and B2P2+

    NASA Astrophysics Data System (ADS)

    Linguerri, Roberto; Komiha, Najia; Oswald, Rainer; Mitrushchenkov, Alexander; Rosmus, Pavel

    2008-05-01

    Using augmented sextuple zeta basis sets and internally contracted multireference configuration interaction (MRCI) wavefunctions, potential energy, electric dipole and transition moments have been computed for the X 3Π, a 1Σ +, b 1Π and A 3Σ - states of BP, X 2Σ + and A 2Π states of BP - and X 4Σ - and A 4Π states of BP +. From these data spectroscopic constants, radiative transition probabilities and photoelectron spectra of BP - and BP have been evaluated. The non-vanishing spin-orbit coupling elements between the four low lying triplet and singlet states of the neutral BP have also been calculated from MRCI wavefunctions. The treatment of the corresponding perturbations in the manifold of dense rovibrational states in the three lowest states would require a precise knowledge of the electronic excitation energies. Our best singlet-triplet separations (X-a) are calculated to be 2412 cm -1 (MRCI) and 2482 cm -1 (restricted coupled cluster with perturbative triples (RCCSD(T))) with an estimated error bound of about ±200 cm -1. All three states have long radiative lifetimes with cascading among the rovibrational levels of different states. The ionization energy IE e of BP is calculated to be 9.22 eV (MRCI) and 9.48 eV (RCCSD(T)), the electron affinity EA e 2.51 eV (MRCI) and 2.74 eV (RCCSD(T)). The photoelectron spectra of BP and BP - have been obtained from the Franck-Condon factors of the MRCI potentials. For the UV spectroscopy the dipole allowed radiative transition probabilities are given for A 3Σ - ↔ X 3Π, b 1Π ↔ a 1Σ + of BP, A 2Π ↔ X 2Σ + of BP - and A 4Π ↔ X 4Σ - of BP +. The ionization energy IE e of B 2P 2 of 8.71 eV and the electron affinity EA e of 2.34 eV have been calculated by the RCCSD(T)/aVQZ approach. Also the harmonic vibrational wavenumbers for the electronic ground states of the ions B2P2+ and B2P2- are given.

  16. Unified interpretation of Hund's first and second rules for 2p and 3p atoms.

    PubMed

    Oyamada, Takayuki; Hongo, Kenta; Kawazoe, Yoshiyuki; Yasuhara, Hiroshi

    2010-10-28

    A unified interpretation of Hund's first and second rules for 2p (C, N, O) and 3p (Si, P, S) atoms is given by Hartree-Fock (HF) and multiconfiguration Hartree-Fock (MCHF) methods. Both methods exactly satisfy the virial theorem, in principle, which enables one to analyze individual components of the total energy E(=T+V(en)+V(ee)), where T, V(en), and V(ee) are the kinetic, the electron-nucleus attraction, and the electron-electron repulsion energies, respectively. The correct interpretation for each of the two rules can only be achieved under the condition of the virial theorem 2T+V=0 by investigating how V(en) and V(ee) interplay to attain the lower total potential energy V(=V(en)+V(ee)). The stabilization of the more stable states for all the 2p and 3p atoms is ascribed to a greater V(en) that is caused by contraction of the valence orbitals accompanied with slight expansion of the core orbitals. The contraction of the valence orbitals for the two rules is a consequence of reducing the Hartree screening of the nucleus at short interelectronic distances. The reduced screening in the first rule is due to a greater amount of Fermi hole contributions in the state with the highest total spin-angular momentum S. The reduced screening in the second rule is due to the fact that two valence electrons are more likely to be on opposite sides of the nucleus in the state with the highest total orbital-angular momentum L. For each of the two rules, the inclusion of correlation does not qualitatively change the HF interpretation, but HF overestimates the energy difference ∣ΔE∣ between two levels being compared. The magnitude of the correlation energy is significantly larger for the lower L states than for the higher L states since two valence electrons in the lower L states are less likely to be on opposite sides of the nucleus. The MCHF evaluation of ∣ΔE∣ is in excellent agreement with experiment. The present HF and MCHF calculations demonstrate the above statements

  17. Unified interpretation of Hund's first and second rules for 2p and 3p atoms.

    PubMed

    Oyamada, Takayuki; Hongo, Kenta; Kawazoe, Yoshiyuki; Yasuhara, Hiroshi

    2010-10-28

    A unified interpretation of Hund's first and second rules for 2p (C, N, O) and 3p (Si, P, S) atoms is given by Hartree-Fock (HF) and multiconfiguration Hartree-Fock (MCHF) methods. Both methods exactly satisfy the virial theorem, in principle, which enables one to analyze individual components of the total energy E(=T+V(en)+V(ee)), where T, V(en), and V(ee) are the kinetic, the electron-nucleus attraction, and the electron-electron repulsion energies, respectively. The correct interpretation for each of the two rules can only be achieved under the condition of the virial theorem 2T+V=0 by investigating how V(en) and V(ee) interplay to attain the lower total potential energy V(=V(en)+V(ee)). The stabilization of the more stable states for all the 2p and 3p atoms is ascribed to a greater V(en) that is caused by contraction of the valence orbitals accompanied with slight expansion of the core orbitals. The contraction of the valence orbitals for the two rules is a consequence of reducing the Hartree screening of the nucleus at short interelectronic distances. The reduced screening in the first rule is due to a greater amount of Fermi hole contributions in the state with the highest total spin-angular momentum S. The reduced screening in the second rule is due to the fact that two valence electrons are more likely to be on opposite sides of the nucleus in the state with the highest total orbital-angular momentum L. For each of the two rules, the inclusion of correlation does not qualitatively change the HF interpretation, but HF overestimates the energy difference ∣ΔE∣ between two levels being compared. The magnitude of the correlation energy is significantly larger for the lower L states than for the higher L states since two valence electrons in the lower L states are less likely to be on opposite sides of the nucleus. The MCHF evaluation of ∣ΔE∣ is in excellent agreement with experiment. The present HF and MCHF calculations demonstrate the above statements

  18. KSi2P3: A new layered phosphidopolysilicate (IV)

    NASA Astrophysics Data System (ADS)

    Feng, Kai; Kang, Lei; Yin, Wenlong; Hao, Wenyu; Lin, Zheshuai; Yao, Jiyong; Wu, Yicheng

    2013-09-01

    A new ternary phosphidopolysilicate (IV), KSi2P3, has been synthesized by high temperature solid state reaction. The compound crystallizes in a new structure type in the monoclinic space group C2/c with a=10.1327(5) Å, b=10.1382(5) Å, c=21.1181(10) Å, β=96.88(0)°, and Z=8. In the structure, all SiP4 tetrahedra are connected with each other by corner-sharing P atoms to form [P3]-∞2 layers, which are stacked along c direction and separated by K+ cations. The two-dimensional structure of KSi2P3 contrasts with those of the two known members in the ternary A/Si/P (A=alkali metal) system, namely Na5SiP3 (zero-dimensional) and K2SiP2 (one-dimensional), which contains less amount of Si. The band gap deduced from UV-vis-IR diffuse reflectance spectrum is 1.72 eV.

  19. Affective Priming with Associatively Acquired Valence

    ERIC Educational Resources Information Center

    Aguado, Luis; Pierna, Manuel; Saugar, Cristina

    2005-01-01

    Three experiments explored the effect of affectively congruent or incongruent primes on evaluation responses to positive or negative valenced targets (the "affective priming" effect). Experiment 1 replicated the basic affective priming effect with Spanish nouns: reaction time for evaluative responses (pleasant/unpleasant) were slower on…

  20. Valence of neptunium in intermetallic compounds

    SciTech Connect

    Spitsyn, V.I.; Ionova, G.V.

    1987-07-01

    The authors use Moessbauer spectroscopy and quantum chemical calculations to determine the valence and electronic structure of neptunium in its intermetallic forms with a variety of alloys. The isomeric shifts are measured on Np 237 nuclei. Quantum electronic properties and population density estimates are calculated within the framework of the Hartree-Fock-Slater method.

  1. Band alignment of ZnO/multilayer MoS2 interface determined by x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Xinke; Zhang, Yuan; Liu, Qiang; He, Jiazhu; Chen, Le; Li, Kuilong; Jia, Fang; Zeng, Yuxiang; Lu, Youming; Yu, Wenjie; Zhu, Deliang; Liu, Wenjun; Wu, Jing; He, Zhubing; Ang, Kah-Wee

    2016-08-01

    The energy band alignment between ZnO and multilayer (ML)-MoS2 was characterized using high-resolution x-ray photoelectron spectroscopy. The ZnO film was deposited using an atomic layer deposition tool, and ML-MoS2 was grown by chemical vapor deposition. A valence band offset (VBO) of 3.32 eV and a conduction band offset (CBO) of 1.12 eV were obtained for the ZnO/ML-MoS2 interface without any treatment. With CHF3 plasma treatment, a VBO and a CBO across the ZnO/ML-MoS2 interface were found to be 3.54 eV and 1.34 eV, respectively. With the CHF3 plasma treatment, the band alignment of the ZnO/ML-MoS2 interface has been changed from type II or staggered band alignment to type III or misaligned one, which favors the electron-hole pair separation. The band alignment difference is believed to be dominated by the down-shift in the core level of Zn 2p or the interface dipoles, which is caused by the interfacial layer rich in F.

  2. Self-trapped exciton and core-valence luminescence in BaF{sub 2} nanoparticles

    SciTech Connect

    Vistovskyy, V. V. Zhyshkovych, A. V.; Chornodolskyy, Ya. M.; Voloshinovskii, A. S.; Myagkota, O. S.; Gloskovskii, A.; Gektin, A. V.; Vasil'ev, A. N.; Rodnyi, P. A.

    2013-11-21

    The influence of the BaF{sub 2} nanoparticle size on the intensity of the self-trapped exciton luminescence and the radiative core-valence transitions is studied by the luminescence spectroscopy methods using synchrotron radiation. The decrease of the self-trapped exciton emission intensity at energies of exciting photons in the range of optical exciton creation (hν ≤ E{sub g}) is less sensitive to the reduction of the nanoparticle sizes than in the case of band-to-band excitation, where excitons are formed by the recombination way. The intensity of the core-valence luminescence shows considerably weaker dependence on the nanoparticle sizes in comparison with the intensity of self-trapped exciton luminescence. The revealed regularities are explained by considering the relationship between nanoparticle size and photoelectron or photohole thermalization length as well as the size of electronic excitations.

  3. Optical properties of Eu{sup 2+}/Eu{sup 3+} mixed valence, silicon nitride based materials

    SciTech Connect

    Kate, Otmar M. ten; Vranken, Thomas; Kolk, Erik van der; Jansen, Antonius P.J.; Hintzen, Hubertus T.

    2014-05-01

    Eu{sub 2}SiN{sub 3}, a mixed valence europium nitridosilicate, has been prepared via solid-state reaction synthesis and its oxidation behavior and optical properties have been determined. Furthermore, the stability of several isostructural compounds of the type M{sup 2+}L{sup 3+}SiN{sub 3} has been predicted by using the density functional theory calculations, and verified by the actual synthesis of CaLaSiN{sub 3}, CaEuSiN{sub 3} and EuLaSiN{sub 3}. The band gap of CaLaSiN{sub 3} was found around 3.2 eV giving the material its yellow color. Eu{sub 2}SiN{sub 3} on the other hand is black due to a combination of the 4f–5d absorption band of Eu{sup 2+} and the charge transfer band of Eu{sup 3+}. Thermogravimetric analysis and Raman spectroscopic study of Eu{sub 2}SiN{sub 3} revealed that oxidation of this compound in dry air takes place via a nitrogen retention complex. - Graphical abstract: Energy level scheme of Eu{sub 2}SiN{sub 3} showing the occupied N{sup 3−} 2p band (blue rectangle), unoccupied Eu{sup 2+} 5d band (white rectangle), occupied Eu{sup 2+} 4f ground states (filled red circles) and unoccupied Eu{sup 2+} ground states (open red circles). - Highlights: • Density functional theory calculations on the stability of M{sup 2+}L{sup 3+}SiN{sub 3} compounds. • Solid-state reaction synthesis of Eu{sub 2}SiN{sub 3}, CaLaSiN{sub 3}, EuLaSiN{sub 3} and CaEuSiN{sub 3}. • Determination of the Eu{sup 2+} 4f–5d and Eu{sup 3+} CT transitions in M{sup 2+}L{sup 3+}SiN{sub 3} compounds. • Oxidation of Eu{sub 2}SiN{sub 3} in dry air takes place via a nitrogen retention complex.

  4. Band-structure analysis from photoreflectance spectroscopy in (Ga,Mn)As

    SciTech Connect

    Yastrubchak, Oksana; Gluba, Lukasz; Zuk, Jerzy; Wosinski, Tadeusz; Andrearczyk, Tomasz; Domagala, Jaroslaw Z.; Sadowski, Janusz

    2013-12-04

    Modulation photoreflectance spectroscopy has been applied to study the band-structure evolution in (Ga,Mn)As epitaxial layers with increasing Mn content. Structural and magnetic properties of the layers were characterized with high-resolution X-ray diffractometry and SQUID magnetometery, respectively. The revealed results of decrease in the band-gap-transition energy in the (Ga,Mn)As layers with increasing Mn content are interpreted in terms of a disordered valence band, extended within the band gap, formed, in highly Mn-doped (Ga,Mn)As, as a result of merging the Mn-related impurity band with the host GaAs valence band.

  5. XPEEM valence state imaging of mineral micro-intergrowths with a spatial resolution of 100nm

    NASA Astrophysics Data System (ADS)

    Smith, A. D.; Schofield, P. F.; Scholl, A.; Pattrick, R. A. D.; Bridges, J. C.

    2003-03-01

    The crystal chemistry and textural relationships of minerals hold a vast amount of information relating to the formation, history and stability of natural materials. The application of soft X-ray spectroscopy to mineralogical material has revealed that 2p (L{2,3}) spectra provide a sensitive fingerprint of the electronic states of 3d metals. In bulk powdered samples much of the textural and microstructural information is lost, but the area-selectivity capability of X-ray Photo-Emission Electron Microscopy (XPEEM) provides the ability to obtain valence state information from mineral intergrowths with a submicron spatial resolution. Using the state-of-the-art PEEM2 facility on beamline 7.3.1.1 at the Advanced Light Source, Berkeley, USA, a range of minerals, mineral intergrowths and mineralogical textures have been studied for a broad suite of geological, planetary and environmental science materials. High-quality, multi-element valence images have been obtained showing the distribution/variation of the metal valence states across single grains or mineral intergrowths/textures at the l00 nm scale and quantitative valence state ratios can be obtained from areas of 0.01 μ m^2.

  6. Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

    PubMed Central

    Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

    2015-01-01

    The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

  7. Distinct cerebellar lobules process arousal, valence and their interaction in parallel following a temporal hierarchy.

    PubMed

    Styliadis, Charis; Ioannides, Andreas A; Bamidis, Panagiotis D; Papadelis, Christos

    2015-04-15

    The cerebellum participates in emotion-related neural circuits formed by different cortical and subcortical areas, which sub-serve arousal and valence. Recent neuroimaging studies have shown a functional specificity of cerebellar lobules in the processing of emotional stimuli. However, little is known about the temporal component of this process. The goal of the current study is to assess the spatiotemporal profile of neural responses within the cerebellum during the processing of arousal and valence. We hypothesized that the excitation and timing of distinct cerebellar lobules is influenced by the emotional content of the stimuli. By using magnetoencephalography, we recorded magnetic fields from twelve healthy human individuals while passively viewing affective pictures rated along arousal and valence. By using a beamformer, we localized gamma-band activity in the cerebellum across time and we related the foci of activity to the anatomical organization of the cerebellum. Successive cerebellar activations were observed within distinct lobules starting ~160ms after the stimuli onset. Arousal was processed within both vermal (VI and VIIIa) and hemispheric (left Crus II) lobules. Valence (left VI) and its interaction (left V and left Crus I) with arousal were processed only within hemispheric lobules. Arousal processing was identified first at early latencies (160ms) and was long-lived (until 980ms). In contrast, the processing of valence and its interaction to arousal was short lived at later stages (420-530ms and 570-640ms respectively). Our findings provide for the first time evidence that distinct cerebellar lobules process arousal, valence, and their interaction in a parallel yet temporally hierarchical manner determined by the emotional content of the stimuli. PMID:25665964

  8. Resonant valence bond states in zinc vacancies induce the ferromagnetism of ZnO

    NASA Astrophysics Data System (ADS)

    Sun, Shih-Jye

    2016-05-01

    A theoretical model was proposed to investigate the mechanism of ferromagnetism in ZnO as well as to simulate the experimental result that the ferromagnetism can be enhanced by UV irradiation as UV photon energy is equivalent to the band gap. In the model, the spin moments arise from the trapped electrons in oxygen vacancy states and coexist with the itinerant electrons which reside in zinc vacancy states and fall into resonant valence bond states. Charge exchange between the conduction band of ZnO and both vacancy states makes electrons on both vacancy states delocalized and results in a decrease of the ferromagnetism as well.

  9. Pion valence-quark parton distribution function

    NASA Astrophysics Data System (ADS)

    Chang, Lei; Thomas, Anthony W.

    2015-10-01

    Within the Dyson-Schwinger equation formulation of QCD, a rainbow ladder truncation is used to calculate the pion valence-quark distribution function (PDF). The gap equation is renormalized at a typical hadronic scale, of order 0.5 GeV, which is also set as the default initial scale for the pion PDF. We implement a corrected leading-order expression for the PDF which ensures that the valence-quarks carry all of the pion's light-front momentum at the initial scale. The scaling behavior of the pion PDF at a typical partonic scale of order 5.2 GeV is found to be (1 - x) ν, with ν ≃ 1.6, as x approaches one.

  10. Valence force field analysis of tetracyanoethylene

    NASA Astrophysics Data System (ADS)

    Michaelian, K. H.; Rieckhoff, K. E.; Voigt, E. M.

    1982-09-01

    A valence force field calculation for the out-of-plane modes of tetracyanoethylene is reported, which makes possible a straightforward assignment of the low-frequency vibrations, including several in-plane modes which previously could not be assigned with certainty. The present set of assignments is consistent with observed vibrational spectra, both for uncomplexed and for complexed tetracyanoethylene, and, for the planar vibrations, is supported by recently published force constant calculations.

  11. Photoswitchable stable charge-distributed states in a new cobalt complex exhibiting photo-induced valence tautomerism.

    PubMed

    Slota, Michael; Blankenhorn, Marian; Heintze, Eric; Vu, Minh; Hübner, Ralph; Bogani, Lapo

    2015-01-01

    We report the synthesis and magnetic and photomagnetic behaviour of a novel valence tautomeric cobalt complex, [Co(3,5-dbbq)2(μ-bpym)] (1) (3,5-dbbq = 3,5-di-tert-butyl-1,2-benzoquinone and μ-bpym = 2,2'-bipyrimidine). The synthesis is performed by reacting Co2(CO)8 and μ-bpym in the presence of the ligand 3,5-dbbq in a mixed solvent under inert atmosphere. The magnetic behavior clearly shows the presence of electron transfer from the catecholate ligand to the cobalt center, producing valence tautomers of [Co(II)(SQ)2] with a transition temperature (T1/2) of 215 K. Photomagnetic studies, performed via both SQUID magnetometry and X-band electron paramagnetic resonance, show the clear presence of photoinduced valence tautomerism, at temperatures considerably higher than previous systems. A metastable charge distribution is observed, strengthening previous investigations on the character of mixed valence ligands. Entropy-driven valence tautomeric interconversion is observed, and drives the transition to the most stable charge distribution. The complex has the ability to coordinate and can be used as a photoswitchable building block, with the photomagnetic characterisation evidencing a metastable state lifetime of the photo-induced valence tautomeric process of ca. 2.9 × 10(4) s below 20 K. The observed yields are higher than ones in similar systems, showing that tiny changes in the molecular structures may have a huge impact. PMID:26470791

  12. Photoswitchable stable charge-distributed states in a new cobalt complex exhibiting photo-induced valence tautomerism.

    PubMed

    Slota, Michael; Blankenhorn, Marian; Heintze, Eric; Vu, Minh; Hübner, Ralph; Bogani, Lapo

    2015-01-01

    We report the synthesis and magnetic and photomagnetic behaviour of a novel valence tautomeric cobalt complex, [Co(3,5-dbbq)2(μ-bpym)] (1) (3,5-dbbq = 3,5-di-tert-butyl-1,2-benzoquinone and μ-bpym = 2,2'-bipyrimidine). The synthesis is performed by reacting Co2(CO)8 and μ-bpym in the presence of the ligand 3,5-dbbq in a mixed solvent under inert atmosphere. The magnetic behavior clearly shows the presence of electron transfer from the catecholate ligand to the cobalt center, producing valence tautomers of [Co(II)(SQ)2] with a transition temperature (T1/2) of 215 K. Photomagnetic studies, performed via both SQUID magnetometry and X-band electron paramagnetic resonance, show the clear presence of photoinduced valence tautomerism, at temperatures considerably higher than previous systems. A metastable charge distribution is observed, strengthening previous investigations on the character of mixed valence ligands. Entropy-driven valence tautomeric interconversion is observed, and drives the transition to the most stable charge distribution. The complex has the ability to coordinate and can be used as a photoswitchable building block, with the photomagnetic characterisation evidencing a metastable state lifetime of the photo-induced valence tautomeric process of ca. 2.9 × 10(4) s below 20 K. The observed yields are higher than ones in similar systems, showing that tiny changes in the molecular structures may have a huge impact.

  13. A single-source precursor approach to solution processed indium arsenide thin films† †Electronic supplementary information (ESI) available: Table listing selected bond lengths and angles for InAs precursor complex. Cross-sectional SEM of InAs thin film. XPS depth profile spectra of InAs thin film. Valence band XPS of InAs thin film and standard. CCDC 1477895. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6tc02293f Click here for additional data file. Click here for additional data file.

    PubMed Central

    Marchand, Peter; Sathasivam, Sanjayan; Williamson, Benjamin A. D.; Pugh, David; Bawaked, Salem M.; Basahel, Sulaiman N.; Obaid, Abdullah Y.; Scanlon, David O.; Parkin, Ivan P.

    2016-01-01

    This paper reports the synthesis of the novel single-source precursor, [{(MeInAstBu)3}2(Me2InAs(tBu)H)2] and the subsequent first report of aerosol-assisted chemical vapour deposition of InAs thin films. Owing to the use of the single-source precursor, highly crystalline and stoichiometric films were grown at a relatively low deposition temperature of 450 °C. Core level XPS depth profiling studies showed some partial oxidation of the film surface, however this was self-limiting and disappeared on etch profiles. Valence band XPS analysis matched well with the simulated density of state spectrum. Hall effect measurements performed on the films showed that the films were n-type with promising resistivity (3.6 × 10–3 Ω cm) and carrier mobility (410 cm2 V–1 s–1) values despite growth on amorphous glass substrates. PMID:27774150

  14. Human Amygdala Represents the Complete Spectrum of Subjective Valence

    PubMed Central

    Jin, Jingwen; Zelano, Christina; Gottfried, Jay A.

    2015-01-01

    Although the amygdala is a major locus for hedonic processing, how it encodes valence information is poorly understood. Given the hedonic potency of odor stimuli and the amygdala's anatomical proximity to the peripheral olfactory system, we combined high-resolution fMRI with pattern-based multivariate techniques to examine how valence information is encoded in the amygdala. Ten human subjects underwent fMRI scanning while smelling 9 odorants that systematically varied in perceived valence. Representational similarity analyses showed that amygdala codes the entire dimension of valence, ranging from pleasantness to unpleasantness. This unidimensional representation significantly correlated with self-reported valence ratings but not with intensity ratings. Furthermore, within-trial valence representations evolved over time, prioritizing earlier differentiation of unpleasant stimuli. Together, these findings underscore the idea that both spatial and temporal features uniquely encode pleasant and unpleasant odor valence in the amygdala. The availability of a unidimensional valence code in the amygdala, distributed in both space and time, would create greater flexibility in determining the pleasantness or unpleasantness of stimuli, providing a mechanism by which expectation, context, attention, and learning could influence affective boundaries for guiding behavior. SIGNIFICANCE STATEMENT Our findings elucidate the mechanisms of affective processing in the amygdala by demonstrating that this brain region represents the entire valence dimension from pleasant to unpleasant. An important implication of this unidimensional valence code is that pleasant and unpleasant valence cannot coexist in the amygdale because overlap of fMRI ensemble patterns for these two valence extremes obscures their unique content. This functional architecture, whereby subjective valence maps onto a pattern continuum between pleasant and unpleasant poles, offers a robust mechanism by which context

  15. Intermediate Band Solar Cell with Extreme Broadband Spectrum Quantum Efficiency

    NASA Astrophysics Data System (ADS)

    Datas, A.; López, E.; Ramiro, I.; Antolín, E.; Martí, A.; Luque, A.; Tamaki, R.; Shoji, Y.; Sogabe, T.; Okada, Y.

    2015-04-01

    We report, for the first time, about an intermediate band solar cell implemented with InAs/AlGaAs quantum dots whose photoresponse expands from 250 to ˜6000 nm . To our knowledge, this is the broadest quantum efficiency reported to date for a solar cell and demonstrates that the intermediate band solar cell is capable of producing photocurrent when illuminated with photons whose energy equals the energy of the lowest band gap. We show experimental evidences indicating that this result is in agreement with the theory of the intermediate band solar cell, according to which the generation recombination between the intermediate band and the valence band makes this photocurrent detectable.

  16. Disentangling the impacts of outcome valence and outcome frequency on the post-error slowing.

    PubMed

    Wang, Lijun; Tang, Dandan; Zhao, Yuanfang; Hitchman, Glenn; Wu, Shanshan; Tan, Jinfeng; Chen, Antao

    2015-01-01

    Post-error slowing (PES) reflects efficient outcome monitoring, manifested as slower reaction time after errors. Cognitive control account assumes that PES depends on error information, whereas orienting account posits that it depends on error frequency. This raises the question how the outcome valence and outcome frequency separably influence the generation of PES. To address this issue, we varied the probability of observation errors (50/50 and 20/80, correct/error) the "partner" committed by employing an observation-execution task and investigated the corresponding behavioral and neural effects. On each trial, participants first viewed the outcome of a flanker-run that was supposedly performed by a 'partner', and then performed a flanker-run themselves afterwards. We observed PES in the two error rate conditions. However, electroencephalographic data suggested error-related potentials (oERN and oPe) and rhythmic oscillation associated with attentional process (alpha band) were respectively sensitive to outcome valence and outcome frequency. Importantly, oERN amplitude was positively correlated with PES. Taken together, these findings support the assumption of the cognitive control account, suggesting that outcome valence and outcome frequency are both involved in PES. Moreover, the generation of PES is indexed by oERN, whereas the modulation of PES size could be reflected on the alpha band.

  17. Disentangling the impacts of outcome valence and outcome frequency on the post-error slowing

    PubMed Central

    Wang, Lijun; Tang, Dandan; Zhao, Yuanfang; Hitchman, Glenn; Wu, Shanshan; Tan, Jinfeng; Chen, Antao

    2015-01-01

    Post-error slowing (PES) reflects efficient outcome monitoring, manifested as slower reaction time after errors. Cognitive control account assumes that PES depends on error information, whereas orienting account posits that it depends on error frequency. This raises the question how the outcome valence and outcome frequency separably influence the generation of PES. To address this issue, we varied the probability of observation errors (50/50 and 20/80, correct/error) the “partner” committed by employing an observation-execution task and investigated the corresponding behavioral and neural effects. On each trial, participants first viewed the outcome of a flanker-run that was supposedly performed by a ‘partner’, and then performed a flanker-run themselves afterwards. We observed PES in the two error rate conditions. However, electroencephalographic data suggested error-related potentials (oERN and oPe) and rhythmic oscillation associated with attentional process (alpha band) were respectively sensitive to outcome valence and outcome frequency. Importantly, oERN amplitude was positively correlated with PES. Taken together, these findings support the assumption of the cognitive control account, suggesting that outcome valence and outcome frequency are both involved in PES. Moreover, the generation of PES is indexed by oERN, whereas the modulation of PES size could be reflected on the alpha band. PMID:25732237

  18. Laser-excited luminescence and absorption study of mixed valence for K 2Pt(CN) 4—K 2Pt(CN) 6 crystals

    NASA Astrophysics Data System (ADS)

    Kasi Viswanath, A.; Smith, Wayne L.; Patterson, H.

    1982-04-01

    Crystals of K 2Pt(CN) 6 doped with Pt(CN) 2-4 show an absorption band at 337 nm which is assigned as a mixed-valence (MV) transition from Pt (II) to Pt(IV). From a Hush model analysis, the absorption band is interpreted to be class II in the Day—Robin scheme. When the MV band is laser excited at 337 nm, emmision is observed from Pt(CN) 2-4 clusters.

  19. The variational subspace valence bond method

    SciTech Connect

    Fletcher, Graham D.

    2015-04-07

    The variational subspace valence bond (VSVB) method based on overlapping orbitals is introduced. VSVB provides variational support against collapse for the optimization of overlapping linear combinations of atomic orbitals (OLCAOs) using modified orbital expansions, without recourse to orthogonalization. OLCAO have the advantage of being naturally localized, chemically intuitive (to individually model bonds and lone pairs, for example), and transferrable between different molecular systems. Such features are exploited to avoid key computational bottlenecks. Since the OLCAO can be doubly occupied, VSVB can access very large problems, and calculations on systems with several hundred atoms are presented.

  20. Strongly correlated valence electrons and core-level chemical bonding of Lithium at terapascal pressures

    NASA Astrophysics Data System (ADS)

    Hu, Anguang; Zhang, Fan

    2015-03-01

    As the simplest pure metal, lithium exhibits some novel properties on electrical conductivity and crystal structures under high pressure. All-electron density functional theory simulations, recently developed by using the linear combination of localized Slater atomic orbitals, revealed that the bandwidth of its valence bands remains almost unchanged within about 3.5 eV even up to a terapascal pressure range. This indicates that the development from delocalized to strongly correlated electronic systems takes place under compression, resulting in metal-semiconductor and superconductivity transitions together with a sequence of new high-pressure crystal phases, discovered experimentally. In contrast to the valence bands, the core-level bands become broadening up to about 10 eV at terapascal pressures. It means the transformation from chemical non-bonding to bonding for core electrons. Thus, dense lithium under compression can be characterized as core-level chemical bonding and a completely new class of strongly correlated materials with narrow bands filled in s-electron shells only.

  1. Valence-electron spectral change and charge transfer mechanism of CaSi 2 during CaSi 2H 2O reaction

    NASA Astrophysics Data System (ADS)

    Abe, S.; Nakayama, H.; Nishino, T.; Iida, S.

    1997-04-01

    The changes in the valence electron states of CaSi 2 during the chemical reaction with H 2O have been investigated by Auger valence electron spectroscopy (AVES). The drastic changes in the valence electron spectra of 3s and 3p states, which are caused by the oxidization of the Si atoms in CaSi 2, were observed in Si[2s, 2p, V] spectra for CaSi 2 after the reaction. In particular, the Si[2s, 2p, V] spectra of CaSi 2 samples reacted with H 2O at 60 or 80°C for 3 h were almost similar to that of SiO 2. The peak shift of Ca[2p, 3p, 3p] Auger transition toward the lower energy side has been observed, suggesting the formation of bonds between Ca 3p and O orbitals. New peaks due to CaO or CaOH bonds also appeared in the valence electron region of Ca[2p, 3p, V] Auger transition. The charge transfer and the chemical-bond formation can be well demonstrated by AVES during the CaSi 2H 2O reaction.

  2. Energies and E1, M1, E2, and M2 transition rates for states of the 2s{sup 2}2p{sup 3}, 2s2p{sup 4}, and 2p{sup 5} configurations in nitrogen-like ions between F III and Kr XXX

    SciTech Connect

    Rynkun, P.; Jönsson, P.; Gaigalas, G.; Froese Fischer, C.

    2014-03-15

    Based on relativistic wavefunctions from multiconfiguration Dirac–Hartree–Fock and configuration interaction calculations, E1, M1, E2, and M2 transition rates, weighted oscillator strengths, and lifetimes are evaluated for the states of the (1s{sup 2})2s{sup 2}2p{sup 3},2s2p{sup 4}, and 2p{sup 5} configurations in all nitrogen-like ions between F III and Kr XXX. The wavefunction expansions include valence, core–valence, and core–core correlation effects through single–double multireference expansions to increasing sets of active orbitals. The computed energies agree very well with experimental values, with differences of only 300–600 cm{sup −1} for the majority of the levels and ions in the sequence. Computed transitions rates are in close agreement with available data from MCHF-BP calculations by Tachiev and Froese Fischer [G.I. Tachiev, C. Froese Fischer, A and A 385 (2002) 716].

  3. Representation of perceived sound valence in the human brain.

    PubMed

    Viinikainen, Mikko; Kätsyri, Jari; Sams, Mikko

    2012-10-01

    Perceived emotional valence of sensory stimuli influences their processing in various cortical and subcortical structures. Recent evidence suggests that negative and positive valences are processed separately, not along a single linear continuum. Here, we examined how brain is activated when subjects are listening to auditory stimuli varying parametrically in perceived valence (very unpleasant-neutral-very pleasant). Seventeen healthy volunteers were scanned in 3 Tesla while listening to International Affective Digital Sounds (IADS-2) in a block design paradigm. We found a strong quadratic U-shaped relationship between valence and blood oxygen level dependent (BOLD) signal strength in the medial prefrontal cortex, auditory cortex, and amygdala. Signals were the weakest for neutral stimuli and increased progressively for more unpleasant or pleasant stimuli. The results strengthen the view that valence is a crucial factor in neural processing of emotions. An alternative explanation is salience, which increases with both negative and positive valences.

  4. Anticipation selectively enhances interference exerted by pictures of negative valence.

    PubMed

    Kleinsorge, Thomas

    2009-01-01

    Recent evidence suggests that anticipation of negatively valenced pictures strongly increases interference exerted by the actual presentation of these pictures, while anticipation of positively valenced pictures leaves the impact of the actual presentation of positive pictures unaffected. However, there is some ambiguity as to whether anticipation of negative valence generally increases the impact of all emotional stimuli, or whether the effect of anticipation is specific for stimuli of negative valence. In the present experiments, different anticipation conditions were contrasted that differed with respect to the specificity of the information on which anticipations could be based. The data show that all anticipation conditions that entailed the possibility of the presentation of unpleasant stimuli selectively enhanced the impact of negatively valenced stimuli without affecting the impact of positively valenced stimuli.

  5. Kinetics of an oxygen - iodine active medium with iodine atoms optically pumped on the 2P1/2 - 2P3/2 transition

    NASA Astrophysics Data System (ADS)

    Zagidullin, M. V.; Malyshev, M. S.; Azyazov, V. N.

    2015-08-01

    The kinetics of the processes occurring in an O2 - I2 - He - H2O gas flow in which photodissociation of molecular iodine at a wavelength close to 500 nm and excitation of atomic iodine on the 2P1/2 - 2P3/2 transition by narrow-band radiation near 1315 nm are implemented successively has been analysed. It is shown that implementation of these processes allows one to form an oxygen - iodine medium with a high degree of dissociation of molecular iodine and a relative content of singlet oxygen O2(a1Δ) exceeding 10%. Having formed a supersonic gas flow with a temperature ~100 K from this medium, one can reach a small-signal gain of about 10-2 cm-1 on the 2P1/2 - 2P3/2 transition in iodine atoms. The specific power per unit flow cross section in the oxygen - iodine laser with this active medium may reach ~100 W cm-2.

  6. Band offsets of TiZnSnO/Si heterojunction determined by x-ray photoelectron spectroscopy

    SciTech Connect

    Sun, R. J.; Jiang, Q. J.; Yan, W. C.; Feng, L. S.; Lu, B.; Ye, Z. Z.; Li, X. F.; Li, X. D.; Lu, J. G.

    2014-09-28

    X-ray photoelectron spectroscopy (XPS) was utilized to measure the valence band offset (ΔE{sub V}) of the TiZnSnO (TZTO)/Si heterojunction. TZTO films were deposited on Si (100) substrates using magnetron sputtering at room temperature. By using the Zn 2p{sub 3/2} and Sn 3d{sub 5/2} energy levels as references, the value of ΔE{sub V} was calculated to be 2.69 ± 0.1 eV. Combining with the experimental optical energy band gap of 3.98 eV for TZTO extracted from the UV-vis transmittance spectrum, the conduction band offset (ΔE{sub C}) was deduced to be 0.17 ± 0.1 eV at the interface. Hence, the energy band alignment of the heterojunction was determined accurately, showing a type-I form. This will be beneficial for the design and application of TZTO/Si hybrid devices.

  7. Band offset studies in pulse laser deposited Zn{sub 1−x}Cd{sub x}O/ZnO hetero-junctions

    SciTech Connect

    Devi, Vanita; Kumar, Ravindra; Joshi, B. C.; Kumar, Manish; Choudhary, R. J.; Phase, D. M.

    2015-06-14

    The valence and conduction band offsets of Zn{sub 1−x}Cd{sub x}O/ZnO hetero-junctions deposited by pulsed laser deposition technique were estimated by X-ray photoelectron, valence band, and UV-visible spectroscopy. Type-II band alignment (staggered gap) with ratios of conduction band to valence band offsets (ΔE{sub C}/ΔE{sub V}) was found to be 0.77 and 0.59 for Zn{sub 0.95}Cd{sub 0.05}O/ZnO and Zn{sub 0.90}Cd{sub 0.10}O/ZnO hetero-structures, respectively, which can be used in longer wavelength regime optoelectronic devices. The higher value of valence band offset as compared to conduction band offset suggests that the transport at interface is mainly due to electrons.

  8. Attosecond band-gap dynamics in silicon

    NASA Astrophysics Data System (ADS)

    Schultze, Martin; Ramasesha, Krupa; Pemmaraju, C. D.; Sato, S. A.; Whitmore, D.; Gandman, A.; Prell, James S.; Borja, L. J.; Prendergast, D.; Yabana, K.; Neumark, Daniel M.; Leone, Stephen R.

    2014-12-01

    Electron transfer from valence to conduction band states in semiconductors is the basis of modern electronics. Here, attosecond extreme ultraviolet (XUV) spectroscopy is used to resolve this process in silicon in real time. Electrons injected into the conduction band by few-cycle laser pulses alter the silicon XUV absorption spectrum in sharp steps synchronized with the laser electric field oscillations. The observed ~450-attosecond step rise time provides an upper limit for the carrier-induced band-gap reduction and the electron-electron scattering time in the conduction band. This electronic response is separated from the subsequent band-gap modifications due to lattice motion, which occurs on a time scale of 60 ± 10 femtoseconds, characteristic of the fastest optical phonon. Quantum dynamical simulations interpret the carrier injection step as light-field-induced electron tunneling.

  9. Electronic Structure and Bonding in Co-Based Single and Mixed Valence Oxides: A Quantum Chemical Perspective.

    PubMed

    Singh, Vijay; Major, Dan Thomas

    2016-04-01

    The mixed valence cobalt oxide, Co3O4, is a potential candidate as a photovoltaic (PV) material, which also exhibits intriguing chemical and catalytic properties. Here, we present a comparative study of the electronic, magnetic, and chemical bonding properties of mixed valence Co3O4 (i.e., Co(2+/3+)) with the related single valence CoO (i.e., Co(2+)) and Co2O3 (i.e., Co(3+)) oxides using density functional theory (DFT). We have employed a range of theoretical methods, including pure DFT, DFT+U, and a range-separated exchange-correlation functional (HSE06). We compare the electronic structure and band gap of the oxide materials, with available photoemission spectroscopy and optical band gaps. Our calculations suggest that the bonding between Co(3+) and O(2-) ions in Co2O3 and Co3O4 and Co(2+) and O(2-) ions in CoO and Co3O4 are rather different. We find that Co2O3 and Co3O4 are weakly correlated materials, whereas CoO is a strongly correlated material. Furthermore, our computed one-electron energy level diagrams reveal that strong Co-O antibonding states are present at the top of the valence band for all the cobalt oxides, hinting at a defect tolerant capacity in these materials. These results, which give a detailed picture of the chemical bonding in related single and mixed valence cobalt oxides, may serve as a guide to enhance the PV or photoelectrochemical activity of Co3O4, by reducing its internal defect states or changing its electronic structure by doping or alloying with suitable elements. PMID:27010797

  10. Electronic Structure and Bonding in Co-Based Single and Mixed Valence Oxides: A Quantum Chemical Perspective.

    PubMed

    Singh, Vijay; Major, Dan Thomas

    2016-04-01

    The mixed valence cobalt oxide, Co3O4, is a potential candidate as a photovoltaic (PV) material, which also exhibits intriguing chemical and catalytic properties. Here, we present a comparative study of the electronic, magnetic, and chemical bonding properties of mixed valence Co3O4 (i.e., Co(2+/3+)) with the related single valence CoO (i.e., Co(2+)) and Co2O3 (i.e., Co(3+)) oxides using density functional theory (DFT). We have employed a range of theoretical methods, including pure DFT, DFT+U, and a range-separated exchange-correlation functional (HSE06). We compare the electronic structure and band gap of the oxide materials, with available photoemission spectroscopy and optical band gaps. Our calculations suggest that the bonding between Co(3+) and O(2-) ions in Co2O3 and Co3O4 and Co(2+) and O(2-) ions in CoO and Co3O4 are rather different. We find that Co2O3 and Co3O4 are weakly correlated materials, whereas CoO is a strongly correlated material. Furthermore, our computed one-electron energy level diagrams reveal that strong Co-O antibonding states are present at the top of the valence band for all the cobalt oxides, hinting at a defect tolerant capacity in these materials. These results, which give a detailed picture of the chemical bonding in related single and mixed valence cobalt oxides, may serve as a guide to enhance the PV or photoelectrochemical activity of Co3O4, by reducing its internal defect states or changing its electronic structure by doping or alloying with suitable elements.

  11. 2p-2p decay of {sup 8}C and isospin-allowed 2p decay of the isobaric-analog state in {sup 8}B

    SciTech Connect

    Charity, R. J.; Elson, J. M.; Manfredi, J.; Shane, R.; Sobotka, L. G.; Chajecki, Z.; Coupland, D.; Iwasaki, H.; Kilburn, M.; Lee, Jenny; Lynch, W. G.; Sanetullaev, A.; Tsang, M. B.; Winkelbauer, J.; Youngs, M.; Marley, S. T.; Shetty, D. V.; Wuosmaa, A. H.; Ghosh, T. K.

    2010-10-15

    {sup 8}C is found to decay to four protons and an {alpha} particle in two 2p emission steps. The correlations between the protons in the first step ({sup 8}C to {sup 6}Be) exhibit a significant enhancement in the region of the decay phase space where the two protons have small relative energy, a region sometimes called the diproton region. The decay of the isobaric analog of {sup 8}C in {sup 8}B is also found to decay by 2p emission. This is the first case of isospin-allowed 2p decay between isobaric analog states.

  12. Valence Effects in Reasoning About Evaluative Traits.

    PubMed

    Heyman, Gail D; Giles, Jessica W

    2004-01-01

    Reasoning about evaluative traits was investigated among a group of 7- and 8-year-olds (N = 34), a group of 11- to 13-year olds (N = 25), and a group of adults (N = 23) to determine whether their inferences would be sensitive to the valence of social and academic traits. Four aspects of trait-relevant beliefs were examined: (1) malleability, (2) stability over time, (3) origin in terms of nature versus nurture, and (4) an inference criterion that concerns how readily traits are inferred. Although there was evidence of an age-related decrease in the tendency to emphasize positive information, participants of all ages responded that positive traits are less malleable and more stable over time than negative traits, that the positive influences of biological and environmental factors are likely to override the negative influences, and that competence can be more readily inferred from positive outcomes than from negative outcomes. PMID:20953297

  13. Valence photoelectron spectroscopy of Gd silicides

    SciTech Connect

    Braicovich, L. ); Puppin, E.; Lindau, I. ); Iandelli, A.; Olcese, G.L.; Palenzona, A. )

    1990-02-15

    Gd{sub 3}Si{sub 5}, GdSi, and Gd{sub 5}Si{sub 3} were investigated with photoemission spectroscopy in the photon-energy range 40.8--149 eV by exploiting the energy dependence of the photoemission cross sections and the valence resonance at the crossing of the Gd 4{ital d}-4{ital f} threshold. The modification of the spectra versus photon energy, along with their stoichiometry dependence, show the relevance of covalent mixed Gd 5{ital d}--Si 3{ital sp} states in the formation of the chemical bond. In the region close to the Fermi level an increase of the {ital d} contribution is observed. These points are discussed in connection with the existing models of the silicide bond.

  14. Seniority Number in Valence Bond Theory.

    PubMed

    Chen, Zhenhua; Zhou, Chen; Wu, Wei

    2015-09-01

    In this work, a hierarchy of valence bond (VB) methods based on the concept of seniority number, defined as the number of singly occupied orbitals in a determinant or an orbital configuration, is proposed and applied to the studies of the potential energy curves (PECs) of H8, N2, and C2 molecules. It is found that the seniority-based VB expansion converges more rapidly toward the full configuration interaction (FCI) or complete active space self-consistent field (CASSCF) limit and produces more accurate PECs with smaller nonparallelity errors than its molecular orbital (MO) theory-based analogue. Test results reveal that the nonorthogonal orbital-based VB theory provides a reverse but more efficient way to truncate the complete active Hilbert space by seniority numbers.

  15. Valence Effects in Reasoning About Evaluative Traits

    PubMed Central

    Heyman, Gail D.; Giles, Jessica W.

    2010-01-01

    Reasoning about evaluative traits was investigated among a group of 7- and 8-year-olds (N = 34), a group of 11- to 13-year olds (N = 25), and a group of adults (N = 23) to determine whether their inferences would be sensitive to the valence of social and academic traits. Four aspects of trait-relevant beliefs were examined: (1) malleability, (2) stability over time, (3) origin in terms of nature versus nurture, and (4) an inference criterion that concerns how readily traits are inferred. Although there was evidence of an age-related decrease in the tendency to emphasize positive information, participants of all ages responded that positive traits are less malleable and more stable over time than negative traits, that the positive influences of biological and environmental factors are likely to override the negative influences, and that competence can be more readily inferred from positive outcomes than from negative outcomes. PMID:20953297

  16. Valence-driven electrical behavior of manganese-modified bismuth ferrite thin films

    SciTech Connect

    Wu Jiagang; Wang, John; Xiao Dingquan; Zhu Jianguo

    2011-06-15

    BiFe{sub 0.95}R{sub 0.05}O{sub 3} (Mn{sup 2+}, Mn{sup 3+}, and Mn{sup 4+}) thin films with (110) orientation were fabricated on SrRuO{sub 3}/Pt/TiO{sub 2}/SiO{sub 2}/Si(100) substrates via rf sputtering. With the increasing valence of Mn in BiFe{sub 0.95}R{sub 0.05}O{sub 3}, the concentration of Fe{sup 2+} increases, whereas the concentration of oxygen vacancies decreases. The electrical properties of BiFe{sub 0.95}R{sub 0.05}O{sub 3} are correlated with the valence of Mn. Their leakage current density is dependent on the concentration of oxygen vacancies caused by different valences of Mn. Their P-E loops become better with the increasing valence of Mn owing to a lower leakage current density in high electric field regions, and a large remanent polarization of 2P{sub r} {approx} 145.2 {mu}C/cm{sup 2} is obtained for the Mn{sup 4+}-doped film. For the Mn{sup 2+}-doped bismuth ferrite film, the space-charge-limited conduction and Schottky barrier dominate its leakage behavior under a negative electric field, the Ohmic conduction and Schottky barrier are involved in the leakage behavior under a positive electric field, and the interface-limited Fowler-Nordheim tunneling is their dominant mechanism in a high electric field region. In contrast, an Ohmic conduction dominates the leakage behavior of Mn{sup 3+}- and Mn{sup 4+}-doped films regardless of negative and positive directions or measurement temperatures.

  17. Relationship Between Iron Valence States of Serpentine in CM Chondrites and Their Aqueous Alteration Degrees

    NASA Technical Reports Server (NTRS)

    Mikouchi, T.; Zolensky, M.; Satake, W.; Le, L.

    2012-01-01

    The 0.6-0.7 micron absorption band observed for C-type asteroids is caused by the presence of Fe(3+) in phyllosilicates . Because Fe-bearing phyllosilicates, especially serpentine, are the most dominant product of aqueous alteration in the most abundant carbonaceous chondrites, CM chondrites, it is important to understand the crystal chemistry of serpentine in CM chondrites to better understand spectral features of C-type asteroids. CM chondrites show variable degrees of aqueous alteration, which should be related to iron valences in serpentine. It is predicted that the Fe(3+)/Sum of (Fe) ratios of serpentine in CM chondrites decrease as alteration proceeds by Si and Fe(3+) substitutions from end-member cronstedtite to serpentine, which should be apparent in the absorption intensity of the 0.6-0.7 micron band from C-type asteroids. In fact, the JAXA Hayabusa 2 target (C-type asteroid: 1993 JU3) exhibits heterogeneous spectral features (0.7 micron absorption band disappears by rotation). From these points of view, we have analyzed iron valences of matrix serpentine in several CM chondrites which span the entire observed range of aqueous alteration using Synchrotron Radiation X-ray Absorption Near-Edge Structure (SR-XANES). In this abstract we discuss the relationship between obtained Fe(3+)/Sum of (Fe) ratios and alteration degrees by adding new data to our previous studies

  18. Gastric Banding

    MedlinePlus

    ... gastric banding before deciding to have the procedure. Advertisements for a device or procedure may not include ... feeds Follow FDA on Twitter Follow FDA on Facebook View FDA videos on YouTube View FDA photos ...

  19. One-pot synthesis of hierarchical Ni2P/MoS2 hybrid electrocatalysts with enhanced activity for hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Liu, Yan-Ru; Hu, Wen-Hui; Li, Xiao; Dong, Bin; Shang, Xiao; Han, Guan-Qun; Chai, Yong-Ming; Liu, Yun-Qi; Liu, Chen-Guang

    2016-10-01

    A simple one-pot synthesis method has been used to fabricate novel Ni2P/MoS2 hybrid electrocatalysts for hydrogen evolution reaction (HER). Owing to the weak conductivity and layered structure of MoS2, Ni2P nanoparticles with excellent conductivity and activity have been doped into MoS2 for improving the electrocatalytic performances for HER. The structure and morphology of the as-prepared Ni2P/MoS2 hybrid nanostructures are characterized. XRD and XPS show the elemental composition and valence of Ni2P/MoS2. SEM and TEM confirm that the close interaction of the hybrid materials and good dispersion of Ni2P nanoparticles. The as-synthesized Ni2P/MoS2 hybrid electrocatalysts exhibit excellent activity with onset overpotential of 75 mV and Tafle slope of 76 mV dec-1, which are much better than that of pure MoS2. The enhanced stability of the as-prepared Ni2P/MoS2 for HER has also been observed. The improved performances for HER may be ascribed to the better conductivity and dispersion of MoS2 nanosheets in Ni2P/MoS2 hybrid electrocatalysts. The small size and good dispersion of Ni2P nanoparticles also contributed to the enhancement of HER activity. Compared with mechanically mixed MoS2 and Ni2P (Ni2P-MoS2), Ni2P/MoS2 hybrid materials demonstrate better electrochemical performances for HER, implying the existence of synergistic effect between Ni2P and MoS2 on HER activity.

  20. Valence bond distribution and correlation in bipartite Heisenberg antiferromagnets

    NASA Astrophysics Data System (ADS)

    Schwandt, David; Alet, Fabien; Oshikawa, Masaki

    2014-03-01

    Every singlet state of a quantum spin-1/2 system can be decomposed into a linear combination of valence bond basis states. The range of valence bonds within this linear combination as well as the correlations between them can reveal the nature of the singlet state and are key ingredients in variational calculations. In this work, we study the bipartite valence bond distributions and their correlations within the ground state of the Heisenberg antiferromagnet on bipartite lattices. In terms of field theory, this problem can be mapped to correlation functions near a boundary. In dimension d ≥2, a nonlinear σ model analysis reveals that at long distances the probability distribution P (r) of valence bond lengths decays as |r|-d-1 and that valence bonds are uncorrelated. By a bosonization analysis, we also obtain P(r )∝|r|-d-1 in d =1 despite the different mechanism. On the other hand, we find that correlations between valence bonds are important even at large distances in d =1, in stark contrast to d ≥2. The analytical results are confirmed by high-precision quantum Monte Carlo simulations in d =1, 2, and 3. We develop a single-projection loop variant of the valence bond projection algorithm, which is well designed to compute valence bond probabilities and for which we provide algorithmic details.

  1. On the Relationship between Value Orientation, Valences, and Academic Achievement

    ERIC Educational Resources Information Center

    Fries, Stefan; Schmid, Sebastian; Hofer, Manfred

    2007-01-01

    Value orientations are believed to influence learning in school. We assume that this influence is mediated by the valences attached to specific school subjects. In a questionnaire study (704 students from 36 classes) achievement and well-being value orientations were measured. Students also rated valence scales for the school subjects German and…

  2. Teaching Valence Shell Electron Pair Repulsion (VSEPR) Theory

    ERIC Educational Resources Information Center

    Talbot, Christopher; Neo, Choo Tong

    2013-01-01

    This "Science Note" looks at the way that the shapes of simple molecules can be explained in terms of the number of electron pairs in the valence shell of the central atom. This theory is formally known as valence shell electron pair repulsion (VSEPR) theory. The article explains the preferred shape of chlorine trifluoride (ClF3),…

  3. Structural, electronic structure, and band alignment properties at epitaxial NiO/Al2O3 heterojunction evaluated from synchrotron based X-ray techniques

    NASA Astrophysics Data System (ADS)

    Singh, S. D.; Nand, Mangla; Das, Arijeet; Ajimsha, R. S.; Upadhyay, Anuj; Kamparath, Rajiv; Shukla, D. K.; Mukherjee, C.; Misra, P.; Rai, S. K.; Sinha, A. K.; Jha, S. N.; Phase, D. M.; Ganguli, Tapas

    2016-04-01

    The valence band offset value of 2.3 ± 0.2 eV at epitaxial NiO/Al2O3 heterojunction is determined from photoelectron spectroscopy experiments. Pulsed laser deposited thin film of NiO on Al2O3 substrate is epitaxially grown along [111] direction with two domain structures, which are in-plane rotated by 60° with respect to each other. Observation of Pendellosung oscillations around Bragg peak confirms high interfacial and crystalline quality of NiO layer deposited on Al2O3 substrate. Surface related feature in Ni 2p3/2 core level spectra along with oxygen K-edge soft X-ray absorption spectroscopy results indicates that the initial growth of NiO on Al2O3 substrate is in the form of islands, which merge to form NiO layer for the larger coverage. The value of conduction band offset is also evaluated from the measured values of band gaps of NiO and Al2O3 layers. A type-I band alignment at NiO and Al2O3 heterojunction is also obtained. The determined values of band offsets can be useful in heterojunction based light emitting devices.

  4. Supporting Collaboration and Creativity Through Mobile P2P Computing

    NASA Astrophysics Data System (ADS)

    Wierzbicki, Adam; Datta, Anwitaman; Żaczek, Łukasz; Rzadca, Krzysztof

    Among many potential applications of mobile P2P systems, collaboration applications are among the most prominent. Examples of applications such as Groove (although not intended for mobile networks), collaboration tools for disaster recovery (the WORKPAD project), and Skype's collaboration extensions, all demonstrate the potential of P2P collaborative applications. Yet, the development of such applications for mobile P2P systems is still difficult because of the lack of middleware.

  5. EEG study on affective valence elicited by novel and familiar pictures using ERD/ERS and SVM-RFE.

    PubMed

    Hidalgo-Muñoz, A R; López, M M; Galvao-Carmona, A; Pereira, A T; Santos, I M; Vázquez-Marrufo, M; Tomé, A M

    2014-02-01

    EEG signals have been widely explored in emotional processing analyses, both in time and frequency domains. However, in such studies, habituation phenomenon is barely considered in the discrimination of different emotional responses. In this work, spectral features of the event-related potentials (ERPs) are studied by means of event-related desynchronization/synchronization computation. In order to determine the most relevant ERP features for distinguishing how positive and negative affective valences are processed within the brain, support vector machine-recursive feature elimination is employed. The proposed approach was applied for investigating in which way the familiarity of stimuli affects the affective valence processing as well as which frequency bands and scalp regions are more involved in this process. In a group composed of young adult women, results prove that parietooccipital region and theta band are especially involved in the processing of novelty in emotional stimuli. Furthermore, the proposed method has shown to perform successfully using a moderated number of trials.

  6. Valence photoionization of small alkaline earth atoms endohedrally confined in C60

    NASA Astrophysics Data System (ADS)

    Javani, M. H.; McCreary, M. R.; Patel, A. B.; Madjet, M. E.; Chakraborty, H. S.; Manson, S. T.

    2012-07-01

    A theoretical study of photoionization from the outermost orbitals of Be, Mg and Ca atoms endohedrally confined in C60 is reported. The fullerene ion core, comprised of sixty C4+, is smudged into a continuous jellium charge distribution, while the delocalized cloud of carbon valence electrons plus the encaged atom are treated in the time-dependent local density approximation (TDLDA). Systematic evolution of the mixing of outer atomic level with states of the C60 valence band is found along the sequence. This is found to influence the plasmonic enhancement of atomic photoionization at low energies and the geometry-revealing confinement oscillations at high energies in significantly different ways: (a) the extent of enhancement is mainly determined by the strength of atomic ionization, giving the strongest enhancement for Be even though Ca suffers the largest mixing. But (b) strongest collateral oscillations are uncovered for Ca, since, relative to Be and Mg, the mixing causes the highest photoelectron production at confining boundaries of Ca. The study paints the first comparative picture of the atomic valence photospectra for alkaline earth metallofullerenes in a dynamical many-electron framework.

  7. Architectural Representation of Valence in the Limbic System.

    PubMed

    Namburi, Praneeth; Al-Hasani, Ream; Calhoon, Gwendolyn G; Bruchas, Michael R; Tye, Kay M

    2016-06-01

    In order to thrive, animals must be able to recognize aversive and appetitive stimuli within the environment and subsequently initiate appropriate behavioral responses. This assignment of positive or negative valence to a stimulus is a key feature of emotional processing, the neural substrates of which have been a topic of study for several decades. Until recently, the result of this work has been the identification of specific brain regions, such as the basolateral amygdala (BLA) and nucleus accumbens (NAc), as important to valence encoding. The advent of modern tools in neuroscience has allowed further dissection of these regions to identify specific populations of neurons signaling the valence of environmental stimuli. In this review, we focus upon recent work examining the mechanisms of valence encoding, and provide a model for the systematic investigation of valence within anatomically-, genetically-, and functionally defined populations of neurons. PMID:26647973

  8. The importance of L1 ORF2p cryptic sequence to ORF2p fragment-mediated cytotoxicity.

    PubMed

    Christian, Claiborne M; Kines, Kristine J; Belancio, Victoria P

    2016-01-01

    The Long Interspersed Element 1 (LINE1 or L1) ORF2 protein (ORF2p) can cause DNA damage through the activity of its endonuclease domain (EN). The DNA double-strand breaks (DSB) introduced by the ORF2p EN have the potential to be mutagenic. Previously, our lab has shown that ORF2p fragments containing the EN domain could be expressed in mammalian cells and have variable cytotoxicity. Inclusion of the ORF2p sequence C-terminal to the EN domain in these fragments both reduced the cytotoxicity of these fragments and increased their presence in the nucleus as detected by Western blot analysis. Here, we identify the amino acids (aa 270-274) in the newly-identified ORF2p Cryptic region (Cry) that may be important to the subcellular localization and cytotoxic potential of these EN-containing ORF2p fragments. PMID:27583184

  9. Band alignment of type I at (100)ZnTe/PbSe interface

    NASA Astrophysics Data System (ADS)

    Konovalov, Igor; Emelianov, Vitali; Linke, Ralf

    2016-06-01

    A junction of lattice-matched cubic semiconductors ZnTe and PbSe results in a band alignment of type I so that the narrow band gap of PbSe is completely within the wider band gap of ZnTe. The valence band offset of 0.27 eV was found, representing a minor barrier during injection of holes from PbSe into ZnTe. Simple linear extrapolation of the valence band edge results in a smaller calculated band offset, but a more elaborate square root approximation was used instead, which accounts for parabolic bands. PbSe was electrodeposited at room temperature with and without Cd2+ ions in the electrolyte. Although Cd adsorbs at the surface, the presence of Cd in the electrolyte does not influence the band offset.

  10. Molecular Orbital Simulations of Metal 1s2p Resonant Inelastic X-ray Scattering.

    PubMed

    Guo, Meiyuan; Källman, Erik; Sørensen, Lasse Kragh; Delcey, Mickaël G; Pinjari, Rahul V; Lundberg, Marcus

    2016-07-28

    For first-row transition metals, high-resolution 3d electronic structure information can be obtained using resonant inelastic X-ray scattering (RIXS). In the hard X-ray region, a K pre-edge (1s→3d) excitation can be followed by monitoring the dipole-allowed Kα (2p→1s) or Kβ (3p→1s) emission, processes labeled 1s2p or 1s3p RIXS. Here the restricted active space (RAS) approach, which is a molecular orbital method, is used for the first time to study hard X-ray RIXS processes. This is achieved by including the two sets of core orbitals in different partitions of the active space. Transition intensities are calculated using both first- and second-order expansions of the wave vector, including, but not limited to, electric dipoles and quadrupoles. The accuracy of the approach is tested for 1s2p RIXS of iron hexacyanides [Fe(CN)6](n-) in ferrous and ferric oxidation states. RAS simulations accurately describe the multiplet structures and the role of 2p and 3d spin-orbit coupling on energies and selection rules. Compared to experiment, relative energies of the two [Fe(CN)6](3-) resonances deviate by 0.2 eV in both incident energy and energy transfer directions, and multiplet splittings in [Fe(CN)6](4-) are reproduced within 0.1 eV. These values are similar to what can be expected for valence excitations. The development opens the modeling of hard X-ray scattering processes for both solution catalysts and enzymatic systems. PMID:27398775

  11. Inelastic neutron scattering in valence fluctuation compounds

    SciTech Connect

    Jon M Lawrence

    2011-02-15

    The valence fluctuation compounds are rare earth intermetallics where hybridization of the nearly-localized 4f electrons with the conduction electrons leads to incorporation of the 4f's into the itinerant states. This hybridization slows down the conduction electrons and hence gives them a heavy effective mass, justifying application of the term 'heavy Fermion' (HF) to these materials. During the project period, we grew large single crystals of several such compounds and measured their properties using both standard thermodynamic probes and state-of-the-art inelastic neutron scattering. We obtained three main results. For the intermediate valence compounds CePd{sub 3} and YbAl{sub 3}, we showed that the scattering of neutrons by the fluctuations of the 4f magnetic moment does not have the momentum dependence expected for the itinerant heavy mass state; rather, the scattering is more typical of a localized spin fluctuation. We believe that incoherent scattering localizes the excitation. For the heavy Fermion compound Ce(Ni{sub 0.935}Pd{sub 0.065}){sub 2}Ge{sub 2}, which sits at a T = 0 critical point for transformation into an antiferromagnetic (AF) phase, we showed that the scattering from the AF fluctuations does not exhibit any of the divergences that are expected at a phase transition. We speculate that alloy disorder profoundly suppresses the growth of the fluctuating AF regions, leading to short range clusters rather than regions of infinite size. Finally, we explored the applicability of key concepts used to describe the behavior of rare earth heavy Fermions to uranium based HF compounds where the 5f electrons are itinerant as opposed to localized. We found that scaling laws relating the spin fluctuation energy measured in neutron scattering to the low temperature specific heat and susceptibility are valid for the uranium compounds, once corrections are made for AF fluctuations; however, the degeneracy of the high temperature moment is smaller than expected

  12. Isotope shifts of the 2 p3 /2-2 p1 /2 transition in B-like ions

    NASA Astrophysics Data System (ADS)

    Zubova, N. A.; Malyshev, A. V.; Tupitsyn, I. I.; Shabaev, V. M.; Kozhedub, Y. S.; Plunien, G.; Brandau, C.; Stöhlker, Th.

    2016-05-01

    Isotope shifts of the 2 p3 /2-2 p1 /2 transition in B-like ions are evaluated for a wide range of the nuclear charge number: Z =8 -92 . The calculations of the relativistic nuclear recoil and nuclear size effects are performed using a large-scale configuration-interaction Dirac-Fock-Sturm method. The corresponding QED corrections are also taken into account. The results of the calculations are compared with the theoretical values obtained with other methods. The accuracy of the isotope shifts of the 2 p3 /2-2 p1 /2 transition in B-like ions is significantly improved.

  13. A study of the valence shell electronic structure and photoionisation dynamics of s-triazine

    NASA Astrophysics Data System (ADS)

    Coriani, S.; Stener, M.; Decleva, P.; Holland, D. M. P.; Potts, A. W.; Karlsson, L.

    2015-04-01

    A joint experimental and theoretical approach has been used to study the valence shell electronic structure and photoionisation dynamics of s-triazine (1,3,5-triazine). Synchrotron radiation has been employed to record angle resolved photoelectron spectra of the complete valence shell for photon energies between 17.5 and 100 eV, thereby allowing photoelectron anisotropy parameters and branching ratios to be determined. Absolute photoionisation partial cross sections have been estimated as the product of these branching ratios and the absolute photoabsorption cross section. The Kohn-Sham and the time-dependent version of density functional theory methods have been used to calculate photoelectron anisotropy parameters and photoionisation partial cross sections, and these have been compared with the corresponding experimental data. The calculations predict that shape resonances affect the photoionisation dynamics of several of the molecular orbitals. The angle resolved photoelectron spectra suggest that the 1 a2″ (π) orbital is more tightly bound than the 5e‧(σ) orbital, and that the 4 a1‧ (σ) orbital is more tightly bound than the 1 a2‧ (σ) orbital, in agreement with the predicted molecular orbital sequence. For the outer valence orbitals the single-particle picture of ionisation holds but electron correlation becomes increasingly important for the inner valence 4e‧, 3e‧ and 3 a1‧ orbitals and leads to a redistribution of intensity. Instead of a readily distinguishable main-line, associated with each of these orbitals, the photoelectron intensity is spread over numerous satellite states and the resulting band is broad and featureless.

  14. Mulliken-Hush analysis of a bis(triarylamine) mixed-valence system with a N...N distance of 28.7 A.

    PubMed

    Heckmann, Alexander; Amthor, Stephan; Lambert, Christoph

    2006-07-28

    An organic mixed valence compound with a spacer length of 25 unsaturated bonds separating two amine redox centres was synthesised and the electron transfer behaviour was investigated in the context of a Mulliken-Hush analysis in order to estimate the longest redox centre separation for which an intervalence charge transfer band can be observed.

  15. Nucleophilic substitution at phosphorus centers (SN2@p).

    PubMed

    van Bochove, Marc A; Swart, Marcel; Bickelhaupt, F Matthias

    2007-12-01

    We have studied the characteristics of archetypal model systems for bimolecular nucleophilic substitution at phosphorus (SN2@P) and, for comparison, at carbon (SN2@C) and silicon (SN2@Si) centers. In our studies, we applied the generalized gradient approximation (GGA) of density functional theory (DFT) at the OLYP/TZ2P level. Our model systems cover nucleophilic substitution at carbon in X(-)+CH3Y (SN2@C), at silicon in X(-)+SiH3Y (SN2@Si), at tricoordinate phosphorus in X(-)+PH2Y (SN2@P3), and at tetracoordinate phosphorus in X(-)+POH2Y (SN2@P4). The main feature of going from SN2@C to SN2@P is the loss of the characteristic double-well potential energy surface (PES) involving a transition state [X--CH3--Y]- and the occurrence of a single-well PES with a stable transition complex, namely, [X--PH2--Y]- or [X--POH2--Y](-). The differences between SN2@P3 and SN2@P4 are relatively small. We explored both the symmetric and asymmetric (i.e. X, Y=Cl, OH) SN2 reactions in our model systems, the competition between backside and frontside pathways, and the dependence of the reactions on the conformation of the reactants. Furthermore, we studied the effect, on the symmetric and asymmetric SN2@P3 and S(N)2@P4 reactions, of replacing hydrogen substituents at the phosphorus centers by chlorine and fluorine in the model systems X(-)+PR2Y and X(-)+POR2Y, with R=Cl, F. An interesting phenomenon is the occurrence of a triple-well PES not only in the symmetric, but also in the asymmetric SN2@P4 reactions of X(-)+POCl2--Y. PMID:17990249

  16. Valence modulates source memory for faces.

    PubMed

    Bell, Raoul; Buchner, Axel

    2010-01-01

    Previous studies in which the effects of emotional valence on old-new discrimination and source memory have been examined have yielded highly inconsistent results. Here, we present two experiments showing that old-new face discrimination was not affected by whether a face was associated with disgusting, pleasant, or neutral behavior. In contrast, source memory for faces associated with disgusting behavior (i.e., memory for the disgusting context in which the face was encountered) was consistently better than source memory for other types of faces. This data pattern replicates the findings of studies in which descriptions of cheating, neutral, and trustworthy behavior were used, which findings were previously ascribed to a highly specific cheater detection module. The present results suggest that the enhanced source memory for faces of cheaters is due to a more general source memory advantage for faces associated with negative or threatening contexts that may be instrumental in avoiding the negative consequences of encounters with persons associated with negative or threatening behaviors.

  17. Emotion and language: Valence and arousal affect word recognition

    PubMed Central

    Brysbaert, Marc; Warriner, Amy Beth

    2014-01-01

    Emotion influences most aspects of cognition and behavior, but emotional factors are conspicuously absent from current models of word recognition. The influence of emotion on word recognition has mostly been reported in prior studies on the automatic vigilance for negative stimuli, but the precise nature of this relationship is unclear. Various models of automatic vigilance have claimed that the effect of valence on response times is categorical, an inverted-U, or interactive with arousal. The present study used a sample of 12,658 words, and included many lexical and semantic control factors, to determine the precise nature of the effects of arousal and valence on word recognition. Converging empirical patterns observed in word-level and trial-level data from lexical decision and naming indicate that valence and arousal exert independent monotonic effects: Negative words are recognized more slowly than positive words, and arousing words are recognized more slowly than calming words. Valence explained about 2% of the variance in word recognition latencies, whereas the effect of arousal was smaller. Valence and arousal do not interact, but both interact with word frequency, such that valence and arousal exert larger effects among low-frequency words than among high-frequency words. These results necessitate a new model of affective word processing whereby the degree of negativity monotonically and independently predicts the speed of responding. This research also demonstrates that incorporating emotional factors, especially valence, improves the performance of models of word recognition. PMID:24490848

  18. Two new barium indium phosphates with intersecting tunnel structures: BaIn{sub 2}P{sub 4}O{sub 14}, and Ba{sub 3}In{sub 2}P{sub 4}O{sub 16}

    SciTech Connect

    Zhang, Wei-Long; Chai, Guo-Liang; Zhang, Hao; Lin, Chen-Sheng; He, Chang-Zhen; Cheng, Wen-Dan

    2010-12-15

    Two new barium indium phosphates BaIn{sub 2}P{sub 4}O{sub 14} and Ba{sub 3}In{sub 2}P{sub 4}O{sub 16} were synthesized by high temperature solution growth method and structurally characterized by single crystal X-ray diffraction analysis. They represent first compounds in the Ba-In-P-O systems. BaIn{sub 2}P{sub 4}O{sub 14} and Ba{sub 3}In{sub 2}P{sub 4}O{sub 16} display different types of 3D architectures. The projections of both structures concern about the existence of the intersecting tunnels. In compound BaIn{sub 2}P{sub 4}O{sub 14}, the tunnels are built up of the corner-sharing InO{sub 6} octahedra and P{sub 2}O{sub 7} groups, whereas in compound Ba{sub 3}In{sub 2}P{sub 4}O{sub 16}, they are formed by corner sharing of PO{sub 4} tetrahedra and InO{sub 6} octahedra. The electronic band structure calculations of two compounds have been performed with the density functional theory method. The study of calculations and optical diffuse reflectance experimental results show both compounds are insulators with direct band-gap.

  19. Energies and E1, M1, E2, and M2 transition rates for states of the 2s22p3, 2s2p4, and 2p5 configurations in nitrogen-like ions between F III and Kr XXX

    NASA Astrophysics Data System (ADS)

    Rynkun, P.; Jönsson, P.; Gaigalas, G.; Froese Fischer, C.

    2014-03-01

    Based on relativistic wavefunctions from multiconfiguration Dirac-Hartree-Fock and configuration interaction calculations, E1, M1, E2, and M2 transition rates, weighted oscillator strengths, and lifetimes are evaluated for the states of the (1s2)2s22p3,2s2p4, and 2p5 configurations in all nitrogen-like ions between F III and Kr XXX. The wavefunction expansions include valence, core-valence, and core-core correlation effects through single-double multireference expansions to increasing sets of active orbitals. The computed energies agree very well with experimental values, with differences of only 300-600 cm-1 for the majority of the levels and ions in the sequence. Computed transitions rates are in close agreement with available data from MCHF-BP calculations by Tachiev and Froese Fischer [G.I. Tachiev, C. Froese Fischer, A&A 385 (2002) 716].

  20. Photoinduced mixed valency in zinc porphyrin dimer of triruthenium cluster dyads.

    PubMed

    Henderson, Jane; Kubiak, Clifford P

    2014-10-20

    The preparation, electrochemistry, and spectroscopic characterization of three new species, (ZnTPPpy)Ru3O(OAc)6(CO)-pz-Ru3O(OAc)6(CO)L, where ZnTPPpy = zinc(II) 5-(4-pyridyl)-10,15,20-triphenylporphyin, L = pyridyl ligand, and pz = pyrazine, are reported. These porphyrin-coordinated Ru3O–BL–Ru3O (BL = bridging ligand) dyads are capable of undergoing intramolecular electron transfer from the photoexcited Zn porphyrin to Ru3O donor–bridge–acceptor dimer systems. Seven reversible redox processes are observed in the cyclic voltammograms of the newly synthesized dyads, showing no significant electrochemical interaction between the redox active porphyrin and the pyrazine-bridged ruthenium dimer of Ru3O trimers. From the electrochemical behavior of the dyads, large comproportionation constants (Kc = 6.0 × 10(7) for L = dmap) were calculated from the reduction potentials of the Ru(III)Ru(III)Ru(II) clusters, indicating a stable mixed-valence state. Electronic absorption spectra of the singly reduced mixed-valence species show two intervalence charge transfer (IVCT) bands assigned within the Brunschwig–Creutz–Sutin semiclassical three-state model as metal-to-bridge and metal-to-metal in character. The progression from most to least delocalized mixed-valence dimer ions, as determined by the divergence of the IVCT bands and in agreement with electrochemical data, follows the order of L = 4-dimethylaminopyridine (dmap) > pyridine (py) > 4-cyanopyridine (cpy). These systems show dynamic coalescence of the infrared spectra in the ν(CO) region of the singly reduced state. This sets the time scale of electron exchange at <10 ps. The electron transfer from the S1 excited state of the coordinated porphyrin to the dimer is predicted to be thermodynamically favorable, with ΔGFET(0) ranging from −0.54 eV for L = dmap to −0.62 eV for L = cpy. Observation of IVCT band growth under continual photolysis (λexc = 568 nm) confirms a phototriggered intramolecular electron

  1. Band offsets and band bending at heterovalent semiconductor interfaces

    NASA Astrophysics Data System (ADS)

    Frey, A.; Bass, U.; Mahapatra, S.; Schumacher, C.; Geurts, J.; Brunner, K.

    2010-11-01

    We present a comprehensive study of band offsets and band bending at heterovalent semiconductor heterointerfaces. A perfectly abrupt heterovalent interface is usually thermodynamically unstable, and atomic intermixing of materials with different numbers of valence electrons causes large variations in band offsets and local doping density, depending on the spatial arrangement of atoms at the interface. The studied prototypical II-VI/III-V semiconductor interfaces are n -doped ZnSe/GaAs (001) heterostructures with varied composition profiles close to the interface, which were realized by molecular-beam epitaxy with different amounts of Zn or Se predeposited on n -GaAs prior to n -ZnSe layer growth. The samples are characterized by temperature-dependent electrical transport across the interface, electrochemical capacitance-voltage profiling, Raman spectroscopy, and high-resolution x-ray diffraction. We find that the potential barrier in the conduction band at a Zn-rich n -ZnSe/ n -GaAs interface is as high as 550 meV and it gradually decreases with Se predeposition down to about 70 meV. A large depletion region at the heterointerface, about 50 nm wide, is assigned to significant intermixing of acceptor-type atoms, resulting in an effective electron deficit of 1.5×1013cm-2 . The depletion width and the acceptor density around the interface are nearly independent from the growth start procedure. Se predeposition, however, partially shifts the depletion region at the heterointerface from GaAs into ZnSe, compared to Zn predeposition. The results are discussed on the basis of a band-bending model accounting for variable band offsets, interface state density and atomic interdiffusion profiles depending on growth start.

  2. Transition state region in the A-Band photodissociation of allyl iodide--A femtosecond extreme ultraviolet transient absorption study.

    PubMed

    Bhattacherjee, Aditi; Attar, Andrew R; Leone, Stephen R

    2016-03-28

    Femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy based on a high-harmonic generation source is used to study the 266 nm induced A-band photodissociation dynamics of allyl iodide (CH2 =CHCH2I). The photolysis of the C-I bond at this wavelength produces iodine atoms both in the ground ((2)P3/2, I) and spin-orbit excited ((2)P1/2, I*) states, with the latter as the predominant channel. Using XUV absorption at the iodine N4/5 edge (45-60 eV), the experiments constitute a direct probe of not only the long-lived atomic iodine reaction products but also the fleeting transition state region of the repulsive nIσ(∗) C-I excited states. Specifically, three distinct features are identified in the XUV transient absorption spectrum at 45.3 eV, 47.4 eV, and 48.4 eV (denoted transients A, B, and C, respectively), which arise from the repulsive valence-excited nσ(∗) states and project onto the high-lying core-excited states of the dissociating molecule via excitation of 4d(I) core electrons. Transients A and B originate from 4d(I) → n(I) core-to-valence transitions, whereas transient C is best assigned to a 4d(I) →σ(∗)(C-I) transition. The measured differential absorbance of these new features along with the I/I* branching ratios known from the literature is used to suggest a more definitive assignment, albeit provisional, of the transients to specific dissociative states within the A-band manifold. The transients are found to peak around 55 fs-65 fs and decay completely by 145 fs-185 fs, demonstrating the ability of XUV spectroscopy to map the evolution of reactants into products in real time. The similarity in the energies of transients A and B with analogous features observed in methyl iodide [Attar et al. J. Phys. Chem. Lett. 6, 5072, (2015)] together with the new observation of transient C in the present work provides a more complete picture of the valence electronic structure in the transition state region. The results provide a benchmark

  3. Transition state region in the A-Band photodissociation of allyl iodide—A femtosecond extreme ultraviolet transient absorption study

    NASA Astrophysics Data System (ADS)

    Bhattacherjee, Aditi; Attar, Andrew R.; Leone, Stephen R.

    2016-03-01

    Femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy based on a high-harmonic generation source is used to study the 266 nm induced A-band photodissociation dynamics of allyl iodide (CH2 =CHCH2I). The photolysis of the C—I bond at this wavelength produces iodine atoms both in the ground (2P3/2, I) and spin-orbit excited (2P1/2, I*) states, with the latter as the predominant channel. Using XUV absorption at the iodine N4/5 edge (45-60 eV), the experiments constitute a direct probe of not only the long-lived atomic iodine reaction products but also the fleeting transition state region of the repulsive nIσ∗C—I excited states. Specifically, three distinct features are identified in the XUV transient absorption spectrum at 45.3 eV, 47.4 eV, and 48.4 eV (denoted transients A, B, and C, respectively), which arise from the repulsive valence-excited nσ∗ states and project onto the high-lying core-excited states of the dissociating molecule via excitation of 4d(I) core electrons. Transients A and B originate from 4d(I) → n(I) core-to-valence transitions, whereas transient C is best assigned to a 4d(I) →σ∗(C—I) transition. The measured differential absorbance of these new features along with the I/I* branching ratios known from the literature is used to suggest a more definitive assignment, albeit provisional, of the transients to specific dissociative states within the A-band manifold. The transients are found to peak around 55 fs-65 fs and decay completely by 145 fs-185 fs, demonstrating the ability of XUV spectroscopy to map the evolution of reactants into products in real time. The similarity in the energies of transients A and B with analogous features observed in methyl iodide [Attar et al. J. Phys. Chem. Lett. 6, 5072, (2015)] together with the new observation of transient C in the present work provides a more complete picture of the valence electronic structure in the transition state region. The results provide a benchmark for

  4. Mixed-valence compound-based biosensor.

    PubMed

    Lin, M S; Wu, Y C; Jan, B I

    1999-01-01

    A cobalt(II)hexacyanoferrate-based biosensor has been prepared simply by codeposition of an enzyme, together with the electrochemical formation of a cobalt (II)hexacyanoferrate compound electrochemically. The compound can be generated at a constant potential of -0.05 V (vs. Ag/AgCl). This compound possesses the catalytic property of reducing hydrogen peroxide to water at the operating potential of 0.0 V vs. Ag/AgCl. The mixed-valence compound-based biosensor possesses an unique interference-independent feature, which is important for biomedical application; this feature is attributed to the low overvoltage characteristic of cobalt (II)hexacyanoferrate. The electrochemical glucose biosensor responds to a series of glucose injections with linearity up to 5 mM (with correlation coefficient R = 0.9999) and the sensitivity of the linear portion is 733 nA/(cm2 x mM). The detection limit is 2 x 10(-6)M (S/N = 3). Both the potential-dependent electron transfer rate constant and the apparent Michaelis-Menten constant were studied in rotating disk experiments. The apparent Michaelis-Menten constant, Km' calculated from the slope of the "Lineweaver-Burke" type reciprocal plot is 28 mM. A fast-response characteristic is observed in the rotating disk experiment and the 95% response time is 14.5 sec. No response was observed from the addition of either 2 x 10(-4)M galactose, acetaminophen, ascorbic acid, uric acid, cysteine, tyrosine, dopamine, or 1,4-dihydroxyquinone in the absence and/or in the presence of 5 x 10(-4)M glucose. PMID:10099513

  5. Valence-state Model of Strain-dependent Mn L2,3 X-ray Magnetic Circular Dichroism from Ferromagnetic Semiconductors

    SciTech Connect

    van der Laan, G.; Edmonds, K. W.; Arenholz, E.; Farley, N. R. S.; Gallagher, B. L.

    2010-03-30

    We present a valence-state model to explain the characteristics of a recently observed pre-edge feature in Mn L{sub 3} x-ray magnetic circular dichroism (XMCD) of ferromagnetic (Ga,Mn)As and (Al,Ga,Mn)As thin films. The prepeak XMCD shows a uniaxial anisotropy, contrary to the cubic symmetry of the main structures induced by the crystalline electric field. Reversing the strain in the host lattice reverses the sign of the uniaxial anisotropy. With increasing carrier localization, the prepeak height increases, indicating an increasing 3d character of the hybridized holes. Hence, the feature is ascribed to transitions from the Mn 2p core level to unoccupied p-d hybridized valence states. The characteristics of the prepeak are readily reproduced by the model calculation taking into account the symmetry of the strain-, spin-orbit-, and exchange-split valence states around the zone center.

  6. Optoelectronic devices based on MoTe2 p-n junction

    NASA Astrophysics Data System (ADS)

    Bie, Ya-Qing; Heuck, Mikkel; Furchi, Marco; Grosso, Gabriele; Zheng, Jiabao; Cao, Yuan; Navarro-Moratalla, Efren; Englund, Dirk; Jarillo-Herrero, Pablo

    2D transition metal dichalcogenides (2D-TMD), such as MoS2, have been verified with many remarkable physical properties, which include an indirect to direct band transition as a function of thickness and a valley dependent spin polarization. One of the 2D-TMD family members, 2H-MoTe2 has been shown to be a direct bandgap semiconductor as a monolayer and bilayer with a near infrared (NIR) bandgap of about 1.1eV. However, optoelectronic devices based on MoTe2 were so far not experimentally demonstrated. Here, we will present a high on-off ratio MoTe2 p-n junction enabled by a hexagonal boron nitride encapsulation technique. Our study of the MoTe2 p-n junction devices sheds light on designing efficient NIR optoelectronic devices such as photodetectors and energy harvesting cells and light emitters.

  7. A Valence Isomer Trapping Procedure for Introductory Organic Laboratory.

    ERIC Educational Resources Information Center

    Kurtz, David W.; Johnson, Richard P.

    1989-01-01

    Described is an experiment which illustrates valence isomerization, the trapping of a reactive intermediate and retrosynthetic analysis applied to the Diels-Alder reaction. Included is a background discussion, experimental procedures, and a discussion of the analysis. (CW)

  8. Candidate Valence as a Predictor of Voter Preference.

    ERIC Educational Resources Information Center

    Andersen, Peter A.; Kibler, Robert J.

    1978-01-01

    Studies the effects of source valence, including source credibility, attraction, and homophyly, on voter preference in a Florida Democratic primary election campaign. Indicates that attitude homophyly is an excellent predictor of voter preference. (JMF)

  9. Differential impact of beliefs on valence and arousal

    PubMed Central

    Nicolle, Antoinette; Goel, Vinod

    2012-01-01

    Many cognitive accounts of emotional processing assume that emotions have representational content that can be influenced by beliefs and desires. It is generally thought that emotions also have non-cognitive, affective components, including valence and arousal. To clarify the impact of cognition on these affective components we asked participants to rate sentences along cognitive and affective dimensions. For the former case, participants rated the believability of the material. For the latter case, they provided valence and arousal ratings. Across two experiments, we show that valence and arousal are differently influenced by beliefs, suggesting that these two largely independent affective components of emotion differ in their cognitive penetrability. While both components depended upon overall comprehension of sentence meaning, only valence was influenced by the consistency of the sentences with participants’ beliefs (i.e., whether it was believable or unbelievable). We discuss the implications of these findings for understanding cognition-emotion relationships. PMID:22783982

  10. Trisomy 2p: Analysis of unusual phenotypic findings

    SciTech Connect

    Lurie, I.W.; Ilyina, H.G.; Gurevich, D.B.

    1995-01-16

    We present three probands with partial trisomies 2p21-23 due to ins(4;2)(q21;p21p23) pat, 2p23-pter due to t(2;4)(p23;q35)mat, and 2p21-pter due to t(2;11)(p21;q23.3)mat. More than 50 cases of partial trisomy 2p have been reviewed and some abnormalities, unusual for most other types of structural autosomal imbalance, have been found in patients with inherited forms of 2p trisomy and in their non-karyotyped sibs. Neural tube defects (anencephaly, occipital encephalocele, and spina bifida) were found in five probands and 4/6 affected non-karyotyped sibs. The only triplicated segment common to all was 2p24. Different forms of {open_quotes}broncho-pulmonary a/hypoplasia{close_quotes} (including two cases of lung agenesis) were described in four patients (overlapping triplicated segment was 2p21-p25). Three patients (with overlapping triplicated segment 2p23-p25) had diaphragmatic hernia. Abnormal rotation of the heart or L-transposition of large vessels (with or without visceral heterotaxia) was found in two infants (overlapping triplicated segment 2p23-p24). In two patients with common triplicated segment 2p22.3-p25, neuroblastoma has been described. The occurrence of all these defects may be explained either by the action of the same gene(s) mapped to 2p24 or by action of some independent factors located in different segments of the short arm. Although the latter hypothesis is much less probable, it can not be rejected at the present time. We propose the existence of a genetic system controlling surveillance of an abnormal embryo to explain the phenotypic differences between patients with the same imbalance within a family. In some {open_quotes}restrictive{close_quotes} combinations the abnormal embryos will die, although in {open_quotes}permissive{close_quotes} combinations they can survive. 47 refs., 2 figs., 3 tabs.

  11. Narrow Band Gap Lead Sulfide Hole Transport Layers for Quantum Dot Photovoltaics.

    PubMed

    Zhang, Nanlin; Neo, Darren C J; Tazawa, Yujiro; Li, Xiuting; Assender, Hazel E; Compton, Richard G; Watt, Andrew A R

    2016-08-24

    The band structure of colloidal quantum dot (CQD) bilayer heterojunction solar cells is optimized using a combination of ligand modification and QD band gap control. Solar cells with power conversion efficiencies of up to 9.33 ± 0.50% are demonstrated by aligning the absorber and hole transport layers (HTL). Key to achieving high efficiencies is optimizing the relative position of both the valence band and Fermi energy at the CQD bilayer interface. By comparing different band gap CQDs with different ligands, we find that a smaller band gap CQD HTL in combination with a more p-type-inducing CQD ligand is found to enhance hole extraction and hence device performance. We postulate that the efficiency improvements observed are largely due to the synergistic effects of narrower band gap QDs, causing an upshift of valence band position due to 1,2-ethanedithiol (EDT) ligands and a lowering of the Fermi level due to oxidation.

  12. Narrow Band Gap Lead Sulfide Hole Transport Layers for Quantum Dot Photovoltaics.

    PubMed

    Zhang, Nanlin; Neo, Darren C J; Tazawa, Yujiro; Li, Xiuting; Assender, Hazel E; Compton, Richard G; Watt, Andrew A R

    2016-08-24

    The band structure of colloidal quantum dot (CQD) bilayer heterojunction solar cells is optimized using a combination of ligand modification and QD band gap control. Solar cells with power conversion efficiencies of up to 9.33 ± 0.50% are demonstrated by aligning the absorber and hole transport layers (HTL). Key to achieving high efficiencies is optimizing the relative position of both the valence band and Fermi energy at the CQD bilayer interface. By comparing different band gap CQDs with different ligands, we find that a smaller band gap CQD HTL in combination with a more p-type-inducing CQD ligand is found to enhance hole extraction and hence device performance. We postulate that the efficiency improvements observed are largely due to the synergistic effects of narrower band gap QDs, causing an upshift of valence band position due to 1,2-ethanedithiol (EDT) ligands and a lowering of the Fermi level due to oxidation. PMID:27421066

  13. Network Awareness in P2P-TV Applications

    NASA Astrophysics Data System (ADS)

    Traverso, Stefano; Leonardi, Emilio; Mellia, Marco; Meo, Michela

    The increasing popularity of applications for video-streaming based on P2P paradigm (P2P-TV) is raising the interest of both broadcasters and network operators. The former see a promising technology to reduce the cost of streaming content over the Internet, while offering a world-wide service. The latter instead fear that the traffic offered by these applications can grow without control, affecting other services, and possibly causing network congestion and collapse. The “Network-Aware P2P-TV Application over Wise Networks” FP7 project aims at studying and developing a novel P2P-TV application offering the chance to broadcast high definition video to broadcasters and to carefully manage the traffic offered by peers to the network, therefore avoiding worries to Internet providers about network overload. In such context, we design a simulator to evaluate performance of different P2P-TV solutions, to compare them both considering end-users’ and network providers’ perspectives, such as quality of service perceived by subscribers and link utilization. In this paper, we provide some results that show how effective can be a network aware P2P-TV system.

  14. Genetic heterogeneity of gingival fibromatosis on chromosome 2p

    PubMed Central

    Shashi, V.; Pallos, D.; Pettenati, M.; Cortelli, J.; Fryns, J.; von Kap-Herr, C.; Hart, T.

    1999-01-01

    Gingival fibromatosis (GF) occurs in several genetic forms as a simple Mendelian trait, in malformation syndromes, and in some chromosomal disorders. Specific genes responsible for GF have not been identified. An autosomal dominant form of hereditary gingival fibromatosis (HGF, MIM 135300) was recently mapped to chromosome 2p21 in a large Brazilian family and there was an earlier report of GF in a boy with a cytogenetic duplication involving 2p13→p21. We thus hypothesised that a common gene locus may be responsible for GF in both the Brazilian family and the boy with the chromosome 2p duplication. We performed additional genetic linkage studies on the Brazilian family and molecular cytogenetic studies on the patient with the cytogenetic duplication to correlate more precisely the genetic interval of the HGF phenotype with the duplicated 2p interval. Additional linkage analysis of new family members resulted in refinement of the candidate region for HGF to an 8 Mb region. Molecular cytogenetic analysis of the 2p13→p21 duplication associated with GF showed that the duplicated region was proximal to the candidate interval for HGF. Thus, our results support the presence of two different gene loci on chromosome 2p that are involved in GF.


Keywords: gingival fibromatosis; chromosome duplication; chromosome 2 PMID:10507724

  15. Emotional Valence and the Free-Energy Principle

    PubMed Central

    Joffily, Mateus; Coricelli, Giorgio

    2013-01-01

    The free-energy principle has recently been proposed as a unified Bayesian account of perception, learning and action. Despite the inextricable link between emotion and cognition, emotion has not yet been formulated under this framework. A core concept that permeates many perspectives on emotion is valence, which broadly refers to the positive and negative character of emotion or some of its aspects. In the present paper, we propose a definition of emotional valence in terms of the negative rate of change of free-energy over time. If the second time-derivative of free-energy is taken into account, the dynamics of basic forms of emotion such as happiness, unhappiness, hope, fear, disappointment and relief can be explained. In this formulation, an important function of emotional valence turns out to regulate the learning rate of the causes of sensory inputs. When sensations increasingly violate the agent's expectations, valence is negative and increases the learning rate. Conversely, when sensations increasingly fulfil the agent's expectations, valence is positive and decreases the learning rate. This dynamic interaction between emotional valence and learning rate highlights the crucial role played by emotions in biological agents' adaptation to unexpected changes in their world. PMID:23785269

  16. Input-specific contributions to valence processing in the amygdala.

    PubMed

    Correia, Susana S; Goosens, Ki A

    2016-10-01

    Reward and punishment are often thought of as opposing processes: rewards and the environmental cues that predict them elicit approach and consummatory behaviors, while punishments drive aversion and avoidance behaviors. This framework suggests that there may be segregated brain circuits for these valenced behaviors. The basolateral amygdala (BLA) is one brain region that contributes to both types of motivated behavior. Individual neurons in the BLA can favor positive over negative valence, or vice versa, but these neurons are intermingled, showing no anatomical segregation. The amygdala receives inputs from many brain areas and current theories posit that encoding of positive versus negative valence by BLA neurons is determined by the wiring of each neuron. Specifically, many projections from other brain areas that respond to positive and negative valence stimuli and predictive cues project strongly to the BLA and likely contribute to valence processing within the BLA. Here we review three of these areas, the basal forebrain, the dorsal raphe nucleus and the ventral tegmental area, and discuss how these may promote encoding of positive and negative valence within the BLA. PMID:27634144

  17. Emotional valence and the free-energy principle.

    PubMed

    Joffily, Mateus; Coricelli, Giorgio

    2013-01-01

    The free-energy principle has recently been proposed as a unified Bayesian account of perception, learning and action. Despite the inextricable link between emotion and cognition, emotion has not yet been formulated under this framework. A core concept that permeates many perspectives on emotion is valence, which broadly refers to the positive and negative character of emotion or some of its aspects. In the present paper, we propose a definition of emotional valence in terms of the negative rate of change of free-energy over time. If the second time-derivative of free-energy is taken into account, the dynamics of basic forms of emotion such as happiness, unhappiness, hope, fear, disappointment and relief can be explained. In this formulation, an important function of emotional valence turns out to regulate the learning rate of the causes of sensory inputs. When sensations increasingly violate the agent's expectations, valence is negative and increases the learning rate. Conversely, when sensations increasingly fulfil the agent's expectations, valence is positive and decreases the learning rate. This dynamic interaction between emotional valence and learning rate highlights the crucial role played by emotions in biological agents' adaptation to unexpected changes in their world.

  18. Laparoscopic gastric banding

    MedlinePlus

    ... adjustable gastric banding; Bariatric surgery - laparoscopic gastric banding; Obesity - gastric banding; Weight loss - gastric banding ... gastric banding is not a "quick fix" for obesity. It will greatly change your lifestyle. You must ...

  19. Synthetic, Spectroscopic, and Electrochemical Studies of the Isomerically-Rich [M(CO)(2)(P(2)P')X](+/0) (M = Mn, Re; X = Cl, Br; P(2)P' = eta(3)-Ph(2)P(CH(2))(2)P(Ph)(CH(2))(2)PPh(2)) System: Structural Characterization of a Novel Pair of Diastereoisomers of cis,mer-Re(CO)(2)(P(2)P')Cl.

    PubMed

    Bond, Alan M.; Colton, Ray; Gable, Robert W.; Mackay, Maureen F.; Walter, Jacky N.

    1997-03-12

    Reaction of Mn(CO)(5)X (X = Cl, Br) with Ph(2)P(CH(2))(2)P(Ph)(CH(2))(2)PPh(2) (P(2)P') in refluxing xylene led to the formation of isomerically pure cis,mer-Mn(CO)(2)(eta(3)-P(2)P')X. Cyclic voltammograms in dichloromethane (0.1 M Bu(4)NPF(6)) show a reversible one-electron oxidation (process 1, E(1/2) = 0.142 V) to give cis,mer-[Mn(CO)(2)(P(2)P')X](+). However, in acetone (0.1 M Bu(4)NPF(6)) at room temperature, process 1 is not reversible and an additional redox process 4 (E(1/2) = 0.048 V) is observed. Process 4 is not observed at low temperatures, and at higher temperatures in acetone it merges with process 1 and also a new reversible redox couple (process 5, E(1/2) = -0.411 V) appears. A combination of electrolyses, chemical oxidation, and subsequent reduction, coupled with IR and (31)P NMR spectroscopies and electrospray mass spectrometry (ESMS), is used to show that processes 1, 4, and 5 are all associated with redox and interconversion reactions of different isomers of Mn(CO)(2)(P(2)P')X and [Mn(CO)(2)(P(2)P')X](+). Other irreversible processes due to oxidation of the different isomers of [Mn(CO)(2)(P(2)P')X](+) are observed at very positive potentials. Reaction between Re(CO)(5)X and P(2)P' in refluxing mesitylene gives a soluble product and a small amount of precipitate. The major soluble product was identified as cis,mer-Re(CO)(2)(P(2)P')X, and the oxidative chemistry is similar to that of the manganese analogues. The precipitate consists of five compounds, one of which was cis,mer-Re(CO)(2)(P(2)P')X. The new compounds A-D were identified as follows: A is cis,mer-{Re(CO)(2)(P(2)P')X}(2), a dimeric species with bridging P(2)P' ligands. The spectroscopic data for B indicated that it was a form of cis,mer-Re(CO)(2)(P(2)P')X, but not the same as the major product. Compound C is cis,fac-Re(CO)(2)(P(2)P')X, and compound D was shown to be fac-[Re(CO)(3)(P(2)P')]X. The crystal structures of cis,mer-Re(CO)(2)(P(2)P')Cl(I) and cis,mer-Re(CO)(2)(P(2)P')Cl(II) show

  20. Band to band tunneling in III-V semiconductors: Implications of complex band structure, strain, orientation, and off-zone center contribution

    SciTech Connect

    Majumdar, Kausik

    2014-05-07

    In this paper, we use a tight binding Hamiltonian with spin orbit coupling to study the real and complex band structures of relaxed and strained GaAs. A simple d orbital on-site energy shift coupled with appropriate scaling of the off-diagonal terms is found to correctly reproduce the band-edge shifts with strain. Four different 〈100〉 strain combinations, namely, uniaxial compressive, uniaxial tensile, biaxial compressive, and biaxial tensile strain are studied, revealing rich valence band structure and strong relative orientation dependent tunneling. It is found that complex bands are unable to provide unambiguous tunneling paths away from the Brillouin zone center. Tunneling current density distribution over the Brillouin zone is computed using non-equilibrium Green's function approach elucidating a physical picture of band to band tunneling.

  1. First-principles energy band calculation of Ruddlesden-Popper compound Sr3Sn2O7 using modified Becke-Johnson exchange potential

    NASA Astrophysics Data System (ADS)

    Kamimura, Sunao; Obukuro, Yuki; Matsushima, Shigenori; Nakamura, Hiroyuki; Arai, Masao; Xu, Chao-Nan

    2015-12-01

    The electronic structure of Sr3Sn2O7 is evaluated by the scalar-relativistic full potential linearized augmented plane wave (FLAPW+lo) method using the modified Becke-Johnson potential (Tran-Blaha potential) combined with the local density approximation correlation (MBJ-LDA). The fundamental gap between the valence band (VB) and conduction band (CB) is estimated to be 3.96 eV, which is close to the experimental value. Sn 5s states and Sr 4d states are predominant in the lower and upper CB, respectively. On the other hand, the lower VB is mainly composed of Sn 5s, 5p, and O 2p states, while the upper VB mainly consists of O 2p states. These features of the DOS are well reflected by the optical transition between the upper VB and lower CB, as seen in the energy dependence of the dielectric function. Furthermore, the absorption coefficient estimated from the MBJ-LDA is similar to the experimental result.

  2. Determinants of Default in P2P Lending

    PubMed Central

    2015-01-01

    This paper studies P2P lending and the factors explaining loan default. This is an important issue because in P2P lending individual investors bear the credit risk, instead of financial institutions, which are experts in dealing with this risk. P2P lenders suffer a severe problem of information asymmetry, because they are at a disadvantage facing the borrower. For this reason, P2P lending sites provide potential lenders with information about borrowers and their loan purpose. They also assign a grade to each loan. The empirical study is based on loans’ data collected from Lending Club (N = 24,449) from 2008 to 2014 that are first analyzed by using univariate means tests and survival analysis. Factors explaining default are loan purpose, annual income, current housing situation, credit history and indebtedness. Secondly, a logistic regression model is developed to predict defaults. The grade assigned by the P2P lending site is the most predictive factor of default, but the accuracy of the model is improved by adding other information, especially the borrower’s debt level. PMID:26425854

  3. An efficient query mechanism base on P2P networks

    NASA Astrophysics Data System (ADS)

    Wang, Xiaohua; Mu, Aiqin; Zhao, Defang

    2013-07-01

    How to implement the efficient query is the key problem deployed on P2P networks. This paper analyses the shortage of several query algorithm, and presents a new algorithm DDI, which means distributed searching with double indices. It discusses the popularity of documents and the linking status of the networks, and calculates the availability of the nodes in whole network, determines the route of the query process. It compares the items of time using, the quantity of requests and update information by the emulate experiments. Along with the rapid development of computer network technology, peer-to-peer (referred to as P2P) network research has gradually become mature, and it is widely used in different fields, some large P2P computing project has entered the implementation stage. At present, many more popular software systems such as Gnutella, Freenet, Napster are deployed based on P2P technology. How to achieve effective information query has become one of the key problems of P2P research.

  4. Determinants of Default in P2P Lending.

    PubMed

    Serrano-Cinca, Carlos; Gutiérrez-Nieto, Begoña; López-Palacios, Luz

    2015-01-01

    This paper studies P2P lending and the factors explaining loan default. This is an important issue because in P2P lending individual investors bear the credit risk, instead of financial institutions, which are experts in dealing with this risk. P2P lenders suffer a severe problem of information asymmetry, because they are at a disadvantage facing the borrower. For this reason, P2P lending sites provide potential lenders with information about borrowers and their loan purpose. They also assign a grade to each loan. The empirical study is based on loans' data collected from Lending Club (N = 24,449) from 2008 to 2014 that are first analyzed by using univariate means tests and survival analysis. Factors explaining default are loan purpose, annual income, current housing situation, credit history and indebtedness. Secondly, a logistic regression model is developed to predict defaults. The grade assigned by the P2P lending site is the most predictive factor of default, but the accuracy of the model is improved by adding other information, especially the borrower's debt level.

  5. Protecting Data Privacy in Structured P2P Networks

    NASA Astrophysics Data System (ADS)

    Jawad, Mohamed; Serrano-Alvarado, Patricia; Valduriez, Patrick

    P2P systems are increasingly used for efficient, scalable data sharing. Popular applications focus on massive file sharing. However, advanced applications such as online communities (e.g., medical or research communities) need to share private or sensitive data. Currently, in P2P systems, untrusted peers can easily violate data privacy by using data for malicious purposes (e.g., fraudulence, profiling). To prevent such behavior, the well accepted Hippocratic database principle states that data owners should specify the purpose for which their data will be collected. In this paper, we apply such principles as well as reputation techniques to support purpose and trust in structured P2P systems. Hippocratic databases enforce purpose-based privacy while reputation techniques guarantee trust. We propose a P2P data privacy model which combines the Hippocratic principles and the trust notions. We also present the algorithms of PriServ, a DHT-based P2P privacy service which supports this model and prevents data privacy violation. We show, in a performance evaluation, that PriServ introduces a small overhead.

  6. Determinants of Default in P2P Lending.

    PubMed

    Serrano-Cinca, Carlos; Gutiérrez-Nieto, Begoña; López-Palacios, Luz

    2015-01-01

    This paper studies P2P lending and the factors explaining loan default. This is an important issue because in P2P lending individual investors bear the credit risk, instead of financial institutions, which are experts in dealing with this risk. P2P lenders suffer a severe problem of information asymmetry, because they are at a disadvantage facing the borrower. For this reason, P2P lending sites provide potential lenders with information about borrowers and their loan purpose. They also assign a grade to each loan. The empirical study is based on loans' data collected from Lending Club (N = 24,449) from 2008 to 2014 that are first analyzed by using univariate means tests and survival analysis. Factors explaining default are loan purpose, annual income, current housing situation, credit history and indebtedness. Secondly, a logistic regression model is developed to predict defaults. The grade assigned by the P2P lending site is the most predictive factor of default, but the accuracy of the model is improved by adding other information, especially the borrower's debt level. PMID:26425854

  7. Character Disposition and Behavior Type: Influences of Valence on Preschool Children's Social Judgments

    ERIC Educational Resources Information Center

    Jones, Elaine F.; Tobias, Marvin; Pauley, Danielle; Thomson, Nicole Renick; Johnson, Shawana Lewis

    2009-01-01

    The authors studied the influences of valence information on preschool children's (n = 47) moral (good or bad), liking (liked or disliked by a friend), and consequence-of-behavior (reward or punishment) judgments. The authors presented 8 scenarios describing the behavior valence, positive valence (help, share), negative valence (verbal insult,…

  8. Band structures in 99Rh

    NASA Astrophysics Data System (ADS)

    Kumar, S.; Singh, V.; Singh, K.; Sihotra, S.; Singh, N.; Goswamy, J.; Malik, S. S.; Ragnarsson, I.; Trivedi, T.; Singh, R. P.; Muralithar, S.; Kumar, R.; Bhowmik, R. K.; Palit, R.; Bharti, A.; Mehta, D.

    2014-10-01

    Excited states in the 99Rh nucleus were populated using the fusion-evaporation reaction 75As(28Si,2p2n) at {{E}_{lab}}=120\\;MeV and the de-excitations were investigated through in-beam γ-ray spectroscopic techniques using the INGA spectrometer consisting of 18 clover detectors. The observed band structures are discussed in the framework of tilted axis cranking shell-model calculations. Level structures at low energies are identified as resulting from the rotational bands based on the \\pi {{p}_{1/2}} and \\pi {{g}_{9/2}} configurations. The \\Delta I = 1 coupled bands are observed at higher excitation energies and have been interpreted as based on the \\pi {{g}_{9/2}}\\otimes \

  9. Valence-band splitting in Mg/W(110) : Neither spin-orbit nor parity effect

    NASA Astrophysics Data System (ADS)

    Shikin, A. M.; Rader, O.

    2007-08-01

    Spin-orbit coupling, e.g., in the form of the Rashba effect, is of high interest due to its role in novel spintronic devices. In connection with the question whether spin-orbit splittings can be induced in a thin film by a buried interface, there is a current controversy as to the origin of measured energy splittings in Mg quantum-well films on W(110) [C. Koitzsch , Phys. Rev. Lett. 95, 126401 (2005); F. Schiller , ibid. 95, 126402 (2005)]. This problem is resolved by comparing Mg/W(110) with Mg/Mo(110) data. At variance with both previous reports, strong interaction of Mg states with surface states of the substrate is identified as the origin of the observations in question.

  10. Tunneling spectroscopy of hole plasmons in a valence-band quantum well

    SciTech Connect

    Neves, B.R.; Foster, T.J.; Eaves, L.; Main, P.C.; Henini, M.; Fisher, D.J.; Lerch, M.L.; Martin, A.D.; Zhang, C.

    1996-10-01

    We investigate the current-voltage characteristics of a {ital p}-doped resonant tunneling diode. In the voltage range slightly above the bias corresponding to resonant tunneling of holes into the first light-hole subband of the quantum well, we observe two satellite peaks which we attribute to plasmon-assisted tunneling transitions. A theoretical model is presented to account for these peaks. The model is based on the excitation of intrasubband and intersubband heavy-hole plasmons in the quantum well by hot holes injected close to the energy of the first light-hole subband. We also study the behavior of the satellites when a magnetic field is applied either parallel to or perpendicular to the current. {copyright} {ital 1996 The American Physical Society.}

  11. Temperature-dependent internal photoemission probe for band parameters

    NASA Astrophysics Data System (ADS)

    Lao, Yan-Feng; Perera, A. G. Unil

    2012-11-01

    The temperature-dependent characteristic of band offsets at the heterojunction interface was studied by an internal photoemission (IPE) method. In contrast to the traditional Fowler method independent of the temperature (T), this method takes into account carrier thermalization and carrier/dopant-induced band-renormalization and band-tailing effects, and thus measures the band-offset parameter at different temperatures. Despite intensive studies in the past few decades, the T dependence of this key band parameter is still not well understood. Re-examining a p-type doped GaAs emitter/undoped AlxGa1-xAs barrier heterojunction system disclosed its previously ignored T dependency in the valence-band offset, with a variation up to ˜-10-4 eV/K in order to accommodate the difference in the T-dependent band gaps between GaAs and AlGaAs. Through determining the Fermi energy level (Ef), IPE is able to distinguish the impurity (IB) and valence bands (VB) of extrinsic semiconductors. One important example is to determine Ef of dilute magnetic semiconductors such as GaMnAs, and to understand whether it is in the IB or VB.

  12. Fragrance material review on 2-(p-tolyloxy)ethyl acetate.

    PubMed

    McGinty, D; Letizia, C S; Api, A M

    2012-09-01

    A toxicologic and dermatologic review of 2-(p-tolyloxy)ethyl acetate when used as a fragrance ingredient is presented. 2-(p-tolyloxy)ethyl acetate is a member of the fragrance structural group aryl alkyl alcohol simple acid esters (AAASAE). The AAASAE fragrance ingredients are prepared by reacting an aryl alkyl alcohol with a simple carboxylic acid (a chain of 1-4 carbons) to generate formate, acetate, propionate, butyrate, isobutyrate and carbonate esters. This review contains a detailed summary of all available toxicology and dermatology papers that are related to this individual fragrance ingredient and is not intended as a stand-alone document. Available data for 2-(p-tolyloxy)ethyl acetate were evaluated, then summarized, and includes physical properties data. A safety assessment of the entire AAASAE will be published simultaneously with this document. Please refer to Belsito et al. (2012) for an overall assessment of the safe use of this material and all AAASAE in fragrances.

  13. Fragrance material review on 2-(p-tolyloxy)ethyl acetate.

    PubMed

    McGinty, D; Letizia, C S; Api, A M

    2012-09-01

    A toxicologic and dermatologic review of 2-(p-tolyloxy)ethyl acetate when used as a fragrance ingredient is presented. 2-(p-tolyloxy)ethyl acetate is a member of the fragrance structural group aryl alkyl alcohol simple acid esters (AAASAE). The AAASAE fragrance ingredients are prepared by reacting an aryl alkyl alcohol with a simple carboxylic acid (a chain of 1-4 carbons) to generate formate, acetate, propionate, butyrate, isobutyrate and carbonate esters. This review contains a detailed summary of all available toxicology and dermatology papers that are related to this individual fragrance ingredient and is not intended as a stand-alone document. Available data for 2-(p-tolyloxy)ethyl acetate were evaluated, then summarized, and includes physical properties data. A safety assessment of the entire AAASAE will be published simultaneously with this document. Please refer to Belsito et al. (2012) for an overall assessment of the safe use of this material and all AAASAE in fragrances. PMID:22414652

  14. Faraday effect in Sn2P2S6 crystals.

    PubMed

    Krupych, Oleh; Adamenko, Dmytro; Mys, Oksana; Grabar, Aleksandr; Vlokh, Rostyslav

    2008-11-10

    We have revealed a large Faraday rotation in tin thiohypodiphosphate (Sn(2)P(2)S(6)) crystals, which makes this material promising for magneto-optics. The effective Faraday tensor component and the Verdet constant for the direction of the optic axis have been determined by measuring the pure Faraday rotation in Sn(2)P(2)S(6) crystals with both the single-ray and small-angular polarimetric methods at the normal conditions and a wavelength of 632.8 nm. The effective Verdet constant is found to be equal to 115 rad/T x m.

  15. Band Offset Characterization of the Atomic Layer Deposited Aluminum Oxide on m-Plane Indium Nitride

    NASA Astrophysics Data System (ADS)

    Jia, Ye; Wallace, Joshua S.; Qin, Yueling; Gardella, Joseph A.; Dabiran, Amir M.; Singisetti, Uttam

    2016-04-01

    In this letter, we report the band offset characterization of the atomic layer deposited aluminum oxide on non-polar m-plane indium nitride grown by plasma-assisted molecular beam epitaxy by using x-ray photoelectron spectroscopy. The valence band offset between aluminum oxide and m-plane indium nitride was determined to be 2.83 eV. The Fermi level of indium nitride was 0.63 eV above valence band maximum, indicated a reduced band bending in comparison to polar indium nitride. The band gap of aluminum oxide was found to be to 6.7 eV, which gave a conduction band offset of 3.17 eV.

  16. Social learning modulates the lateralization of emotional valence.

    PubMed

    Shamay-Tsoory, Simone G; Lavidor, Michal; Aharon-Peretz, Judith

    2008-08-01

    Although neuropsychological studies of lateralization of emotion have emphasized valence (positive vs. negative) or type (basic vs. complex) dimensions, the interaction between the two dimensions has yet to be elucidated. The purpose of the current study was to test the hypothesis that recognition of basic emotions is processed preferentially by the right prefrontal cortex (PFC), whereas recognition of complex social emotions is processed preferentially by the left PFC. Experiment 1 assessed the ability of healthy controls and patients with right and left PFC lesions to recognize basic and complex emotions. Experiment 2 modeled the patient's data of Experiment 1 on healthy participants under lateralized displays of the emotional stimuli. Both experiments support the Type as well as the Valence Hypotheses. However, our findings indicate that the Valence Hypothesis holds for basic but less so for complex emotions. It is suggested that, since social learning overrules the basic preference of valence in the hemispheres, the processing of complex emotions in the hemispheres is less affected by valence. PMID:18343548

  17. Effects of valence and divided attention on cognitive reappraisal processes

    PubMed Central

    Leclerc, Christina M.; Kensinger, Elizabeth A.

    2014-01-01

    Numerous studies have investigated the neural substrates supporting cognitive reappraisal, identifying the importance of cognitive control processes implemented by prefrontal cortex (PFC). This study examined how valence and attention affect the processes used for cognitive reappraisal by asking participants to passively view or to cognitively reappraise positive and negative images with full or divided attention. When participants simply viewed these images, results revealed few effects of valence or attention. However, when participants engaged in reappraisal, there was a robust effect of valence, with the reappraisal of negative relative to positive images associated with more widespread activation, including within regions of medial and lateral PFC. There also was an effect of attention, with more lateral PFC recruitment when regulating with full attention and more medial PFC recruitment when regulating with divided attention. Within two regions of medial PFC and one region of ventrolateral PFC, there was an interaction between valence and attention: in these regions, divided attention reduced activity during reappraisal of positive but not negative images. Critically, participants continued to report reappraisal success even during the Divided Attention condition. These results suggest multiple routes to successful cognitive reappraisal, depending upon image valence and the availability of attentional resources. PMID:24493837

  18. The acoustic correlates of valence depend on emotion family.

    PubMed

    Belyk, Michel; Brown, Steven

    2014-07-01

    The voice expresses a wide range of emotions through modulations of acoustic parameters such as frequency and amplitude. Although the acoustics of individual emotions are well understood, attempts to describe the acoustic correlates of broad emotional categories such as valence have yielded mixed results. In the present study, we analyzed the acoustics of emotional valence for different families of emotion. We divided emotional vocalizations into "motivational," "moral," and "aesthetic" families as defined by the OCC (Ortony, Clore, and Collins) model of emotion. Subjects viewed emotional scenarios and were cued to vocalize congruent exclamations in response to them, for example, "Yay!" and "Damn!". Positive valence was weakly associated with high-pitched and loud vocalizations. However, valence interacted with emotion family for both pitch and amplitude. A general acoustic code for valence does not hold across families of emotion, whereas family-specific codes provide a more accurate description of vocal emotions. These findings are consolidated into a set of "rules of expression" relating vocal dimensions to emotion dimensions.

  19. Intermediate band solar cell with extreme broadband spectrum quantum efficiency.

    PubMed

    Datas, A; López, E; Ramiro, I; Antolín, E; Martí, A; Luque, A; Tamaki, R; Shoji, Y; Sogabe, T; Okada, Y

    2015-04-17

    We report, for the first time, about an intermediate band solar cell implemented with InAs/AlGaAs quantum dots whose photoresponse expands from 250 to ∼6000  nm. To our knowledge, this is the broadest quantum efficiency reported to date for a solar cell and demonstrates that the intermediate band solar cell is capable of producing photocurrent when illuminated with photons whose energy equals the energy of the lowest band gap. We show experimental evidence indicating that this result is in agreement with the theory of the intermediate band solar cell, according to which the generation recombination between the intermediate band and the valence band makes this photocurrent detectable. PMID:25933339

  20. Intermediate band solar cell with extreme broadband spectrum quantum efficiency.

    PubMed

    Datas, A; López, E; Ramiro, I; Antolín, E; Martí, A; Luque, A; Tamaki, R; Shoji, Y; Sogabe, T; Okada, Y

    2015-04-17

    We report, for the first time, about an intermediate band solar cell implemented with InAs/AlGaAs quantum dots whose photoresponse expands from 250 to ∼6000  nm. To our knowledge, this is the broadest quantum efficiency reported to date for a solar cell and demonstrates that the intermediate band solar cell is capable of producing photocurrent when illuminated with photons whose energy equals the energy of the lowest band gap. We show experimental evidence indicating that this result is in agreement with the theory of the intermediate band solar cell, according to which the generation recombination between the intermediate band and the valence band makes this photocurrent detectable.

  1. Measurement and Analysis of P2P IPTV Program Resource

    PubMed Central

    Chen, Xingshu; Wang, Haizhou; Zhang, Qi

    2014-01-01

    With the rapid development of P2P technology, P2P IPTV applications have received more and more attention. And program resource distribution is very important to P2P IPTV applications. In order to collect IPTV program resources, a distributed multi-protocol crawler is proposed. And the crawler has collected more than 13 million pieces of information of IPTV programs from 2009 to 2012. In addition, the distribution of IPTV programs is independent and incompact, resulting in chaos of program names, which obstructs searching and organizing programs. Thus, we focus on characteristic analysis of program resources, including the distributions of length of program names, the entropy of the character types, and hierarchy depth of programs. These analyses reveal the disorderly naming conventions of P2P IPTV programs. The analysis results can help to purify and extract useful information from chaotic names for better retrieval and accelerate automatic sorting of program and establishment of IPTV repository. In order to represent popularity of programs and to predict user behavior and popularity of hot programs over a period, we also put forward an analytical model of hot programs. PMID:24772008

  2. Measurement and analysis of P2P IPTV program resource.

    PubMed

    Wang, Wenxian; Chen, Xingshu; Wang, Haizhou; Zhang, Qi; Wang, Cheng

    2014-01-01

    With the rapid development of P2P technology, P2P IPTV applications have received more and more attention. And program resource distribution is very important to P2P IPTV applications. In order to collect IPTV program resources, a distributed multi-protocol crawler is proposed. And the crawler has collected more than 13 million pieces of information of IPTV programs from 2009 to 2012. In addition, the distribution of IPTV programs is independent and incompact, resulting in chaos of program names, which obstructs searching and organizing programs. Thus, we focus on characteristic analysis of program resources, including the distributions of length of program names, the entropy of the character types, and hierarchy depth of programs. These analyses reveal the disorderly naming conventions of P2P IPTV programs. The analysis results can help to purify and extract useful information from chaotic names for better retrieval and accelerate automatic sorting of program and establishment of IPTV repository. In order to represent popularity of programs and to predict user behavior and popularity of hot programs over a period, we also put forward an analytical model of hot programs.

  3. Inter-band optoelectronic properties in quantum dot structure of low band gap III-V semiconductors

    SciTech Connect

    Dey, Anup; Maiti, Biswajit; Chanda, Debasree

    2014-04-14

    A generalized theory is developed to study inter-band optical absorption coefficient (IOAC) and material gain (MG) in quantum dot structures of narrow gap III-V compound semiconductor considering the wave-vector (k{sup →}) dependence of the optical transition matrix element. The band structures of these low band gap semiconducting materials with sufficiently separated split-off valance band are frequently described by the three energy band model of Kane. This has been adopted for analysis of the IOAC and MG taking InAs, InSb, Hg{sub 1−x}Cd{sub x}Te, and In{sub 1−x}Ga{sub x}As{sub y}P{sub 1−y} lattice matched to InP, as example of III–V compound semiconductors, having varied split-off energy band compared to their bulk band gap energy. It has been found that magnitude of the IOAC for quantum dots increases with increasing incident photon energy and the lines of absorption are more closely spaced in the three band model of Kane than those with parabolic energy band approximations reflecting the direct the influence of energy band parameters. The results show a significant deviation to the MG spectrum of narrow-gap materials having band nonparabolicity compared to the parabolic band model approximations. The results reflect the important role of valence band split-off energies in these narrow gap semiconductors.

  4. Nonequilibrium Green's function formulation of intersubband absorption for nonparabolic single-band effective mass Hamiltonian

    NASA Astrophysics Data System (ADS)

    Kolek, Andrzej

    2015-05-01

    The formulas are derived that enable calculations of intersubband absorption coefficient within nonequilibrium Green's function method applied to a single-band effective-mass Hamiltonian with the energy dependent effective mass. The derivation provides also the formulas for the virtual valence band components of the two-band Green's functions which can be used for more exact estimation of the density of states and electrons and more reliable treatment of electronic transport in unipolar n-type heterostructure semiconductor devices.

  5. Nonequilibrium Green's function formulation of intersubband absorption for nonparabolic single-band effective mass Hamiltonian

    SciTech Connect

    Kolek, Andrzej

    2015-05-04

    The formulas are derived that enable calculations of intersubband absorption coefficient within nonequilibrium Green's function method applied to a single-band effective-mass Hamiltonian with the energy dependent effective mass. The derivation provides also the formulas for the virtual valence band components of the two-band Green's functions which can be used for more exact estimation of the density of states and electrons and more reliable treatment of electronic transport in unipolar n-type heterostructure semiconductor devices.

  6. Recognizing the emotional valence of names: an ERP study.

    PubMed

    Wang, Lin; Zhu, Zude; Bastiaansen, Marcel; Hagoort, Peter; Yang, Yufang

    2013-04-01

    Unlike common nouns, person names refer to unique entities and generally have a referring function. We used event-related potentials to investigate the time course of identifying the emotional meaning of nouns and names. The emotional valence of names and nouns were manipulated separately. The results show early N1 effects in response to emotional valence only for nouns. This might reflect automatic attention directed towards emotional stimuli. The absence of such an effect for names supports the notion that the emotional meaning carried by names is accessed after word recognition and person identification. In addition, both names with negative valence and emotional nouns elicited late positive effects, which have been associated with evaluation of emotional significance. This positive effect started earlier for nouns than for names, but with similar durations. Our results suggest that distinct neural systems are involved in the retrieval of names' and nouns' emotional meaning.

  7. Processing emotional pictures and words: effects of valence and arousal.

    PubMed

    Kensinger, Elizabeth A; Schacter, Daniel L

    2006-06-01

    There is considerable debate regarding the extent to which limbic regions respond differentially to items with different valences (positive or negative) or to different stimulus types (pictures or words). In the present event-related fMRI study, 21 participants viewed words and pictures that were neutral, negative, or positive. Negative and positive items were equated on arousal. The participants rated each item for whether it depicted or described something animate or inanimate or something common or uncommon. For both pictures and words, the amygdala, dorsomedial prefrontal cortex (PFC), and ventromedial PFC responded equally to all high-arousal items, regardless of valence. Laterality effects in the amygdala were based on the stimulus type (word = left, picture = bilateral). Valence effects were most apparent when the individuals processed pictures, and the results revealed a lateral/medial distinction within the PFC: The lateral PFC responded differentially to negative items, whereas the medial PFC was more engaged during the processing of positive pictures.

  8. Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Seidel, Robert; Winter, Bernd; Bradforth, Stephen E.

    2016-05-01

    The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway.

  9. Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy.

    PubMed

    Seidel, Robert; Winter, Bernd; Bradforth, Stephen E

    2016-05-27

    The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway.

  10. Localized Multi-Reference Approach for Mixed-Valence Systems

    NASA Astrophysics Data System (ADS)

    Helal, W.; Evangelisti, S.; Leininger, T.; Maynau, D.

    2008-09-01

    The electronic structure and some important intra-molecular charge transfer parameters were investigated at CAS-SCF, MRCI, CAS+S and multi-reference localization levels of theory for purely organic mixed-valence molecules. In particular, a spiro cation has been taken as a model system. The potential energy surfaces of the ground and the lower three excited electronic states have been computed within a two-state model, at CAS-SCF using TZP basis for the spiro cation, and an adiabatic double-well potential has been obtained for the ground electronic state. Our analysis of the geometry through the reaction coordinate indicate that the spiro cation is a valence trapped bistable system. The effect of non-dynamical correlation, using a localized orbital approach, was found to be crucial for a quantitative description of the electronic structure and some important electron transfer parameters of these organic mixed-valence systems.

  11. Dimensionality and its effects upon the valence electronic structure of ordered metallic systems

    SciTech Connect

    Tobin, J.G.

    1983-07-01

    The system c(10x2)Ag/Cu(001) was investigated with Angle-Resolved Photoemission (ARP), Low Energy Electron Diffraction (LEED) and Auger Electron Spectroscopy (AES). LEED and AES provided the calibration of a quartz microbalance used to measure the amount of silver evaporated onto the copper single crystal and also established the monolayer geometrical structure at one monolayer exposure. An off-normal ARP bandmapping study performed with polarized HeI and NeI radiation demonstrated the electronically two-dimensional nature of the silver d-bands at coverages of near one monolayer. The states at the surface Brillouin Zone center were assigned upon the basis of their polarization dependences and a structural model of hexagonal symmetry. A normal emission ARP experiment was performed at the Stanford Synchrotron Radiation Laboratory (SSRL) over the photon energy range of 6 to 32 eV. Data from it documented the evolution of the valence electronic structure of the silver overlayer from a two-dimensional hexagonal valence to a three-dimensional behavior converging towards that of bulk Ag(111). A structural study was attempted using the ARP technique of Normal Emission Photoelectron Diffraction over the photon energy range of 3.4 to 3.7 keV at SSRL, the results of which are inconclusive.

  12. Bond-valence methods for pKa prediction. II. Bond-valence, electrostatic, molecular geometry, and solvation effects

    SciTech Connect

    Bickmore, Barry R.; Rosso, Kevin M.; Tadanier, Christopher J.; Bylaska, Eric J.; Doud, Darrin

    2006-08-15

    In a previous contribution, we outlined a method for predicting (hydr)oxy-acid and oxide surface acidity constants based on three main factors: bond valence, Me?O bond ionicity, and molecular shape. Here electrostatics calculations and ab initio molecular dynamics simulations are used to qualitatively show that Me?O bond ionicity controls the extent to which the electrostatic work of proton removal departs from ideality, bond valence controls the extent of solvation of individual functional groups, and bond valence and molecular shape controls local dielectric response. These results are consistent with our model of acidity, but completely at odds with other methods of predicting acidity constants for use in multisite complexation models. In particular, our ab initio molecular dynamics simulations of solvated monomers clearly indicate that hydrogen bonding between (hydr)oxo-groups and water molecules adjusts to obey the valence sum rule, rather than maintaining a fixed valence based on the coordination of the oxygen atom as predicted by the standard MUSIC model.

  13. Bernauer's bands.

    PubMed

    Shtukenberg, Alexander; Gunn, Erica; Gazzano, Massimo; Freudenthal, John; Camp, Eric; Sours, Ryan; Rosseeva, Elena; Kahr, Bart

    2011-06-01

    Ferdinand Bernauer proposed in his monograph, "Gedrillte" Kristalle (1929), that a great number of simple, crystalline substances grow from solution or from the melt as polycrystalline spherulites with helically twisting radii that give rise to distinct bull's-eye patterns of concentric optical bands between crossed polarizers. The idea that many common molecular crystals can be induced to grow as mesoscale helices is a remarkable proposition poorly grounded in theories of polycrystalline pattern formation. Recent reinvestigation of one of the systems Bernauer described revealed that rhythmic precipitation in the absence of helical twisting accounted for modulated optical properties [Gunn, E. et al. J. Am. Chem. Soc. 2006, 128, 14234-14235]. Herein, the Bernauer hypothesis is re-examined in detail for three substances described in "Gedrillte" Kristalle, potassium dichromate, hippuric acid, and tetraphenyl lead, using contemporary methods of analysis not available to Bernauer, including micro-focus X-ray diffraction, electron microscopy, and Mueller matrix imaging polarimetry. Potassium dichromate is shown to fall in the class of rhythmic precipitates of undistorted crystallites, while hippuric acid spherulites are well described as helical fibrils. Tetraphenyl lead spherulites grow by twisting and rhythmic precipitation. The behavior of tetraphenyl lead is likely typical of many substances in "Gedrillte" Kristalle. Rhythmic precipitation and helical twisting often coexist, complicating optical analyses and presenting Bernauer with difficulties in the characterization and classification of the objects of his interest.

  14. The use and misuse of some positively valenced community concepts.

    PubMed

    Cowen, E L

    2001-02-01

    Considers the usage of four somewhat amorphous, but positively valenced, community mental health terms: primary prevention in mental health (and closely related notions such as wellness enhancement and positive psychology); resilience; charter schools; and empowerment. Use of these concepts often reflects a need to align with currently popular, "in"-terminology, rather than an intrinsic connection between what is being written about and a tight definition of the concept in question. Usages built primarily around a concept's positive valence and glitter tend to: (a) break down communication; (b) confuse rather than clarify; and (c) ultimately retard a field's growth and progress. PMID:11300664

  15. Valence QCD: Connecting QCD to the quark model

    SciTech Connect

    Liu, K.F.; Dong, S.J.; Draper, T.; Sloan, J.; Leinweber, D.; Wilcox, W.; Woloshyn, R.M.

    1999-06-01

    A valence QCD theory is developed to study the valence quark properties of hadrons. To keep only the valence degrees of freedom, the pair creation through the {ital Z} graphs is deleted in the connected insertions, whereas the sea quarks are eliminated in the disconnected insertions. This is achieved with a new {open_quotes}valence QCD{close_quotes} Lagrangian where the action in the time direction is modified so that the particle and antiparticle decouple. It is shown in this valence version of QCD that the ratios of isovector to isoscalar matrix elements (e.g., F{sub A}/D{sub A} and F{sub S}/D{sub S} ratios) in the nucleon reproduce the SU(6) quark model predictions in a lattice QCD calculation. We also consider how the hadron masses are affected on the lattice and discover new insights into the origin of dynamical mass generation. It is found that, within statistical errors, the nucleon and the {Delta} become degenerate for the quark masses we have studied (ranging from 1 to 4 times the strange mass). The {pi} and {rho} become nearly degenerate in this range. It is shown that valence QCD has the {ital C}, {ital P}, {ital T} symmetries. The lattice version is reflection positive. It also has the vector and axial symmetries. The latter leads to a modified partially conserved axial Ward identity. As a result, the theory has a U(2N{sub F}) symmetry in the particle-antiparticle space. Through lattice simulation, it appears that this is dynamically broken down to U{sub q}(N{sub F}){times}U{sub {bar q}}(N{sub F}). Furthermore, the lattice simulation reveals spin degeneracy in the hadron masses and various matrix elements. This leads to an approximate U{sub q}(2N{sub F}){times}U{sub {bar q}}(2N{sub F}) symmetry which is the basis for the valence quark model. In addition, we find that the masses of {ital N}, {Delta},{rho},{pi},a{sub 1}, and a{sub 0} all drop precipitously compared to their counterparts in the quenched QCD calculation. This is interpreted as due to the

  16. Role of the coordinating histidine in altering the mixed valency of Cu(A): an electron nuclear double resonance-electron paramagnetic resonance investigation.

    PubMed Central

    Lukoyanov, Dmitriy; Berry, Steven M; Lu, Yi; Antholine, William E; Scholes, Charles P

    2002-01-01

    The binuclear Cu(A) site engineered into Pseudomonas aeruginosa azurin has provided a Cu(A)-azurin with a well-defined crystal structure and a CuSSCu core having two equatorial histidine ligands, His120 and His46. The mutations His120Asn and His120Gly were made at the equatorial His120 ligand to understand the histidine-related modulation to Cu(A), notably to the valence delocalization over the CuSSCu core. For these His120 mutants Q-band electron nuclear double resonance (ENDOR) and multifrequency electron paramagnetic resonance (EPR) (X, C, and S-band), all carried out under comparable cryogenic conditions, have provided markedly different electronic measures of the mutation-induced change. Q-band ENDOR of cysteine C(beta) protons, of weakly dipolar-coupled protons, and of the remaining His46 nitrogen ligand provided hyperfine couplings that were like those of other binuclear mixed-valence Cu(A) systems and were essentially unperturbed by the mutation at His120. The ENDOR findings imply that the Cu(A) core electronic structure remains unchanged by the His120 mutation. On the other hand, multifrequency EPR indicated that the H120N and H120G mutations had changed the EPR hyperfine signature from a 7-line to a 4-line pattern, consistent with trapped-valence, Type 1 mononuclear copper. The multifrequency EPR data imply that the electron spin had become localized on one copper by the His120 mutation. To reconcile the EPR and ENDOR findings for the His120 mutants requires that either: if valence localization to one copper has occurred, the spin density on the cysteine sulfurs and the remaining histidine (His46) must remain as it was for a delocalized binuclear Cu(A) center, or if valence delocalization persists, the hyperfine coupling for one copper must markedly diminish while the overall spin distribution on the CuSSCu core is preserved. PMID:11964261

  17. Valence electron photoemission spectrum of semiconductors: ab initio description of multiple satellites.

    PubMed

    Guzzo, Matteo; Lani, Giovanna; Sottile, Francesco; Romaniello, Pina; Gatti, Matteo; Kas, Joshua J; Rehr, John J; Silly, Mathieu G; Sirotti, Fausto; Reining, Lucia

    2011-10-14

    The experimental valence band photoemission spectrum of semiconductors exhibits multiple satellites that cannot be described by the GW approximation for the self-energy in the framework of many-body perturbation theory. Taking silicon as a prototypical example, we compare experimental high energy photoemission spectra with GW calculations and analyze the origin of the GW failure. We then propose an approximation to the functional differential equation that determines the exact one-body Green's function, whose solution has an exponential form. This yields a calculated spectrum, including cross sections, secondary electrons, and an estimate for extrinsic and interference effects, in excellent agreement with experiment. Our result can be recast as a dynamical vertex correction beyond GW, giving hints for further developments. PMID:22107408

  18. The determination of dopant ion valence distributions in insulating crystals using XANES measurements.

    PubMed

    Hughes-Currie, Rosa B; Ivanovskikh, Konstantin V; Wells, Jon-Paul R; Reid, Michael F; Gordon, Robert A

    2016-04-01

    Ytterbium-doped wide-bandgap fluoride crystals CaF2, SrF2 and NaMgF3 have been measured using x-ray absorption near edge structure (XANES) on the L3 edge to determine the ratio of trivalent to divalent Yb ions present in the crystals. This study improves upon previous XANES measurements of dopant ion valency by taking into account the x-ray emission transition probabilities for the divalent and trivalent species instead of simply assuming that the relative concentrations may be determined by the ratio of the x-ray excitation band areas. Trivalent to divalent ratios as high as 5 are inferred even at low total dopant ion concentrations of 0.05 mol% Yb. PMID:26941175

  19. Compounds with mixed and intermediate sulfur valences in pyrite from the Amelia Mine, Southwest Wisconsin

    NASA Astrophysics Data System (ADS)

    Kucha, H.; Barnes, H. L.

    1995-02-01

    Compounds with mixed and intermediate sulfur valences form cloudy small inclusions in banded pyrite and 2 4 mm large rounded aggregates in pyrite stalactites. Such areas under high magnification of SEM appear to be a mixture of FeS2 with FeS2O3. Some of the microareas of 40 50 μm are homogeneous and can be identified by reflected light microscopy, microprobe and soft X-ray spectroscopy as Fe-thiosulphate, FeS2O3 or (Fe, Pb)2S3O7 with this compound having one sulfur -2 and two sulfurs +6. The intermediate sulfur compounds are enriched in Pb, Ni, Co and As.

  20. K2P potassium channels, mysterious and paradoxically exciting.

    PubMed

    Goldstein, Steve A N

    2011-08-01

    New evidence reveals that the common electrolyte disorder hypokalemia can induce K2P1 channels that are normally selective for K+ to break the rules and conduct Na+. This defiant behavior leads to paradoxical depolarization of many cells in the heart, increasing the risk for lethal arrhythmia. The new research resolves a mystery uncovered 50 years ago and bestows an array of new riddles. Here, I discuss how K2P1 might achieve this alchemy--through stable residence of the K+ selectivity filter in a Na+-conductive state between its open and C-inactive configurations--and predict that other K+ channels and environmental stimuli will be discovered to produce the same excitatory misconduct. PMID:21868351

  1. A micro-payment architecture for P2P networks

    NASA Astrophysics Data System (ADS)

    Zhang, Jie; Zhao, Zheng; Xiong, Xiao; Shi, Qingwei

    2007-09-01

    An important goal in P2P networks is that all peers provide resources. However, free riding and tragedy of common are real issues in P2P networks. To resolve these problems, most of the existing work is concerning probabilistic estimation to evaluate the trustworthiness or mechanism design to provide incentive. Instead of design a protocol to solve free riding, we build a micro-payment architecture for these existing protocols using virtual currency which can be more precisely measured and easily be replaced by reputation or other tokens. Our system can avoid from long-term trust learning interactions and high cost of collecting and analyzing reputation information. It can also provide peers incentive to truly report their connection type and security to malicious attacks.

  2. Supporting seamless mobility for P2P live streaming.

    PubMed

    Kim, Eunsam; Kim, Sangjin; Lee, Choonhwa

    2014-01-01

    With advent of various mobile devices with powerful networking and computing capabilities, the users' demand to enjoy live video streaming services such as IPTV with mobile devices has been increasing rapidly. However, it is challenging to get over the degradation of service quality due to data loss caused by the handover. Although many handover schemes were proposed at protocol layers below the application layer, they inherently suffer from data loss while the network is being disconnected during the handover. We therefore propose an efficient application-layer handover scheme to support seamless mobility for P2P live streaming. By simulation experiments, we show that the P2P live streaming system with our proposed handover scheme can improve the playback continuity significantly compared to that without our scheme.

  3. Supporting Seamless Mobility for P2P Live Streaming

    PubMed Central

    Kim, Eunsam; Kim, Sangjin; Lee, Choonhwa

    2014-01-01

    With advent of various mobile devices with powerful networking and computing capabilities, the users' demand to enjoy live video streaming services such as IPTV with mobile devices has been increasing rapidly. However, it is challenging to get over the degradation of service quality due to data loss caused by the handover. Although many handover schemes were proposed at protocol layers below the application layer, they inherently suffer from data loss while the network is being disconnected during the handover. We therefore propose an efficient application-layer handover scheme to support seamless mobility for P2P live streaming. By simulation experiments, we show that the P2P live streaming system with our proposed handover scheme can improve the playback continuity significantly compared to that without our scheme. PMID:24977171

  4. Protected Fe valence in quasi-two-dimensional α-FeSi2.

    PubMed

    Miiller, W; Tomczak, J M; Simonson, J W; Smith, G; Kotliar, G; Aronson, M C

    2015-05-01

    We report the first comprehensive study of the high temperature form (α-phase) of iron disilicide. Measurements of the magnetic susceptibility, magnetization, heat capacity and resistivity were performed on well characterized single crystals. With a nominal iron d(6) configuration and a quasi-two-dimensional crystal structure that strongly resembles that of LiFeAs, α-FeSi2 is a potential candidate for unconventional superconductivity. Akin to LiFeAs, α-FeSi2 does not develop any magnetic order and we confirm its metallic state down to the lowest temperatures (T = 1.8 K). However, our experiments reveal that paramagnetism and electronic correlation effects in α-FeSi2 are considerably weaker than in the pnictides. Band theory calculations yield small Sommerfeld coefficients of the electronic specific heat γ = Ce/T that are in excellent agreement with experiment. Additionally, realistic many-body calculations further corroborate that quasi-particle mass enhancements are only modest in α-FeSi2. Remarkably, we find that the natural tendency to vacancy formation in the iron sublattice has little influence on the iron valence and the density of states at the Fermi level. Moreover, Mn doping does not significantly change the electronic state of the Fe ion. This suggests that the iron valence is protected against hole doping and indeed the substitution of Co for Fe causes a rigid-band like response of the electronic properties. As a key difference from the pnictides, we identify the smaller inter-iron layer spacing, which causes the active orbitals near the Fermi level to be of a different symmetry in α-FeSi2. This change in orbital character might be responsible for the lack of superconductivity in this system, providing constraints on pairing theories in the iron based pnictides and chalcogenides. PMID:25837013

  5. Protected Fe valence in quasi-two-dimensional α-FeSi2

    NASA Astrophysics Data System (ADS)

    Miiller, W.; Tomczak, J. M.; Simonson, J. W.; Smith, G.; Kotliar, G.; Aronson, M. C.

    2015-05-01

    We report the first comprehensive study of the high temperature form (α-phase) of iron disilicide. Measurements of the magnetic susceptibility, magnetization, heat capacity and resistivity were performed on well characterized single crystals. With a nominal iron d6 configuration and a quasi-two-dimensional crystal structure that strongly resembles that of LiFeAs, α-FeSi2 is a potential candidate for unconventional superconductivity. Akin to LiFeAs, α-FeSi2 does not develop any magnetic order and we confirm its metallic state down to the lowest temperatures (T = 1.8 K). However, our experiments reveal that paramagnetism and electronic correlation effects in α-FeSi2 are considerably weaker than in the pnictides. Band theory calculations yield small Sommerfeld coefficients of the electronic specific heat γ = Ce/T that are in excellent agreement with experiment. Additionally, realistic many-body calculations further corroborate that quasi-particle mass enhancements are only modest in α-FeSi2. Remarkably, we find that the natural tendency to vacancy formation in the iron sublattice has little influence on the iron valence and the density of states at the Fermi level. Moreover, Mn doping does not significantly change the electronic state of the Fe ion. This suggests that the iron valence is protected against hole doping and indeed the substitution of Co for Fe causes a rigid-band like response of the electronic properties. As a key difference from the pnictides, we identify the smaller inter-iron layer spacing, which causes the active orbitals near the Fermi level to be of a different symmetry in α-FeSi2. This change in orbital character might be responsible for the lack of superconductivity in this system, providing constraints on pairing theories in the iron based pnictides and chalcogenides.

  6. DNA Compaction by Yeast Mitochondrial Protein ABF2p

    SciTech Connect

    Friddle, R W; Klare, J E; Noy, A; Corzett, M; Balhorn, R; Baskin, R J; Martin, S S; Baldwin, E P

    2003-05-09

    We used high resolution Atomic Force Microscopy (AFM) to image compaction of linear and circular DNA by the yeast mitochondrial protein ABF2p , which plays a major role in maintaining mitochondrial DNA. AFM images show that protein binding induces drastic bends in the DNA backbone for both linear and circular DNA. At high concentration of ABF2p DNA collapses into a tight globular structure. We quantified the compaction of linear DNA by measuring the end-to-end distance of the DNA molecule at increasing concentrations of ABF2p. We also derived a polymer statistical mechanics model that gives quantitative description of compaction observed in our experiments. This model shows that a number of sharp bends in the DNA backbone is often sufficient to cause DNA compaction. Comparison of our model with the experimental data showed excellent quantitative correlation and allowed us to determine binding characteristics for ABF2. Our studies indicate that ABF2 compacts DNA through a novel mechanism that involves bending of DNA backbone. We discuss the implications of such a mechanism for mitochondrial DNA maintenance.

  7. Pure P2P mediation system: A mappings discovery approach

    NASA Astrophysics Data System (ADS)

    selma, El yahyaoui El idrissi; Zellou, Ahmed; Idri, Ali

    2015-02-01

    The information integration systems consist in offering a uniform interface to provide access to a set of autonomous and distributed information sources. The most important advantage of this system is that it allows users to specify what they want, rather than thinking about how to get the responses. The works realized in this area have particular leads to two major classes of integration systems: the mediation systems based on the paradigm mediator / adapter and peer to peer systems (P2P). The combination of both systems has led to a third type; is the mediation P2P systems. The P2P systems are large-scale systems, self-organized and distributed. They allow the resource management in a completely decentralized way. However, the integration of structured information sources, heterogeneous and distributed proves to be a complex problem. The objective of this work is to propose an approach to resolve conflicts and establish a mapping between the heterogeneous elements. This approach is based on clustering; the latter is to group similar Peers that share common information in the same subnet. Thus, to facilitate the heterogeneity, we introduced three additional layers of our hierarchy of peers: internal schema, external schema and Schema directory peer. We used linguistic techniques, and precisely the name correspondence technique, that is based on the similarity of names to propose a correspondence.

  8. A Measurement of g2p at Low Q2

    NASA Astrophysics Data System (ADS)

    Cummings, M.

    2016-02-01

    Jefferson Lab has been at the forefront of a program to study the polarized structure of nucleons using electron scattering. Measurements of the spin dependent structure functions, g1 and g2, have proven to be powerful tools in testing and understanding QCD. The neutron structure function g2n has been measured extensively in Hall A at Jefferson Lab over a wide range of Q2, but data for g2p remains scarce. This docment will discuss the g2p experiment, which ran in Hall A at Jefferson Lab in the spring of 2012, and will provide the first measurement of g2p in the resonance region; covering 0.02 < Q2 < 0.2 GeV2. The 0th moment of g2 provides a test of the Burkhardt-Cottingham sum rule, which states that the integral of g2 over the Bjorken scaling variable x goes to zero. This sum rule, valid for all values of Q2, has been satisfied for the neutron, but a violation is suggested for the proton at high Q2. The 2nd moment allows for a benchmark test of χPT at low Q2. Specifically, the behavior of the longitudinally-transverse spin polarizability (δLT), as χPT calculations of this quantity deviate significantly from the measured neutron data. This document will discuss the current status of the analysis along with preliminary results.

  9. Recognizing the Emotional Valence of Names: An ERP Study

    ERIC Educational Resources Information Center

    Wang, Lin; Zhu, Zude; Bastiaansen, Marcel; Hagoort, Peter; Yang, Yufang

    2013-01-01

    Unlike common nouns, person names refer to unique entities and generally have a referring function. We used event-related potentials to investigate the time course of identifying the emotional meaning of nouns and names. The emotional valence of names and nouns were manipulated separately. The results show early N1 effects in response to emotional…

  10. Inner valence-shell vacancy production and molecular fragmentation

    NASA Astrophysics Data System (ADS)

    Montenegro, E. C.; Tavares, A. C.; Luna, H.; Wolff, W.

    2015-09-01

    Fragmentation of complex molecules is studied linking the fragment-ions to the primary vacancies produced in their molecular orbitals. It is observed that a model based in such association describes well rather complex molecules. Deviations from this model are clear indications that inner valence-shells and double ionization plays a key role in the production of some fragments.

  11. Emotional Valence and Arousal Effects on Memory and Hemispheric Asymmetries

    ERIC Educational Resources Information Center

    Mneimne, Malek; Powers, Alice S.; Walton, Kate E.; Kosson, David S.; Fonda, Samantha; Simonetti, Jessica

    2010-01-01

    This study examined predictions based upon the right hemisphere (RH) model, the valence-arousal model, and a recently proposed integrated model (Killgore & Yurgelun-Todd, 2007) of emotion processing by testing immediate recall and recognition memory for positive, negative, and neutral verbal stimuli among 35 right-handed women. Building upon…

  12. Tagging Multiple Emotional Stimuli: Negative Valence Has Little Benefit

    ERIC Educational Resources Information Center

    Watson, Derrick G.; Blagrove, Elisabeth

    2012-01-01

    Six experiments examined the influence of emotional valence on the tagging and enumeration of multiple targets. Experiments 1, 5 and 6 found that there was no difference in the efficiency of tagging/enumerating multiple negative or positive stimuli. Experiment 2 showed that, when neutral-expression face distractors were present, enumerating…

  13. Valence and spectral properties of rare-earth clusters

    NASA Astrophysics Data System (ADS)

    Peters, L.; Di Marco, I.; Litsarev, M. S.; Delin, A.; Katsnelson, M. I.; Kirilyuk, A.; Johansson, B.; Sanyal, B.; Eriksson, O.

    2015-07-01

    The rare earths are known to have intriguing changes of the valence, depending on the chemical surrounding or geometry. Here, we aim at predicting the transition of valence when passing from the atomic divalent limit to the bulk trivalent limit. This transition is analyzed by addressing clusters of various size for selected rare-earth elements, i.e., Sm, Tb, and Tm, via a theoretical treatment that combines density functional theory with atomic multiplet theory. Our results show that Tm clusters change from pure divalent to pure trivalent at a size of six atoms, while Tb clusters are already divalent for two atoms and stay so until eight atoms and the bulk limit. Instead, Sm clusters are respectively purely divalent up to eight atoms. For larger Sm clusters, a transition to a trivalent configuration is expected and likely accompanied by a regime of mixed valence. The valence of all rare-earth clusters, as a function of size, is predicted from the interpolation of our calculated results. These predictions are argued to be best investigated by spectroscopic measurements. To ease experimental analysis, we provide theoretical spectra, based on dynamical mean-field theory in the Hubbard I approximation.

  14. Social Learning Modulates the Lateralization of Emotional Valence

    ERIC Educational Resources Information Center

    Shamay-Tsoory, Simone G.; Lavidor, Michal; Aharon-Peretz, Judith

    2008-01-01

    Although neuropsychological studies of lateralization of emotion have emphasized valence (positive vs. negative) or type (basic vs. complex) dimensions, the interaction between the two dimensions has yet to be elucidated. The purpose of the current study was to test the hypothesis that recognition of basic emotions is processed preferentially by…

  15. Valence, Covalence, Hypervalence, Oxidation State, and Coordination Number

    ERIC Educational Resources Information Center

    Smith, Derek W.

    2005-01-01

    Valence as a numerical measure of an atom's combining power, expressed by the number of bonds it forms in a molecular formulation of the compound in question, was unable to cope with coordination compounds. The covalence of an atom is the nearest model equivalent, but is subject to ambiguity since it often depends on which bonding model is being…

  16. Vection Modulates Emotional Valence of Autobiographical Episodic Memories

    ERIC Educational Resources Information Center

    Seno, Takeharu; Kawabe, Takahiro; Ito, Hiroyuki; Sunaga, Shoji

    2013-01-01

    We examined whether illusory self-motion perception ("vection") induced by viewing upward and downward grating motion stimuli can alter the emotional valence of recollected autobiographical episodic memories. We found that participants recollected positive episodes more often while perceiving upward vection. However, when we tested a small moving…

  17. Mobile linkers on DNA-coated colloids: valency without patches.

    PubMed

    Angioletti-Uberti, Stefano; Varilly, Patrick; Mognetti, Bortolo M; Frenkel, Daan

    2014-09-19

    Colloids coated with single-stranded DNA (ssDNA) can bind selectively to other colloids coated with complementary ssDNA. The fact that DNA-coated colloids (DNACCs) can bind to specific partners opens the prospect of making colloidal "molecules." However, in order to design DNACC-based molecules, we must be able to control the valency of the colloids, i.e., the number of partners to which a given DNACC can bind. One obvious, but not very simple approach is to decorate the colloidal surface with patches of single-stranded DNA that selectively bind those on other colloids. Here we propose a design principle that exploits many-body effects to control the valency of otherwise isotropic colloids. Using a combination of theory and simulation, we show that we can tune the valency of colloids coated with mobile ssDNA, simply by tuning the nonspecific repulsion between the particles. Our simulations show that the resulting effective interactions lead to low-valency colloids self-assembling in peculiar open structures, very different from those observed in DNACCs with immobile DNA linkers.

  18. Heavy Drinking Relates to Positive Valence Ratings of Alcohol Cues

    PubMed Central

    Pulido, Carmen; Mok, Alex; Brown, Sandra A.; Tapert, Susan F.

    2009-01-01

    Background A positive family history of alcohol use disorders (FH) is a robust predictor of personal alcohol abuse and dependence. Exposure to problem-drinking models is one mechanism through which family history influences alcohol-related cognitions and drinking patterns. Similarly, exposure to alcohol advertisements is associated with alcohol involvement and the relationship between affective response to alcohol cues and drinking behavior has not been well established. In addition, the collective contribution that FH, exposure to different types of problem-drinking models (e.g., parents, peers), and personal alcohol use have on appraisal of alcohol-related stimuli has not been evaluated with a large sample. Objective We investigated the independent effects of FH, exposure to problem-drinking models, and personal alcohol use on valence ratings of alcohol pictures in a college sample. Method College students (N=227) completed measures of personal drinking and substance use, exposure to problem-drinking models, FH, and ratings on affective valence of 60 alcohol pictures. Results Greater exposure to non-familial problem-drinkers predicted greater drinking among college students (β = .17, p < .01). However, personal drinking was the only predictor of valence ratings of alcohol pictures (β= −.53, p < .001). Conclusions Personal drinking level predicted valence ratings of alcohol cues over and above FH, exposure to problem-drinking models, and demographic characteristics. This suggests that positive affective responses to alcohol pictures are more a function of personal experience (i.e., repeated heavy alcohol use) than vicarious learning. PMID:18855802

  19. "Plug-and-go" strategy to manipulate streptavidin valencies.

    PubMed

    Sun, Xun; Montiel, Daniel; Li, Hao; Yang, Haw

    2014-08-20

    The streptavidin-biotin set is one of the most widely utilized conjugation pairs in biotechnological applications. The tetravalent nature of streptavidin and its homologues, however, tends to result in such undesirable complications as cross-linking or ill-defined stoichiometry. Here, we describe a mutagenesis-free strategy to manipulate the valencies of wild-type streptavidin that only requires commercially available reagents. The basic idea is simple: one obtains the desired streptavidin valency by blocking off unwanted binding sites using ancillary biotin ("plug"); this way, the extraordinary fM-biotin-binding affinity is fully retained for the remaining sites in streptavidin. In the present implementation, the ancillary biotin is attached to an auxiliary separation handle, negatively charged DNA or His-tagged protein, via a photochemically or enzymatically cleavable linker. Mixing streptavidin with the ancillary biotin construct produces a distribution of streptavidin valencies. The subsequent chromatographic separation readily isolates the construct of desired streptavidin valency, and the auxiliary handles are easily removed afterward ("go"). We demonstrate how this "plug-and-go" strategy allows a precise control for the compositions of streptavidin-biotin conjugates at the single-molecule level. This low-entry-barrier protocol could further expand the application scope of the streptavidin technology.

  20. Voice and Valency in San Luis Potosi Huasteco

    ERIC Educational Resources Information Center

    Munoz Ledo Yanez, Veronica

    2014-01-01

    This thesis presents an analysis of the system of transitivity, voice and valency alternations in Huasteco of San Luis Potosi (Mayan) within a functional-typological framework. The study is based on spoken discourse and elicited data collected in the municipalities of Aquismon and Tancanhuitz de Santos in the state of San Luis Potosi, Mexico. The…

  1. Heavy drinking relates to positive valence ratings of alcohol cues.

    PubMed

    Pulido, Carmen; Mok, Alex; Brown, Sandra A; Tapert, Susan F

    2009-01-01

    A positive family history of alcohol use disorders (FH) is a robust predictor of personal alcohol abuse and dependence. Exposure to problem-drinking models is one mechanism through which family history influences alcohol-related cognitions and drinking patterns. Similarly, exposure to alcohol advertisements is associated with alcohol involvement and the relationship between affective response to alcohol cues and drinking behavior has not been well established. In addition, the collective contribution that FH, exposure to different types of problem-drinking models (e.g. parents, peers) and personal alcohol use have on appraisal of alcohol-related stimuli has not been evaluated with a large sample. We investigated the independent effects of FH, exposure to problem-drinking models and personal alcohol use on valence ratings of alcohol pictures in a college sample. College students (n = 227) completed measures of personal drinking and substance use, exposure to problem-drinking models, FH and ratings on affective valence of 60 alcohol pictures. Greater exposure to non-familial problem-drinkers predicted greater drinking among college students (beta = 0.17, P < 0.01). However, personal drinking was the only predictor of valence ratings of alcohol pictures (beta = -0.53, P < 0.001). Personal drinking level predicted valence ratings of alcohol cues over and above FH, exposure to problem-drinking models and demographic characteristics. This suggests that positive affective responses to alcohol pictures are more a function of personal experience (i.e. repeated heavy alcohol use) than vicarious learning.

  2. Intruder bands in ({ital Z}=53) {sup 113}I: Band termination interpretation

    SciTech Connect

    Waring, M.P.; Paul, E.S.; Beausang, C.W.; Clark, R.M.; Cunningham, R.A.; Davinson, T.; Forbes, S.A.; Fossan, D.B.; Gale, S.J.; Gizon, A.; Gizon, J.; Hauschild, K.; Hibbert, I.M.; James, A.N.; Jones, P.M.; Joyce, M.J.; LaFosse, D.R.; Page, R.D.; Ragnarsson, I.; Schnare, H.; Sellin, P.J.; Simpson, J.; Vaska, P.; Wadsworth, R.; Woods, P.J. ||||||

    1995-05-01

    High spin states in {sup 113}I were studied with the {sup 58}Ni({sup 58}Ni, 3{ital p}{gamma}) reaction at 240 MeV, using the EUROGAM array in Daresbury, United Kingdom, with 45 Ge detectors. A total of five deformed intruder bands extending to spins {ital I} ranging from (73/2--89/2){h_bar} have been identified, all of which reach frequencies {h_bar}{omega}{gt}1.0 MeV and excitation energies {similar_to}25 MeV. A gradual dropoff of the dynamic moment of inertia {ital scrI}{sup (2)} with increasing rotational frequency has been observed and attributed to a mode of ``soft`` band termination involving valence particle alignment. In this process, the nucleus progresses gradually, over many transitions, towards a noncollective oblate ({gamma}=+60{degree}) band terminating state.

  3. Multi-configuration Dirac-Hartree-Fock calculations of the transition rates of 2s22p2 - 2s2p3 and 2s2p3 - 2s22pnl (n ≥ 3) E1 transitions of N+

    NASA Astrophysics Data System (ADS)

    Shen, Xiaozhi; Liu, Juan; Zhou, Fuyang

    2016-10-01

    Wavefunctions were determined using the multi-configuration Dirac-Hartree-Fock method. The core-core, core-valence, valence correlation, Breit interaction and quantum electrodynamics effects, as well as some higher-order correlation effects, were considered to obtain accurate wavelengths (λ), oscillator strengths (gf) and transition rates (A) of 2s22p2 - 2s2p3, 2s2p3 - 2s22pnl (n ≥ 3) and 2s2p3 - 2s2p23s E1 transitions. The branching ratio of 2s2p3 5S^o_2 (namely Aλ2143.45/Aλ2139.68) based on the latest calculation of 2.462 ± 0.119 is recommended for the determination of a nebula's electron temperature and electron density. The largest calculated gf value of 2s2p3 - 2s22p4p is λ630.65, differing from that of λ1060.2 (i.e. 2s2p3 3P^o_2 - 2s22p4p 3S1) that was observed with the largest intensities in the Orion Nebula spectrum. In addition, the energy levels and the splittings of 2s2p3, the extremely difficult calculations of the rates of two-electron one-photon transitions as well as those of the very small intercombination A of 2s2p3 5S^o_2 were studied in detail. Because of the weak spin-orbit interaction, accurately calculating the levels 3P^o_{1,2,0} (or 3D^o_{3,2,1}) and their transition matrix elements is very sensitive to relativistic and electron correlation effects. A special case for this is when the transition operators synchronously applied to wavefunctions with regard to 2s2p3 3Po and 2s22pnl (n = 4) become extremely sensitive to some higher-order correlation effects.

  4. Uncovering the behavior of Hf2Te2P and the candidate Dirac metal Zr2Te2P

    NASA Astrophysics Data System (ADS)

    Chen, K.-W.; Das, S.; Rhodes, D.; Memaran, S.; Besara, T.; Siegrist, T.; Manousakis, E.; Balicas, L.; Baumbach, R. E.

    2016-04-01

    Results are reported for single crystal specimens of Hf2Te2P and compared to its structural analogue Zr2Te2P, which was recently proposed to be a potential reservoir for Dirac physics [1]. Both materials are produced using the iodine vapor phase transport method and the resulting crystals are exfoliable. The bulk electrical transport and thermodynamic properties indicate Fermi liquid behavior at low temperature for both compounds. Quantum oscillations are observed in magnetization measurements for fields applied parallel but not perpendicular to the c-axis, suggesting that the Fermi surfaces are quasi-two dimensional. Frequencies are determined from quantum oscillations for several parts of the Fermi surfaces. Lifshitz-Kosevich fits to the temperature dependent amplitudes of the oscillations reveal small effective masses, with a particularly small value {{m}\\ast}=0.046{{m}0} for the α branch of Zr2Te2P. Electronic structure calculations are in good agreement with quantum oscillation results and illustrate the effect of a stronger spin-orbit interaction going from Zr to Hf. These results suggest that by using appropriate tuning parameters this class of materials may deepen the pool of novel Dirac phenomena.

  5. Band Anticrossing in Highly Mismatched Compound Semiconductor Alloys

    NASA Technical Reports Server (NTRS)

    Yu, Kin Man; Wu, J.; Walukiewicz, W.; Ager, J. W.; Haller, E. E.; Miotkowski, I.; Su, Ching-Hua; Curreri, Peter A. (Technical Monitor)

    2001-01-01

    Compound semiconductor alloys in which metallic anions are partially replaced with more electronegative isoelectronic atoms have recently attracted significant attention. Group IIIN(sub x)V(sub 1-x) alloys with a small amount of the electronegative N substituting more metallic column V elements has been the most extensively studied class of such Highly Mismatched Alloys (HMAs). We have shown that many of the unusual properties of the IIIN(sub x)V(sub 1-x) alloys can be well explained by the Band Anticrossing (BAC) model that describes the electronic structure in terms of an interaction between highly localized levels of substitutional N and the extended states of the host semiconductor matrix. Most recently the BAC model has been also used to explain similar modifications of the electronic band structure observed in Te-rich ZnS(sub x)Te(sub 1-x) and ZnSe(sub y)Te(sub 1-y) alloys. To date studies of HMAs have been limited to materials with relatively small concentrations of highly electronegative atoms. Here we report investigations of the electronic structure of ZnSe(sub y)Te(sub 1-y) alloys in the entire composition range, y between 0 and 1. The samples used in this study are bulk ZnSe(sub y)Te(sub 1-y) crystals grown by either a modified Bridgman method or by physical vapor transport. Photomodulated reflection (PR) spectroscopy was used to measure the composition dependence of optical transitions from the valence band edge and from the spin-orbit split off band to the conduction band. The pressure dependence of the band gap was measured using optical absorption in a diamond anvil cell. We find that the energy of the spin-orbit split off valence band edge does not depend on composition and is located at about 3 eV below the conduction band edge of ZnSe. On the Te-rich side the pressure and the composition dependence of the optical transitions are well explained by the BAC model which describes the downward shift of the conduction band edge in terms of the

  6. Band Anticrossing in Highly Mismatched Compound Semiconductor Alloys

    NASA Technical Reports Server (NTRS)

    Yu, Kin Man; Wu, J.; Walukiewicz, W.; Ager, J. W.; Haller, E. E.; Miotkowski, I.; Ramdas, A.; Su, Ching-Hua; Whitaker, Ann F. (Technical Monitor)

    2001-01-01

    Compound semiconductor alloys in which metallic anions are partially replaced with more electronegative isoelectronic atoms have recently attracted significant attention. Group IIIN(x)V(1-x), alloys with a small amount of the electronegative N substituting more metallic column V elements has been the most extensively studied class of such Highly Mismatched Alloys (HMAs). We have shown that many of the unusual properties of the IIIN(x),V(1-x) alloys can be well explained by the Band Anticrossing (BAC) model that describes the electronic structure in terms of an interaction between highly localized levels of substitutional N and the extended states of the host semiconductor matrix. Most recently the BAC model has been also used to explain similar modifications of the electronic band structure observed in Te-rich ZnS(x)Te(l-x) and ZnSe(Y)Te(1-y) alloys. To date studies of HMAs have been limited to materials with relatively small concentrations of highly electronegative atoms. Here we report investigations of the electronic structure of ZnSe(y)Te(1-y) alloys in the entire composition range, 0 less than or equal to y less than or equal to 1. The samples used in this study are bulk ZnSe(y)Te(1-y) crystals grown by either a modified Bridgman method or by physical vapor transport. Photomodulated reflection (PR) spectroscopy was used to measure the composition dependence of optical transitions from the valence band edge and from the spin-orbit split off band to the conduction band. The pressure dependence of the band gap was measured using optical absorption in a diamond anvil cell. We find that the energy of the spin-orbit split off valence band edge does not depend on composition and is located at about 3 eV below the conduction band edge of ZnSe. On the Te-rich side the pressure and the composition dependence of the optical transitions are well explained by the BAC model which describes the downward shift of the conduction band edge in terms of the interaction between

  7. Ultrafast dynamics. Attosecond band-gap dynamics in silicon.

    PubMed

    Schultze, Martin; Ramasesha, Krupa; Pemmaraju, C D; Sato, S A; Whitmore, D; Gandman, A; Prell, James S; Borja, L J; Prendergast, D; Yabana, K; Neumark, Daniel M; Leone, Stephen R

    2014-12-12

    Electron transfer from valence to conduction band states in semiconductors is the basis of modern electronics. Here, attosecond extreme ultraviolet (XUV) spectroscopy is used to resolve this process in silicon in real time. Electrons injected into the conduction band by few-cycle laser pulses alter the silicon XUV absorption spectrum in sharp steps synchronized with the laser electric field oscillations. The observed ~450-attosecond step rise time provides an upper limit for the carrier-induced band-gap reduction and the electron-electron scattering time in the conduction band. This electronic response is separated from the subsequent band-gap modifications due to lattice motion, which occurs on a time scale of 60 ± 10 femtoseconds, characteristic of the fastest optical phonon. Quantum dynamical simulations interpret the carrier injection step as light-field-induced electron tunneling.

  8. Band gap engineering via doping: A predictive approach

    NASA Astrophysics Data System (ADS)

    Andriotis, Antonis N.; Menon, Madhu

    2015-03-01

    We employ an extension of Harrison's theory at the tight binding level of approximation to develop a predictive approach for band gap engineering involving isovalent doping of wide band gap semiconductors. Our results indicate that reasonably accurate predictions can be achieved at qualitative as well as quantitative levels. The predictive results were checked against ab initio ones obtained at the level of DFT/SGGA + U approximation. The minor disagreements between predicted and ab initio results can be attributed to the electronic processes not incorporated in Harrison's theory. These include processes such as the conduction band anticrossing [Shan et al., Phys. Rev. Lett. 82, 1221 (1999); Walukiewicz et al., Phys. Rev. Lett. 85, 1552 (2000)] and valence band anticrossing [Alberi et al., Phys. Rev. B 77, 073202 (2008); Appl. Phys. Lett. 92, 162105 (2008); Appl. Phys. Lett. 91, 051909 (2007); Phys. Rev. B 75, 045203 (2007)], as well as the multiorbital rehybridization. Another cause of disagreement between the results of our predictive approach and the ab initio ones is shown to be the result of the shift of Fermi energy within the impurity band formed at the edge of the valence band maximum due to rehybridization. The validity of our approach is demonstrated with example applications for the systems GaN1-xSbx, GaP1-xSbx, AlSb1-xPx, AlP1-xSbx, and InP1-xSbx.

  9. Increasing efficiency in intermediate band solar cells with overlapping absorptions

    NASA Astrophysics Data System (ADS)

    Krishna, Akshay; Krich, Jacob J.

    2016-07-01

    Intermediate band (IB) materials are promising candidates for realizing high efficiency solar cells. In IB photovoltaics, photons are absorbed in one of three possible electronic transitions—valence to conduction band, valence to intermediate band, or intermediate to conduction band. With fully concentrated sunlight, when the band gaps have been chosen appropriately, the highest efficiency IB solar cells require that these three absorptions be non-overlapping, so absorbed photons of fixed energy contribute to only one transition. The realistic case of overlapping absorptions, where the transitions compete for photons, is generally considered to be a source of loss. We show that overlapping absorptions can in fact lead to significant improvements in IB solar cell efficiencies, especially for IB that are near the middle of the band gap. At low to moderate concentration, the highest efficiency requires overlapping absorptions. We use the detailed-balance method and indicate how much overlap of the absorptions is required to achieve efficiency improvements, comparing with some known cases. These results substantially broaden the set of materials that can be suitable for high-efficiency IB solar cells.

  10. Production of photocurrent due to intermediate-to-conduction-band transitions: a demonstration of a key operating principle of the intermediate-band solar cell.

    PubMed

    Martí, A; Antolín, E; Stanley, C R; Farmer, C D; López, N; Díaz, P; Cánovas, E; Linares, P G; Luque, A

    2006-12-15

    We present intermediate-band solar cells manufactured using quantum dot technology that show for the first time the production of photocurrent when two sub-band-gap energy photons are absorbed simultaneously. One photon produces an optical transition from the intermediate-band to the conduction band while the second pumps an electron from the valence band to the intermediate-band. The detection of this two-photon absorption process is essential to verify the principles of operation of the intermediate-band solar cell. The phenomenon is the cornerstone physical principle that ultimately allows the production of photocurrent in a solar cell by below band gap photon absorption, without degradation of its output voltage. PMID:17280325

  11. Scandium Selenophosphates: Structure and Properties of K4Sc2(PSe4)2(P2Se6).

    PubMed

    Syrigos, Jonathan C; Kanatzidis, Mercouri G

    2016-05-01

    The new compound K4Sc2P4Se14 was synthesized via the polychalcogenide flux method. It crystallizes in the space group C2/c, and the structure is composed of (1)/∞[Sc2P4Se14(4-)] chains that are separated by K(+) cations. The structural motif features two [PSe4](3-) units and one [P2Se6](4-) unit bridging the Sc centers and has not been reported for any other compound. The (1)/∞[Sc2P4Se14(4-)] chains pack in a crosshatched pattern perpendicular to the c axis of the crystal, forming channels for half of the K(+) atoms while the other half occupy empty space between the chains. The orange-yellow crystals of K4Sc2P4Se14 are air-sensitive and gradually turn red over the course of a couple hours. The band gap of the phase is 2.25(2) eV, and Raman spectroscopy shows the symmetric stretches of the selenophosphate groups to be at 231 and 216 cm(-1) for the [PSe4](3-) and [P2Se6](4-) units, respectively. Solid-state (31)P MAS NMR of K4Sc2P4Se14 shows two prominent peaks at 11.31 and -23.07 ppm and one minor peak at -106.36 ppm, most likely due to degradation of the product or an unknown second phase.

  12. Dual doped monolayer and bilayer graphene: The case of 4p and 2p elements

    NASA Astrophysics Data System (ADS)

    Denis, Pablo A.; Iribarne, Federico

    2016-08-01

    4p/2p dual-doped monolayer and bilayer graphene were studied via first principle calculations. Generally, dopants prefer to be agglomerated. A second dopant significantly reduces formation energies. Thus, partially reduced graphene oxide would favor substitutional doping by facilitating the introduction of the 4p dopants. Dual-doping can tune the band gap from 0.1 to 0.8 eV. For bilayer graphene, large atomic radii elements (Gallium and Germanium) form interlayer bonds with the undoped sheet. For some dual-doped graphenes, interlayer GaC and GeC bonds were formed, increasing the chemical reactivity of the undoped layer and affecting its electronic structure, with metallic or semiconducting characters observed.

  13. Precision lifetime measurements of the 2p levels in lithium

    SciTech Connect

    Berry, H.G.; Kurtz, C.; Tanner, C.E.

    1995-08-01

    These measurements are motivated by the theoretical challenges posed by lithium. The three-electron lithium atom is one of the simplest atomic systems with which to test atomic structure calculations. Recently, there were several ab initio calculations of the lithium 2s-2p oscillator strengths, which agree to 0.15%. However, the theoretical results differ by 5 sigma from the precise fast-beam-laser lifetime measurement of Gaupp and Andra (Berlin). Hence the need for a new independent and precise measurement. Improvements were added to the fast beam laser techniques developed for cesium in order to measure the lithium 2p state lifetime. Although the technique is similar to that of cesium, the lithium atom presents a few new complications. Since the atom is lighter, it travels more quickly through the interaction and detection regions. Therefore, the 670 nm wavelength requires a dye laser to produce sufficient intensity to populate the excited state. Unfortunately, the intensity of the dye laser is inherently less stable than that of a diode laser. Another complication is that the ion-beam intensity is much more sensitive to fluctuations in the accelerating voltage. Two detectors were added: one to monitor the ion-beam intensity, and the other to monitor the laser power. With the information from the additional detectors, a new data analysis scheme was developed. Sufficient data were taken to evaluate the benefits of the new detectors. No additional work is planned at Argonne for this experiment.

  14. Spectrometer Optics Calibration for Jefferson Lab g2^p Experiment

    NASA Astrophysics Data System (ADS)

    Gu, Chao

    2013-04-01

    The proton spin-dependent structure function g2^p in the resonance region has been measured in a recent experiment at Jefferson Lab's Hall A. The goal of this experiment is to determine the g2^p structure function in the Q^2 region of 0.02-0.20 GeV^2 by using a transversely polarized NH3 target. The Hall A High Resolution Spectrometers (HRS) were used to provide an inclusive measurement of scattered electrons at 5.69^o. A pair of septum magnets were used to bend the 5.69^o scatted electrons into the 12.5^o spectrometers. A full optics calibration of the spectrometer is required to extract the kinematic quantities at the interaction vertex. However, the calibration procedure is challenging due to the complications from the strong transverse target field (2.5 T and 5.0 T) and the varied field configurations of the septum magnets. The details of the optics calibration and the progress will be described in this talk.

  15. Fragrance material review on 2-p-tolylethanol.

    PubMed

    Scognamiglio, J; Jones, L; Letizia, C S; Api, A M

    2012-09-01

    A toxicologic and dermatologic review of 2-p-tolylethanol when used as a fragrance ingredient is presented. 2-p-tolylethanol is a member of the fragrance structural group Aryl Alkyl Alcohols and is a primary alcohol. The AAAs are a structurally diverse class of fragrance ingredients that includes primary, secondary, and tertiary alkyl alcohols covalently bonded to an aryl (Ar) group, which may be either a substituted or unsubstituted benzene ring. The common structural element for the AAA fragrance ingredients is an alcohol group-C-(R1)(R2)OH and generically the AAA fragrances can be represented as an Ar-C-(R1)(R2)OH or Ar-Alkyl-C-(R1)(R2)OH group. This review contains a detailed summary of all available toxicology and dermatology papers that are related to this individual fragrance ingredient and is not intended as a stand-alone document. A safety assessment of the entire Aryl Alkyl Alcohols will be published simultaneously with this document; please refer to Belsito et al. (2012) for an overall assessment of the safe use of this material and all other branched chain saturated alcohols in fragrances.

  16. The RP-Mdm2-p53 Pathway and Tumorigenesis

    PubMed Central

    Miliani de Marval, Paula L.; Zhang, Yanping

    2011-01-01

    The dynamic processes of cell growth and division are under constant surveillance. As one of the primary “gatekeepers” of the cell, the p53 tumor suppressor plays a major role in sensing and responding to a variety of stressors to maintain cellular homeostasis. Recent studies have shown that inhibition of ribosomal biogenesis can activate p53 through ribosomal protein (RP)-mediated suppression of Mdm2 E3 ligase activity. Mutations in Mdm2 that disrupt RP binding have been detected in human cancers; however, the physiological significance of the RP-Mdm2 interaction is not completely understood. We generated mice carrying a single cysteine-to-phenylalanine substitution in the central zinc finger of Mdm2 (Mdm2C305F) that disrupts Mdm2’s binding to RPL11 and RPL5. Despite being developmentally normal and maintaining an intact p53 response to DNA damage, the Mdm2C305F mice demonstrate a diminished p53 response to perturbations in ribosomal biogenesis, providing the first in vivo evidence for an RP-Mdm2-p53 signaling pathway. Here we review some recent studies about RP-Mdm2-p53 signaling and speculate on the relevance of this pathway to human cancer. PMID:21406728

  17. Affinity Purification and Characterization of a G-Protein Coupled Receptor, Saccharomyces cerevisiae Ste2p

    SciTech Connect

    Lee, Byung-Kwon; Jung, Kyung-Sik; Son, Cagdas D; Kim, Heejung; Verberkmoes, Nathan C; Arshava, Boris; Naider, Fred; Becker, Jeffrey Marvin

    2007-01-01

    We present a rare example of a biologically active G protein coupled receptor (GPCR) whose purity and identity were verified by mass spectrometry after being purified to near homogeneity from its native system. An overexpression vector was constructed to encode the Saccharomyces cerevisiae GPCR -factor receptor (Ste2p, the STE2 gene product) containing a 9-amino acid sequence of rhodopsin that served as an epitope/affinity tag. In the construct, two glycosylation sites and two cysteine residues were removed to aid future structural and functional studies. The receptor was expressed in yeast cells and was detected as a single band in a western blot indicating the absence of glycosylation. Tests of the epitope-tagged, mutated receptor showed it maintained its full biological activity. For extraction of Ste2p, yeast membranes were solubilized with 0.5 % n-dodecyl maltoside (DM). Approximately 120 g of purified -factor receptor was obtained per liter of culture by single-step affinity chromatography using a monoclonal antibody to the rhodopsin epitope. The binding affinity (Kd) of the purified -factor receptor in DM micelles was 28 nM as compared to Kd = 12.7 nM for Ste2p in cell membranes, and approximately 40 % of the purified receptor was correctly folded as judged by ligand saturation binding. About 50 % of the receptor sequence was retrieved from MALDITOF and nanospray mass spectrometry after CNBr digestion of the purified receptor. The methods described will enable structural studies of the -factor receptor and may provide an efficient technique to purify other GPCRs that have been functionally expressed in yeast.

  18. Identification of lysines within membrane-anchored Mga2p120 that are targets of Rsp5p ubiquitination and mediate mobilization of tethered Mga2p90

    PubMed Central

    Bhattacharya, Sabyasachi; Shcherbik, Natalia; Vasilescu, Julian; Smith, Jeffrey C.; Figeys, Daniel; Haines, Dale S.

    2009-01-01

    Summary Mga2p90 is an endoplasmic reticulum (ER) localized transcription factor that is released from the ER membrane by a unique ubiquitin-dependent mechanism. Mga2p90 mobilization requires poly-ubiquitination of its associating membrane-bound Mga2p120 anchor and subsequent Mga2p120-Mga2p90 complex disassembly that is mediated by ATPase Cdc48p and its heteromeric ubiquitin-binding adaptor Npl4p-Ufd1p. Although previous studies have identified the ubiquitin ligase (i.e. Rsp5p) and ligase binding site on Mga2p120 that play a role in this process, the amino acids of Mga2p120 that are targets of ubiquitination and promote Mga2p90 mobilization are unknown. We have identified using mass spectrometry analysis of in vitro ubiquitinated Mga2p120-Mga2p90 complex that lysines 983 and 985 contained within the carboxy-terminal domain of Mga2p120 are Rsp5p-directed ubiquitin conjugation sites. Mutation of these residues as well as proximally located lysine 980 results in suppression of Mga2p120 ubiquitination in vitro and in vivo, inefficient liberation of Mga2p90 by Cdc48pNpl4p/Ufd1p in vitro, and ER retention of Mga2p in cells. Moreover, mga2Δ/spt23ts harboring Rsp5p binding and conjugation mga2 mutants express low OLE1 (an Mga2p90 target gene) transcripts and display reduced growth. We conclude that residues 980, 983 and 985 are targets of Rsp5p-induced poly-ubiquitination and mediate Cdc48pNpl4p/Ufd1p-dependent Mga2p90-Mga2p120 separation and Mga2p90 mobilization. PMID:19061897

  19. Effects of valence-valence, core-valence and core-core correlations on the fine-structure energy levels in Zn-like ions

    NASA Astrophysics Data System (ADS)

    Hu, F.; Jiang, G.; Yang, J. M.; Wang, C. K.; Zhao, X. F.; Hao, L. H.

    2011-01-01

    We report on large ab initio calculation for the 4s^2- 4s4p transitions in the Zinc-like sequence, using the multi-configuration Dirac-Hartree-Fock method. Results for fine-structure energy levels, the wavelengths, transition rates and lifetimes between Z = 70 (Yb) and Z= 92 (U) are presented and compared with other theories and experiments. The calculated values including core-valence correlation are found to be similar and to compare very well with other theories and experiments values. We believe that our extensive calculated values can guide experimentalists in identifying the fine-structure levels in their future work.

  20. Kinetics of the Reactions of F((sup 2)P) and Cl((sup 2)P) with HNO3

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Wells, J. R.; Nicovich, J. M.

    1997-01-01

    The kinetics of the reactions of HNO3 with fluorine (k(sub 1)) and Chlorine (k(sub 2)) atoms have been studied by using a time-resolved long-path laser absorption technique to monitor the appearance of product NO3 radicals following 351-nm pulsed laser photolysis of X2/HNO3/He mixtures (X = F,Cl). Absolute rate coefficients for the F((sup 2)P) + HNO reaction have been determined over the temperature range 260-373 K. Between 260 and 320 K, the data are adequately represented by the Arrhenius expression k(sub 1)(T) = (6.0 +/- 2.6) x 10(exp -12) exp[(40 +/- 120)/T]cu cm/(molecule.s). Between 335 and 373 K, the rate coefficient is found to be (2.0 +/- 0.3) x 10(exp -11)cu cm/(molecule.s) independent of temperature. The observed temperature dependence suggests that reaction proceeds via competing direct abstraction and complex pathways. No NO3 production was observed in the experiments with X equals Cl, thus establishing that k(sub 2)(298 K) is less than 2 x 10(exp -16) cu cm/(molecule.s). The Cl((sup 2)P) + HNO reaction was also investigated by using a pulsed laser photolysis-resonance fluorescence technique to monitor the decay of Cl((sup 2)P). Upper limit values for k(sub 2) obtained from these experiments, in units of 10(exp -16)cu cm/(molecule.s), are 13 at 298 K and 10 at 400 K.

  1. Band-gap and band-edge engineering of multicomponent garnet scintillators from first principles

    DOE PAGES

    Yadav, Satyesh K.; Uberuaga, Blas P.; Nikl, Martin; Jiang, Chao; Stanek, Christopher R.

    2015-11-24

    Complex doping schemes in R3Al5O12 (where R is the rare-earth element) garnet compounds have recently led to pronounced improvements in scintillator performance. Specifically, by admixing lutetium and yttrium aluminate garnets with gallium and gadolinium, the band gap is altered in a manner that facilitates the removal of deleterious electron trapping associated with cation antisite defects. Here, we expand upon this initial work to systematically investigate the effect of substitutional admixing on the energy levels of band edges. Density-functional theory and hybrid density-functional theory (HDFT) are used to survey potential admixing candidates that modify either the conduction-band minimum (CBM) or valence-bandmore » maximum (VBM). We consider two sets of compositions based on Lu3B5O12 where B is Al, Ga, In, As, and Sb, and R3Al5O12, where R is Lu, Gd, Dy, and Er. We find that admixing with various R cations does not appreciably affect the band gap or band edges. In contrast, substituting Al with cations of dissimilar ionic radii has a profound impact on the band structure. We further show that certain dopants can be used to selectively modify only the CBM or the VBM. Specifically, Ga and In decrease the band gap by lowering the CBM, while As and Sb decrease the band gap by raising the VBM, the relative change in band gap is quantitatively validated by HDFT. These results demonstrate a powerful approach to quickly screen the impact of dopants on the electronic structure of scintillator compounds, identifying those dopants which alter the band edges in very specific ways to eliminate both electron and hole traps responsible for performance limitations. Furthermore, this approach should be broadly applicable for the optimization of electronic and optical performance for a wide range of compounds by tuning the VBM and CBM.« less

  2. Work Valence as a Predictor of Academic Achievement in the Family Context

    ERIC Educational Resources Information Center

    Porfeli, Erik; Ferrari, Lea; Nota, Laura

    2013-01-01

    This study asserts a theoretical model of academic and work socialization within the family setting. The presumed associations between parents' work valences, children's work valences and valence perceptions, and children's academic interest and achievement are tested. The results suggest that children's perceptions of parents…

  3. Distinct Brain Systems Underlie the Processing of Valence and Arousal of Affective Pictures

    ERIC Educational Resources Information Center

    Nielen, M. M. A.; Heslenfeld, D. J.; Heinen, K.; Van Strien, J. W.; Witter, M. P.; Jonker, C.; Veltman, D. J.

    2009-01-01

    Valence and arousal are thought to be the primary dimensions of human emotion. However, the degree to which valence and arousal interact in determining brain responses to emotional pictures is still elusive. This functional MRI study aimed to delineate neural systems responding to valence and arousal, and their interaction. We measured neural…

  4. Characterization of p-type wide band gap transparent oxide for heterojunction devices

    NASA Astrophysics Data System (ADS)

    Lim, Sang-Hyun

    Transparent p-type CuCr1-xMgxO2 wide band gap oxide semiconductor thin films were deposited over quartz substrates by chemical spray pyrolysis technique using metalloorganic precursors. A mechanism of synthesis of CuCrO2 films involving precursor decomposition, oxidation, and reaction between constituent oxides in the spray deposition process is presented. Crystalline single phase CuCrO2 delafossite structure was dominant in ≥700ºC argon ambient annealed films but the as-deposited films contained spinel CuCr2O4 mixed phases as shown by XRD and XPS studies. Spin-orbital energy ˜9.8eV in Cr 2p electron spectra consistent with Cr3+ valence state and Cr 2p3/2 resolved peaks show mixed valence state on Cr4+ /Cr6+ confirming CuCr1-xMgxO 2 compound phase in the films. Effect of substrate temperature, film thickness, and acceptor Mg2+ doping on crystallographic structure, optical, electrical conductivity and thermoelectric coefficient was investigated. The invariance of the alpha- and increase of the c-lattice parameter with Mg concentration suggests that Mg2+ ions are introduced at the Cr3+ site. Highly transparent ≥80% CuCr 0.93Mg0.07O2 films with direct and indirect optical band gaps 3.08 and 2.58eV for 155 nm and 3.14 and 2.79eV for 305nm thin films, respectively were obtained. Photoluminescence emission bands at 532 and 484nm interpreted to arise from 3d94s1 and 3d 10 Cu+ intra-band transitions. Electrical conductivity of CuCr0.93Mg0.07O 2 films ranged from 0.6-1.0 Scm-1 and exhibits activation energies ˜0.11eV in 300-420K and ˜0.23eV in ≥ 420K region ascribed to activated conduction and grain boundary trap assisted conduction, respectively. Restricted by the Mg solubility, the substituted Mg dopants limited to x≤0.05 are only able to contribute to the optimum hole carrier in the range ˜2-4x1019cm-3 and thus no substantial increase of electrical conductivity could be realized with increased Mg concentration. A major fraction of Mg atoms do not act as

  5. Laparoscopic gastric banding - discharge

    MedlinePlus

    ... laparoscopic gastric banding - discharge; Obesity gastric banding discharge; Weight loss - gastric banding discharge ... as your body gets used to your weight loss and your weight becomes stable. Weight loss may be slower after ...

  6. Interchannel coupling effects in the valence photoionization of SF6

    NASA Astrophysics Data System (ADS)

    Jose, Jobin; Lucchese, Robert; Rescigno, Tom

    2014-05-01

    The complex Kohn and polyatomic Schwinger variational techniques have been employed to illustrate the interchannel coupling correlation effects in the valence photoionization dynamics of SF6. Partial photoionization cross sections and asymmetry parameters of six valence subshells (1t1 g, 5t1 u, 1t2 u, 3eg, 1t2 g, 4t1 u) are discussed in the framework of several theoretical and experimental studies. The complex Kohn results are in rather good agreement with experimental results, indicative of the fact that the interchannel coupling effects alter the photoionization dynamics significantly. We find that the dominant effect of interchannel coupling is to reduce the magnitude of shape resonant cross sections near threshold and to induce resonant features in other channels to which resonances are coupled.

  7. Covert face recognition relies on affective valence in congenital prosopagnosia.

    PubMed

    Bate, Sarah; Haslam, Catherine; Jansari, Ashok; Hodgson, Timothy L

    2009-06-01

    Dominant accounts of covert recognition in prosopagnosia assume subthreshold activation of face representations created prior to onset of the disorder. Yet, such accounts cannot explain covert recognition in congenital prosopagnosia, where the impairment is present from birth. Alternatively, covert recognition may rely on affective valence, yet no study has explored this possibility. The current study addressed this issue in 3 individuals with congenital prosopagnosia, using measures of the scanpath to indicate recognition. Participants were asked to memorize 30 faces paired with descriptions of aggressive, nice, or neutral behaviours. In a later recognition test, eye movements were monitored while participants discriminated studied from novel faces. Sampling was reduced for studied--nice compared to studied--aggressive faces, and performance for studied--neutral and novel faces fell between these two conditions. This pattern of findings suggests that (a) positive emotion can facilitate processing in prosopagnosia, and (b) covert recognition may rely on emotional valence rather than familiarity.

  8. Valence space techniques and QRPA vibrational mass parameters

    NASA Astrophysics Data System (ADS)

    Deloncle, I.; Lechaftois, F.; Péru, S.

    2016-06-01

    The vibrational mass parameters entering the quadrupolar 5DCH Hamiltonian are commonly obtained neglecting beyond mean-field correlations and the dynamical mean-field rearrangement. The Quasiparticle Random Phase Approximation (QRPA) framework would allow to avoid these disadvantages [1], if the computation time, when using density dependent force, was not prohibitive. Here, a significant time reduction is obtained by applying valence space (VS) techniques (energy cut-off and inert core) in QRPA calculations. The VS techniques allow to probe the physical content of the mass parameter. The QRPA mass parameter exhibit robustness toward VS limitations contrarily to the intrinsic QRPA outputs, that show deceptive appearance when an inert core is used. Excited states energy, and associated transition probabilities, should not be considered for optimizing the valence space limits.

  9. Energy-band diagram configuration of Al2O3/oxygen-terminated p-diamond metal-oxide-semiconductor

    NASA Astrophysics Data System (ADS)

    Maréchal, A.; Aoukar, M.; Vallée, C.; Rivière, C.; Eon, D.; Pernot, J.; Gheeraert, E.

    2015-10-01

    Diamond metal-oxide-semiconductor capacitors were prepared using atomic layer deposition at 250 °C of Al2O3 on oxygen-terminated boron doped (001) diamond. Their electrical properties were investigated in terms of capacitance and current versus voltage measurements. Performing X-ray photoelectron spectroscopy based on the measured core level energies and valence band maxima, the interfacial energy band diagram configuration of the Al2O3/O-diamond is established. The band diagram alignment is concluded to be of type I with valence band offset Δ E v of 1.34 ± 0.2 eV and conduction band offset Δ E c of 0.56 ± 0.2 eV considering an Al2O3 energy band gap of 7.4 eV. The agreement with electrical measurement and the ability to perform a MOS transistor are discussed.

  10. Heavy drinking relates to positive valence ratings of alcohol cues.

    PubMed

    Pulido, Carmen; Mok, Alex; Brown, Sandra A; Tapert, Susan F

    2009-01-01

    A positive family history of alcohol use disorders (FH) is a robust predictor of personal alcohol abuse and dependence. Exposure to problem-drinking models is one mechanism through which family history influences alcohol-related cognitions and drinking patterns. Similarly, exposure to alcohol advertisements is associated with alcohol involvement and the relationship between affective response to alcohol cues and drinking behavior has not been well established. In addition, the collective contribution that FH, exposure to different types of problem-drinking models (e.g. parents, peers) and personal alcohol use have on appraisal of alcohol-related stimuli has not been evaluated with a large sample. We investigated the independent effects of FH, exposure to problem-drinking models and personal alcohol use on valence ratings of alcohol pictures in a college sample. College students (n = 227) completed measures of personal drinking and substance use, exposure to problem-drinking models, FH and ratings on affective valence of 60 alcohol pictures. Greater exposure to non-familial problem-drinkers predicted greater drinking among college students (beta = 0.17, P < 0.01). However, personal drinking was the only predictor of valence ratings of alcohol pictures (beta = -0.53, P < 0.001). Personal drinking level predicted valence ratings of alcohol cues over and above FH, exposure to problem-drinking models and demographic characteristics. This suggests that positive affective responses to alcohol pictures are more a function of personal experience (i.e. repeated heavy alcohol use) than vicarious learning. PMID:18855802

  11. Lateral MoS2 p-n junctions formed by chemical doping method

    NASA Astrophysics Data System (ADS)

    Yoo, Won Jong; Choi, Min Sup; Qu, Deshun; Lee, Daeyeong; Liu, Xiaochi; Jang, Youngdae; Kim, Changsik; Ryu, Jungjin

    2015-03-01

    Interests on transition metal dichalcogenides, especially MoS2, are growing immensely due to its semiconducting nature with visible light range bandgap and strong light absorption property, which can pave the way to replace Si-based electronics and realize flexible and transparent electronics. For more versatile applications and industrialization, however, a proper doping process is required because various devices such as photonics and tunneling devices are composed of p-n junctions. Here, we demonstrated the formation of lateral MoS2 p-n junction by using partially stacked of hBN and p-doping with Au Cl3 solution. The fabricated devices showed an ideal rectifying behavior with ideality factor about 1. Under the exposure of monochromatic light, it revealed the properties of conventional p-n diode and also highly efficient photonic properties, showing feasibility to be applied for photovoltaic cells and photodetectors. Furthermore, we fabricated novel tunneling devices with similar device structure where local gates are located under MoS2. Its Fermi level can be effectively controlled by local gate modulation, so that the tunneling current can flow by band-to-band tunneling. This study provides an effective way to realize the practical devices such as photonics and tun

  12. Valence state change and defect centers induced by infrared femtosecond laser in Yb:YAG crystals

    SciTech Connect

    Wang, Xinshun Liu, Yang; Zhao, Panjuan; Guo, Zhongyi; Li, Yan; Qu, Shiliang

    2015-04-21

    The broad band upconversion luminescence in Yb{sup 3+}:YAG crystal has been observed in experiments under the irradiation of focused infrared femtosecond laser. The dependence of the fluorescence intensity on the pump power shows that the upconversion luminescence is due to simultaneous two-photon absorption process, which indicates that the broad emission bands at 365 and 463 nm could be assigned to the 5d → 4f transitions of Yb{sup 2+} ions and the one at 692 nm could be attributed to the electron-hole recombination process on (Yb{sup 2+}-F{sup +}) centers. The absorption spectra of the Yb:YAG crystal samples before and after femtosecond laser irradiation, and after further annealing reveal that permanent valence state change of Yb ions from Yb{sup 3+} to Yb{sup 2+} and (Yb{sup 2+}-F{sup +}) centers have been induced by infrared femtosecond laser irradiation in Yb{sup 3+}:YAG crystal.

  13. Ba6Sn6Se13: a new mixed valence selenostannate with NLO property.

    PubMed

    Feng, Kai; Jiang, Xingxing; Kang, Lei; Yin, Wenlong; Hao, Wenyu; Lin, Zheshuai; Yao, Jiyong; Wu, Yicheng; Chen, Chuangtian

    2013-10-01

    A new ternary selenostannate Ba6Sn6Se13 has been synthesized by a high temperature solid-state method. The compound crystallizes in the non-centrosymmetric orthorhombic space group P2(1)2(1)2(1) and may be represented as Ba6Sn5(2+)Sn(4+)Se13 with mixed valence Sn atoms. Sn(4+) cations lie in a tetrahedral environment, while Sn(2+) cations are found in two kinds of coordination environments: the trigonal pyramid and quadrangular pyramid. SnSe(n) (n = 3, 4, 5) polyhedra are further connected to generate a three-dimensional framework with Ba(2+) residing in cavities. Ba6Sn6Se13 shows moderate nonlinear optical response and is the first reported NLO compound in the Ba-Sn-Se system. In addition, diffuse reflectance spectroscopy measurement indicates that the band gap of Ba6Sn6Se13 is 1.52(2) eV and thermal analysis suggests that the compound melts incongruently. The theoretically calculated SHG response and band gap are in good agreement with experimental results.

  14. EEG study on affective valence elicited by novel and familiar pictures using ERD/ERS and SVM-RFE.

    PubMed

    Hidalgo-Muñoz, A R; López, M M; Galvao-Carmona, A; Pereira, A T; Santos, I M; Vázquez-Marrufo, M; Tomé, A M

    2014-02-01

    EEG signals have been widely explored in emotional processing analyses, both in time and frequency domains. However, in such studies, habituation phenomenon is barely considered in the discrimination of different emotional responses. In this work, spectral features of the event-related potentials (ERPs) are studied by means of event-related desynchronization/synchronization computation. In order to determine the most relevant ERP features for distinguishing how positive and negative affective valences are processed within the brain, support vector machine-recursive feature elimination is employed. The proposed approach was applied for investigating in which way the familiarity of stimuli affects the affective valence processing as well as which frequency bands and scalp regions are more involved in this process. In a group composed of young adult women, results prove that parietooccipital region and theta band are especially involved in the processing of novelty in emotional stimuli. Furthermore, the proposed method has shown to perform successfully using a moderated number of trials. PMID:24257836

  15. Predicting the Valence of a Scene from Observers’ Eye Movements

    PubMed Central

    R.-Tavakoli, Hamed; Atyabi, Adham; Rantanen, Antti; Laukka, Seppo J.; Nefti-Meziani, Samia; Heikkilä, Janne

    2015-01-01

    Multimedia analysis benefits from understanding the emotional content of a scene in a variety of tasks such as video genre classification and content-based image retrieval. Recently, there has been an increasing interest in applying human bio-signals, particularly eye movements, to recognize the emotional gist of a scene such as its valence. In order to determine the emotional category of images using eye movements, the existing methods often learn a classifier using several features that are extracted from eye movements. Although it has been shown that eye movement is potentially useful for recognition of scene valence, the contribution of each feature is not well-studied. To address the issue, we study the contribution of features extracted from eye movements in the classification of images into pleasant, neutral, and unpleasant categories. We assess ten features and their fusion. The features are histogram of saccade orientation, histogram of saccade slope, histogram of saccade length, histogram of saccade duration, histogram of saccade velocity, histogram of fixation duration, fixation histogram, top-ten salient coordinates, and saliency map. We utilize machine learning approach to analyze the performance of features by learning a support vector machine and exploiting various feature fusion schemes. The experiments reveal that ‘saliency map’, ‘fixation histogram’, ‘histogram of fixation duration’, and ‘histogram of saccade slope’ are the most contributing features. The selected features signify the influence of fixation information and angular behavior of eye movements in the recognition of the valence of images. PMID:26407322

  16. Valence Parity Renders z•-Type Ions Chemically Distinct

    PubMed Central

    Hubler, Shane L.; Jue, April; Keith, Jason; McAlister, Graeme C.; Craciun, Gheorghe; Coon, Joshua J.

    2009-01-01

    Here we report that the odd electron z•-type ions formed by the electron-based peptide dissociation methods (electron capture or transfer, ECD or ETD) have distinctive chemical compositions from other common product ion types. Specifically, b-, c-, and y-type ions have an odd number of atoms with an odd valence (e.g., N and H), while z•-type ions contain an even number of atoms with an odd valence. This tenet, referred to as the valence parity rule, mandates that no c-type ion shall have the same chemical composition, and by extension mass, as a z•-type ion. By experiment we demonstrate that nearly half of all observed c- and z•-type product ions resulting from 226 ETD product ion spectra can be assigned to a single, correct, chemical composition and ion type by simple inspection of the m/z peaks. The assignments provide (1) a platform to directly determine amino acid composition, (2) an input for database search algorithms, or (3) a basis for de novo sequence analysis. PMID:18444621

  17. Optoelectronic properties of valence-state-controlled amorphous niobium oxide

    NASA Astrophysics Data System (ADS)

    Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

    2016-06-01

    In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications.

  18. Core-core and core-valence correlation

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

    1988-01-01

    The effect of (1s) core correlation on properties and energy separations was analyzed using full configuration-interaction (FCI) calculations. The Be 1 S - 1 P, the C 3 P - 5 S and CH+ 1 Sigma + or - 1 Pi separations, and CH+ spectroscopic constants, dipole moment and 1 Sigma + - 1 Pi transition dipole moment were studied. The results of the FCI calculations are compared to those obtained using approximate methods. In addition, the generation of atomic natural orbital (ANO) basis sets, as a method for contracting a primitive basis set for both valence and core correlation, is discussed. When both core-core and core-valence correlation are included in the calculation, no suitable truncated CI approach consistently reproduces the FCI, and contraction of the basis set is very difficult. If the (nearly constant) core-core correlation is eliminated, and only the core-valence correlation is included, CASSCF/MRCI approached reproduce the FCI results and basis set contraction is significantly easier.

  19. Chromium valences in ureilite olivine and implications for ureilite petrogenesis

    NASA Astrophysics Data System (ADS)

    Goodrich, C. A.; Sutton, S. R.; Wirick, S.; Jercinovic, M. J.

    2013-12-01

    Ureilites are a group of ultramafic achondrites commonly thought to be residues of partial melting on a carbon-rich asteroid. They show a large variation in FeO content (olivine Fo values ranging from ∼74 to 95) that cannot be due to igneous fractionation and suggests instead variation in oxidation state. The presence of chromite in only a few of the most ferroan (Fo 75-76) samples appears to support such a model. MicroXANES analyses were used in this study to determine the valence states of Cr (previously unknown) in olivine cores of 11 main group ureilites. The goal of this work was to use a method that is independent of Fo to determine the oxidation conditions under which ureilites formed, in order to evaluate whether the ureilite FeO-variation is correlated with oxidation state, and whether it is nebular or planetary in origin. Two of the analyzed samples, LEW 88774 (Fo 74.2) and NWA 766 (Fo 76.7) contain primary chromite; two others, LAP 03587 (Fo 74.4) and CMS 04048 (Fo 76.2) contain sub-micrometer-sized exsolutions of chromite + Ca-rich pyroxene in olivine; and one, EET 96328 (Fo 85.2) contains an unusual chromite grain of uncertain origin. No chromite has been observed in the remaining six samples (Fo 77.4-92.3). Chromium in olivine in all eleven samples was found to be dominated by the divalent species, with valences ranging from 2.10 ± 0.02 (1σ) to 2.46 ± 0.04. The non-chromite-bearing ureilites have the most reduced Cr, with a weighted mean valence of 2.12 ± 0.01, i.e., Cr2+/Cr3+ = 7.33. All low-Fo chromite-bearing ureilites have more oxidized Cr, with valences ranging from 2.22 ± 0.03 to 2.46 ± 0.04. EET 96328, whose chromite grain we interpret as a late-crystallizing phase, yielded a reduced Cr valence of 2.15 ± 0.07, similar to the non-chromite-bearing samples. Based on the measured Cr valences, magmatic (1200-1300 °C) oxygen fugacities (fO2) of the non-chromite-bearing samples were estimated to be in the range IW-1.9 to IW-2.8 (assuming

  20. Predicting the Valence of a Scene from Observers' Eye Movements.

    PubMed

    R-Tavakoli, Hamed; Atyabi, Adham; Rantanen, Antti; Laukka, Seppo J; Nefti-Meziani, Samia; Heikkilä, Janne

    2015-01-01

    Multimedia analysis benefits from understanding the emotional content of a scene in a variety of tasks such as video genre classification and content-based image retrieval. Recently, there has been an increasing interest in applying human bio-signals, particularly eye movements, to recognize the emotional gist of a scene such as its valence. In order to determine the emotional category of images using eye movements, the existing methods often learn a classifier using several features that are extracted from eye movements. Although it has been shown that eye movement is potentially useful for recognition of scene valence, the contribution of each feature is not well-studied. To address the issue, we study the contribution of features extracted from eye movements in the classification of images into pleasant, neutral, and unpleasant categories. We assess ten features and their fusion. The features are histogram of saccade orientation, histogram of saccade slope, histogram of saccade length, histogram of saccade duration, histogram of saccade velocity, histogram of fixation duration, fixation histogram, top-ten salient coordinates, and saliency map. We utilize machine learning approach to analyze the performance of features by learning a support vector machine and exploiting various feature fusion schemes. The experiments reveal that 'saliency map', 'fixation histogram', 'histogram of fixation duration', and 'histogram of saccade slope' are the most contributing features. The selected features signify the influence of fixation information and angular behavior of eye movements in the recognition of the valence of images. PMID:26407322

  1. Predicting the Valence of a Scene from Observers' Eye Movements.

    PubMed

    R-Tavakoli, Hamed; Atyabi, Adham; Rantanen, Antti; Laukka, Seppo J; Nefti-Meziani, Samia; Heikkilä, Janne

    2015-01-01

    Multimedia analysis benefits from understanding the emotional content of a scene in a variety of tasks such as video genre classification and content-based image retrieval. Recently, there has been an increasing interest in applying human bio-signals, particularly eye movements, to recognize the emotional gist of a scene such as its valence. In order to determine the emotional category of images using eye movements, the existing methods often learn a classifier using several features that are extracted from eye movements. Although it has been shown that eye movement is potentially useful for recognition of scene valence, the contribution of each feature is not well-studied. To address the issue, we study the contribution of features extracted from eye movements in the classification of images into pleasant, neutral, and unpleasant categories. We assess ten features and their fusion. The features are histogram of saccade orientation, histogram of saccade slope, histogram of saccade length, histogram of saccade duration, histogram of saccade velocity, histogram of fixation duration, fixation histogram, top-ten salient coordinates, and saliency map. We utilize machine learning approach to analyze the performance of features by learning a support vector machine and exploiting various feature fusion schemes. The experiments reveal that 'saliency map', 'fixation histogram', 'histogram of fixation duration', and 'histogram of saccade slope' are the most contributing features. The selected features signify the influence of fixation information and angular behavior of eye movements in the recognition of the valence of images.

  2. Interchannel coupling effects in the valence photoionization of SF6

    NASA Astrophysics Data System (ADS)

    Jose, J.; Lucchese, R. R.; Rescigno, T. N.

    2014-05-01

    The complex Kohn and polyatomic Schwinger variational techniques have been employed to illustrate the interchannel coupling correlation effects in the valence photoionization dynamics of SF6. Partial photoionization cross sections and asymmetry parameters of six valence subshells (1t1g, 5t1u, 1t2u, 3eg, 1t2g, 4t1u) are discussed in the framework of several theoretical and experimental studies. The complex Kohn results are in rather good agreement with experimental results, indicative of the fact that the interchannel coupling effects alter the photoionization dynamics significantly. We find that the dominant effect of interchannel coupling is to reduce the magnitude of shape resonant cross sections near the threshold and to induce resonant features in other channels to which resonances are coupled. The long-standing issue concerning ordering of the valence orbitals is addressed and confirmed 4t1u61t2g63eg4(5t1u6+1t2u6) 1t1g6 as the most likely ordering.

  3. Optoelectronic properties of valence-state-controlled amorphous niobium oxide.

    PubMed

    Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

    2016-06-29

    In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications. PMID:27168317

  4. On the valence fluctuation in the early actinide metals

    DOE PAGES

    Soderlind, P.; Landa, A.; Tobin, J. G.; Allen, P.; Medling, S.; Booth, C. H.; Bauer, E. D.; Cooley, J. C.; Sokaras, D.; Weng, T. -C.; et al

    2015-12-15

    In this study, recent X-ray measurements suggest a degree of valence fluctuation in plutonium and uranium intermetallics. We are applying a novel scheme, in conjunction with density functional theory, to predict 5f configuration fractions of states with valence fluctuations for the early actinide metals. For this purpose we perform constrained integer f-occupation calculations for the α phases of uranium, neptunium, and plutonium metals. For plutonium we also investigate the δ phase. The model predicts uranium and neptunium to be dominated by the f3 and f4 configurations, respectively, with only minor contributions from other configurations. For plutonium (both α and δmore » phase) the scenario is dramatically different. Here, the calculations predict a relatively even distribution between three valence configurations. The δ phase has a greater configuration fraction of f6 compared to that of the α phase. The theory is consistent with the interpretations of modern X-ray experiments and we present resonant X-ray emission spectroscopy results for α-uranium.« less

  5. On the valence fluctuation in the early actinide metals

    SciTech Connect

    Soderlind, P.; Landa, A.; Tobin, J. G.; Allen, P.; Medling, S.; Booth, C. H.; Bauer, E. D.; Cooley, J. C.; Sokaras, D.; Weng, T. -C.; Nordlund, D.

    2015-12-15

    In this study, recent X-ray measurements suggest a degree of valence fluctuation in plutonium and uranium intermetallics. We are applying a novel scheme, in conjunction with density functional theory, to predict 5f configuration fractions of states with valence fluctuations for the early actinide metals. For this purpose we perform constrained integer f-occupation calculations for the α phases of uranium, neptunium, and plutonium metals. For plutonium we also investigate the δ phase. The model predicts uranium and neptunium to be dominated by the f3 and f4 configurations, respectively, with only minor contributions from other configurations. For plutonium (both α and δ phase) the scenario is dramatically different. Here, the calculations predict a relatively even distribution between three valence configurations. The δ phase has a greater configuration fraction of f6 compared to that of the α phase. The theory is consistent with the interpretations of modern X-ray experiments and we present resonant X-ray emission spectroscopy results for α-uranium.

  6. Mott Transition of MnO under Pressure: A Comparison of Correlated Band Theories

    SciTech Connect

    Kasinathan, Deepa; Kunes, Jan; Koepernik, K; Diaconu, Cristian V; Martin, Richard L; Prodan, Ionut; Scuseria, Gustavo E; Spaldin, Nicola; Petit, Leon; Schulthess, Thomas C; Pickett, W. E.

    2006-01-01

    The electronic structure, magnetic moment, and volume collapse of MnO under pressure are obtained from four different correlated band theory methods; local density approximation+Hubbard U (LDA+U), pseudopotential self-interaction correction (pseudo-SIC), the hybrid functional (combined local exchange plus Hartree-Fock exchange), and the local spin density SIC (SIC-LSD) method. Each method treats correlation among the five Mn 3d orbitals (per spin), including their hybridization with three O 2p orbitals in the valence bands and their changes with pressure. The focus is on comparison of the methods for rock salt MnO (neglecting the observed transition to the NiAs structure in the 90-100 GPa range). Each method predicts a first-order volume collapse, but with variation in the predicted volume and critical pressure. Accompanying the volume collapse is a moment collapse, which for all methods is from high-spin to low-spin ((5/2){yields}(1/2)), not to nonmagnetic as the simplest scenario would have. The specific manner in which the transition occurs varies considerably among the methods: pseudo-SIC and SIC-LSD give insulator-to-metal, while LDA+U gives insulator-to-insulator and the hybrid method gives an insulator-to-semimetal transition. Projected densities of states above and below the transition are presented for each of the methods and used to analyze the character of each transition. In some cases the rhombohedral symmetry of the antiferromagnetically ordered phase clearly influences the character of the transition.

  7. Determination of band alignment in the single-layer MoS2/WSe2 heterojunction

    PubMed Central

    Chiu, Ming-Hui; Zhang, Chendong; Shiu, Hung-Wei; Chuu, Chih-Piao; Chen, Chang-Hsiao; Chang, Chih-Yuan S.; Chen, Chia-Hao; Chou, Mei-Yin; Shih, Chih-Kang; Li, Lain-Jong

    2015-01-01

    The emergence of two-dimensional electronic materials has stimulated proposals of novel electronic and photonic devices based on the heterostructures of transition metal dichalcogenides. Here we report the determination of band offsets in the heterostructures of transition metal dichalcogenides by using microbeam X-ray photoelectron spectroscopy and scanning tunnelling microscopy/spectroscopy. We determine a type-II alignment between MoS2 and WSe2 with a valence band offset value of 0.83 eV and a conduction band offset of 0.76 eV. First-principles calculations show that in this heterostructure with dissimilar chalcogen atoms, the electronic structures of WSe2 and MoS2 are well retained in their respective layers due to a weak interlayer coupling. Moreover, a valence band offset of 0.94 eV is obtained from density functional theory, consistent with the experimental determination. PMID:26179885

  8. Determination of band alignment in the single-layer MoS2/WSe2 heterojunction.

    PubMed

    Chiu, Ming-Hui; Zhang, Chendong; Shiu, Hung-Wei; Chuu, Chih-Piao; Chen, Chang-Hsiao; Chang, Chih-Yuan S; Chen, Chia-Hao; Chou, Mei-Yin; Shih, Chih-Kang; Li, Lain-Jong

    2015-07-16

    The emergence of two-dimensional electronic materials has stimulated proposals of novel electronic and photonic devices based on the heterostructures of transition metal dichalcogenides. Here we report the determination of band offsets in the heterostructures of transition metal dichalcogenides by using microbeam X-ray photoelectron spectroscopy and scanning tunnelling microscopy/spectroscopy. We determine a type-II alignment between MoS2 and WSe2 with a valence band offset value of 0.83 eV and a conduction band offset of 0.76 eV. First-principles calculations show that in this heterostructure with dissimilar chalcogen atoms, the electronic structures of WSe2 and MoS2 are well retained in their respective layers due to a weak interlayer coupling. Moreover, a valence band offset of 0.94 eV is obtained from density functional theory, consistent with the experimental determination.

  9. Electronic Structure and Valence of Mn impurities in III-V semiconductors

    NASA Astrophysics Data System (ADS)

    Schulthess, Thomas C.

    2003-11-01

    Mn doped III-V semiconductors have recently become very popular materials since they are ferromagnetic at reasonably high temperatures and in some cases show carrier induced magnetism, where the Curie temperature can be altered by changes in the carrier concentration. It is expected that these materials will play an important role in Spintronics devices. Substitutional Mn impurities in III-V semiconductors can acquire either a divalent or a trivalent configuration. For example, it is generally accepted that Mn in GaAs is in a (d^5+h) configuration with five occupied Mn d-orbitals and a delocalized hole in the valence band. In contrast, Mn in GaN is believed to be in a d^4 configuration with a deep impurity state that has d-character. But there have recently been some discussions about the possibility of having some Mn ion in GaN assuming a divalent (d^5+h) type configuration. In order to achieve carrier induced ferromagnetism, the desired state of the Mn ions in III-V semiconductors is the (d^5+h) configuration. We have therefore performed ab-initio calculations of the Mn valence when it substitutes Ga in various III-V semiconductor hosts. We use the self-interaction corrected local spin density (SIC-LSD) method which is able to treat localized impurity orbitals properly. In particular we find that the method is capable of predicting the (d^5+h) state of Mn in GaAs. For Mn in GaP and GaN the calculations predict a trivalent d^4 state in the idealized system. The energy differences between d^4 and (d^5+h) configurations in GaP are, however, very small. Introduction of defects or donors does change the valence of Mn in GaP, favoring the divalent state under certain circumstances. Work done in collaboration with W. Temmerman and S. Szotek, Daresbury Laboratory, G. M. Stocks, ORNL, and W. H. Butler, MINT Center University of Alabama. This work supported by the Defense Advanced Research Agency and by DOE Office of Science trough ASCR/MICS and BES/DMSE under Contract No

  10. Excitations of one-valence-proton, one-valence-neutron nucleus {sup 210}Bi from cold-neutron capture

    SciTech Connect

    Cieplicka-Oryńczak, N.; Fornal, B.; Szpak, B.; Leoni, S.; Bottoni, S.; Bazzacco, D.; Blanc, A.; Jentschel, M.; Köster, U.; Mutti, P.; Soldner, T.; Bocchi, G.; France, G. de; Simpson, G.; Urban, W.

    2015-10-15

    The low-spin structure of one-proton, one-neutron {sup 210}Bi nucleus was investigated in cold-neutron capture reaction on {sup 209}Bi. The γ-coincidence measurements were performed with use of EXILL array consisted of 16 HPGe detectors. The experimental results were compared to shell-model calculations involving valence particles excitations. The {sup 210}Bi nucleus offers the potential to test the effective proton-neutron interactions because most of the states should arise from the proton-neutron excitations. Additionally, it was discovered that a few states should come from the couplings of valence particles to the 3{sup −} octupole vibration in {sup 208}Pb which provides also the possibility of testing the calculations involving the core excitations.

  11. Energetic Landscape of MDM2-p53 Interactions by Computational Mutagenesis of the MDM2-p53 Interaction

    PubMed Central

    Thayer, Kelly M.; Beyer, George A.

    2016-01-01

    The ubiquitin ligase MDM2, a principle regulator of the tumor suppressor p53, plays an integral role in regulating cellular levels of p53 and thus a prominent role in current cancer research. Computational analysis used MUMBO to rotamerize the MDM2-p53 crystal structure 1YCR to obtain an exhaustive search of point mutations, resulting in the calculation of the ΔΔG comprehensive energy landscape for the p53-bound regulator. The results herein have revealed a set of residues R65-E69 on MDM2 proximal to the p53 hydrophobic binding pocket that exhibited an energetic profile deviating significantly from similar residues elsewhere in the protein. In light of the continued search for novel competitive inhibitors for MDM2, we discuss possible implications of our findings on the drug discovery field. PMID:26992014

  12. Energetic Landscape of MDM2-p53 Interactions by Computational Mutagenesis of the MDM2-p53 Interaction.

    PubMed

    Thayer, Kelly M; Beyer, George A

    2016-01-01

    The ubiquitin ligase MDM2, a principle regulator of the tumor suppressor p53, plays an integral role in regulating cellular levels of p53 and thus a prominent role in current cancer research. Computational analysis used MUMBO to rotamerize the MDM2-p53 crystal structure 1YCR to obtain an exhaustive search of point mutations, resulting in the calculation of the ΔΔG comprehensive energy landscape for the p53-bound regulator. The results herein have revealed a set of residues R65-E69 on MDM2 proximal to the p53 hydrophobic binding pocket that exhibited an energetic profile deviating significantly from similar residues elsewhere in the protein. In light of the continued search for novel competitive inhibitors for MDM2, we discuss possible implications of our findings on the drug discovery field. PMID:26992014

  13. Compositional dependence of the band gap in Ga(NAsP) quantum well heterostructures

    SciTech Connect

    Jandieri, K. Ludewig, P.; Wegele, T.; Beyer, A.; Kunert, B.; Springer, P.; Baranovskii, S. D.; Koch, S. W.; Volz, K.; Stolz, W.

    2015-08-14

    We present experimental and theoretical studies of the composition dependence of the direct band gap energy in Ga(NAsP)/GaP quantum well heterostructures grown on either (001) GaP- or Si-substrates. The theoretical description takes into account the band anti-crossing model for the conduction band as well as the modification of the valence subband structure due to the strain resulting from the pseudomorphic epitaxial growth on the respective substrate. The composition dependence of the direct band gap of Ga(NAsP) is obtained for a wide range of nitrogen and phosphorus contents relevant for laser applications on Si-substrate.

  14. Features of the band structure for semiconducting iron, ruthenium, and osmium monosilicides

    SciTech Connect

    Shaposhnikov, V. L. Migas, D. B.; Borisenko, V. E.; Dorozhkin, N. N.

    2009-02-15

    The pseudopotential method has been used to optimize the crystal lattice and calculate the energy band spectra for iron, ruthenium and, osmium monosilicides. It is found that all these compounds are indirect-gap semiconductors with band gaps of 0.17, 0.22, and 0.50 eV (FeSi, RuSi, and OsSi, respectively). A distinctive feature of their band structure is the 'loop of extrema' both in the valence and conduction bands near the center of the cubic Brillouin zone.

  15. Temperature dependent band offsets in PbSe/PbEuSe quantum well heterostructures

    SciTech Connect

    Simma, M.; Bauer, G.; Springholz, G.

    2012-10-22

    The band offsets of PbSe/Pb{sub 1-x}Eu{sub x}Se multi-quantum wells grown by molecular beam epitaxy are determined as a function of temperature and europium content using temperature-modulated differential transmission spectroscopy. The confined quantum well states in the valence and conduction bands are analyzed using a k{center_dot}p model with envelope function approximation. From the fit of the experimental data, the normalized conduction band offset is determined as 0.45{+-}0.15 of the band gap difference, independently of Eu content up to 14% and temperature from 20 to 300 K.

  16. Composite Chiral Bands in the A{approx}105 Mass Region

    SciTech Connect

    Timar, J.; Sohler, D.; Molnar, J.; Algora, A.; Dombradi, Zs.; Krasznahorkay, A.; Zolnai, L.; Vaman, C.; Starosta, K.; Joshi, P.; Wadsworth, R.; Jenkins, D.G.; Raddon, P.M.; Simons, A.J.; Wilkinson, A.R.; Dimitrov, V.I.; Fossan, D.B.; Koike, T.; Bednarczyk, P.; Curien, D.

    2005-11-21

    Composite chiral bands, corresponding to the {pi}g9/2v(h11/2)2 quasiparticle configuration, have been observed in 103Rh and 105Rh. The behaviour of these bands is compared with that of the chiral bands with a {pi}g9/2vh11/2 quasiparticle configuration observed in the odd-odd 102Rh and 104Rh nuclei. This comparison shows in a model independent way that the energy separation pattern of the chiral partner bands depends strongly on the properties of the triaxial core whilst the dependence on the valence quasiparticle coupling and on the Fermi level is weaker.

  17. Character disposition and behavior type: influences of valence on preschool children's social judgments.

    PubMed

    Jones, Elaine F; Tobias, Marvin; Pauley, Danielle; Thomson, Nicole Renick; Johnson, Shawana Lewis

    2009-12-01

    The authors studied the influences of valence information on preschool children's (n = 47) moral (good or bad), liking (liked or disliked by a friend), and consequence-of-behavior (reward or punishment) judgments. The authors presented 8 scenarios describing the behavior valence, positive valence (help, share), negative valence (verbal insult, physical aggression), and disposition valence (nice or mean) of characters in social interaction with a friend. Overall, character disposition and behavior valence significantly influenced children's judgments. Moral, liking, and consequence-of-behavior judgments varied significantly by character disposition for both positive behavior scenarios. In contrast, there were fewer significant findings as a function of character disposition for negative behavior scenarios, suggesting that the negative behavior cue somewhat diminished the effect of character disposition on children's judgments. The authors discuss preschool students' coordination of information about valence of behavior and character disposition and the students' reluctance to judge that misbehavior warrants punitive consequence.

  18. Band offsets in c-Si/Si-XII heterojunctions

    NASA Astrophysics Data System (ADS)

    Mustafa, Jamal I.; Malone, Brad D.; Cohen, Marvin L.; Louie, Steven G.

    2014-08-01

    Silicon has a rich phase diagram with a multitude of phases existing over a wide range of pressures and temperatures, in addition to the common cubic silicon (c-Si) phase. One such phase, Si-XII, was first observed less than 2 decades ago in diamond anvil experiments, and more recently as a product of nanoindentation. In some of these latter experiments, I-V measurements were performed to characterize the c-Si/Si-XII interface that results when Si-XII is formed in cubic silicon substrates. In this paper we describe calculations of the band offsets in c-Si/Si-XII heterojunctions. We find that the heterojunction is of Type I and that the band offsets are estimated to be ΔEv=0.3 eV and ΔEc=0.5 eV for the valence bands and conduction bands, respectively.

  19. Infrared band intensities of saturated hydrocarbons

    NASA Technical Reports Server (NTRS)

    Pinkley, L. W.; Sethna, P. P.; Williams, D.

    1978-01-01

    Kramers-Kronig analysis is applied to measured values of spectral reflectance at near-normal incidence to determine the real and the imaginary parts of the complex index of refraction for methane, ethane, propane, n-butane, n-hexane, n-heptane, and n-decane in the liquid state. The results indicate that the strengths of the characteristic bands as measured by the integral of the imaginary part are roughly constant for all the liquid alkanes except for methane. The intensity of the CH valence vibration bands in the spectra of the alkanes except methane is directly proportional to the number of CH groups per unit volume. The relations for the intensity of the bands due to CH2 and CH3 deformations are examined. Characteristic band intensities of the type established for NH4(+) and SO4(2-) groups in solutions and crystals cannot be extended to the more closely coupled CH2 and CH3 groups in alkane molecules.

  20. P2P proteomics -- data sharing for enhanced protein identification

    PubMed Central

    2012-01-01

    Background In order to tackle the important and challenging problem in proteomics of identifying known and new protein sequences using high-throughput methods, we propose a data-sharing platform that uses fully distributed P2P technologies to share specifications of peer-interaction protocols and service components. By using such a platform, information to be searched is no longer centralised in a few repositories but gathered from experiments in peer proteomics laboratories, which can subsequently be searched by fellow researchers. Methods The system distributively runs a data-sharing protocol specified in the Lightweight Communication Calculus underlying the system through which researchers interact via message passing. For this, researchers interact with the system through particular components that link to database querying systems based on BLAST and/or OMSSA and GUI-based visualisation environments. We have tested the proposed platform with data drawn from preexisting MS/MS data reservoirs from the 2006 ABRF (Association of Biomolecular Resource Facilities) test sample, which was extensively tested during the ABRF Proteomics Standards Research Group 2006 worldwide survey. In particular we have taken the data available from a subset of proteomics laboratories of Spain's National Institute for Proteomics, ProteoRed, a network for the coordination, integration and development of the Spanish proteomics facilities. Results and Discussion We performed queries against nine databases including seven ProteoRed proteomics laboratories, the NCBI Swiss-Prot database and the local database of the CSIC/UAB Proteomics Laboratory. A detailed analysis of the results indicated the presence of a protein that was supported by other NCBI matches and highly scored matches in several proteomics labs. The analysis clearly indicated that the protein was a relatively high concentrated contaminant that could be present in the ABRF sample. This fact is evident from the information that

  1. The electronic band character of Ru dichalcogenides and its significance for the photoelectrolysis of water

    NASA Astrophysics Data System (ADS)

    Kühne, H.-M.; Jaegermann, W.; Tributsch, H.

    1984-11-01

    Electrodes of Ru dichalcogenides show different electrochemical behavior in contact with aqeuous electrolytes. Whereas RuS 2 is most stable, considerable anodic corrosion occurs at RuSe 2 and RuTe 2. XPS measurements performed to analyse surface species, formed after electrochemical treatment, and to identify the band character of the compounds. A correlation between variations in valence band character and the kinetics of the dissolution reaction is suggested.

  2. Come Join the Band

    ERIC Educational Resources Information Center

    Olson, Cathy Applefeld

    2011-01-01

    A growing number of students in Blue Springs, Missouri, are joining the band, drawn by a band director who emphasizes caring and inclusiveness. In the four years since Melissia Goff arrived at Blue Springs High School, the school's extensive band program has swelled. The marching band alone has gone from 100 to 185 participants. Also under Goff's…

  3. Multicast Services over Structured P2P Networks

    NASA Astrophysics Data System (ADS)

    Manzanares-Lopez, Pilar; Malgosa-Sanahuja, Josemaria; Muñoz-Gea, Juan Pedro; Sanchez-Aarnoutse, Juan Carlos

    IP multicast functionality was defined as an efficient method to transmit datagrams to a group of receivers. However, although a lot of research work has been done in this technology, IP multicast has not spread out over the Internet as much as expected, reducing its use for local environments (i.e., LANs). The peer-to-peer networks paradigm can be used to overcome the IP multicast limitations. In this new scenario (called Application Layer Multicast or ALM), the multicast functionality is changed from network to application layer. Although ALM solution can be classified into unstructured and structured solutions, the last ones are the best option to offer multicast services due to the effectiveness in the discovery nodes, their mathematical definition and the totally decentralized management. In this chapter we are going to offer a tutorial of the main structured ALM solutions, but introducing two novelties with respect to related surveys in the past: first, the systematic description of most representative structured ALM solution in OverSim (one of the most popular p2p simulation frameworks). Second, some simulation comparatives between flooding-based and tree-based structured ALM solution are also presented.

  4. Migration of Dust Particles from Comet 2P Encke

    NASA Technical Reports Server (NTRS)

    Ipatov, S. I.

    2003-01-01

    We investigated the migration of dust particles under the gravitational influence of all planets (except for Pluto), radiation pressure, Poynting-Robertson drag and solar wind drag for Beta equal to 0.002, 0.004, 0.01, 0.05, 0.1, 0.2, and 0.4. For silicate particles such values of Beta correspond to diameters equal to about 200, 100, 40, 9, 4, 2, and 1 microns, respectively. We used the Bulirsh-Stoer method of integration, and the relative error per integration step was taken to be less than lo-'. Initial orbits of the particles were close to the orbit of Comet 2P Encke. We considered initial particles near perihelion (runs denoted as Delta tsub o, = 0), near aphelion (Delta tsub o, = 0.5), and also studied their initial positions when the comet moved for Pa/4 after perihelion passage (such runs are denoted as Delta tsub o, =i 0.25), where Pa is the period of the comet. Variations in time T when perihelion was passed was varied with a step 0.1 day for series 'S' and with a step 1 day for series 'L'. For each Beta we considered N = 101 particles for "S" runs and 150 particles for "L" runs.

  5. The casein kinases Yck1p and Yck2p act in the secretory pathway, in part, by regulating the Rab exchange factor Sec2p

    PubMed Central

    Stalder, Danièle; Novick, Peter J.

    2016-01-01

    Sec2p is a guanine nucleotide exchange factor that activates Sec4p, the final Rab GTPase of the yeast secretory pathway. Sec2p is recruited to secretory vesicles by the upstream Rab Ypt32p acting in concert with phosphatidylinositol-4-phosphate (PI(4)P). Sec2p also binds to the Sec4p effector Sec15p, yet Ypt32p and Sec15p compete against each other for binding to Sec2p. We report here that the redundant casein kinases Yck1p and Yck2p phosphorylate sites within the Ypt32p/Sec15p binding region and in doing so promote binding to Sec15p and inhibit binding to Ypt32p. We show that Yck2p binds to the autoinhibitory domain of Sec2p, adjacent to the PI(4)P binding site, and that addition of PI(4)P inhibits Sec2p phosphorylation by Yck2p. Loss of Yck1p and Yck2p function leads to accumulation of an intracellular pool of the secreted glucanase Bgl2p, as well as to accumulation of Golgi-related structures in the cytoplasm. We propose that Sec2p is phosphorylated after it has been recruited to secretory vesicles and the level of PI(4)P has been reduced. This promotes Sec2p function by stimulating its interaction with Sec15p. Finally, Sec2p is dephosphorylated very late in the exocytic reaction to facilitate recycling. PMID:26700316

  6. Gold atomic clusters extracting the valence electrons to shield the carbon monoxide passivation on near-monolayer core-shell nanocatalysts in methanol oxidation reactions.

    PubMed

    Chen, Tsan-Yao; Li, Hong Dao; Lee, Guo-Wei; Huang, Po-Chun; Yang, Po-Wei; Liu, Yu-Ting; Liao, Yen-Fa; Jeng, Horng-Tay; Lin, Deng-Sung; Lin, Tsang-Lang

    2015-06-21

    Atomic-scale gold clusters were intercalated at the inter-facet corner sites of Pt-shell Ru-core nanocatalysts with near-monolayer shell thickness. We demonstrated that these unique clusters could serve as a drain of valence electrons in the kink region of the core-shell heterojunction. As jointly revealed by density functional theory calculations and valence band spectra, these Au clusters extract core-level electrons to the valence band. They prevent corrosion due to protonation and enhance the tolerance of CO by increasing the electronegativity at the outermost surface of the NCs during the methanol oxidation reaction (MOR). In these circumstances, the retained current density of Pt-shell Ru-core NCs is doubled in a long-term (2 hours) MOR at a fixed voltage (0.5 V vs. SCE) by intercalating these sub-nanometer gold clusters. Such novel structural confinement provides a possible strategy for developing direct-methanol fuel cell (DMFC) modules with high power and stability.

  7. Generally Contracted Valence-Core/Valence Basis Sets for Use with Relativistic Effective Core Potentials and Spin-Orbit Coupling Operators

    SciTech Connect

    Ermler, Walter V.; Tilson, Jeffrey L.

    2012-12-15

    A procedure for structuring generally contracted valence-core/valence basis sets of Gaussian-type functions for use with relativistic effective core potentials (gcv-c/v-RECP basis sets) is presented. Large valence basis sets are enhanced using a compact basis set derived for outer core electrons in the presence of small-core RECPs. When core electrons are represented by relativistic effective core potentials (RECPs), and appropriate levels of theory, these basis sets are shown to provide accurate representations of atomic and molecular valence and outer-core electrons. Core/valence polarization and correlation effects can be calculated using these basis sets through standard methods for treating electron correlation. Calculations of energies and spectra for Ru, Os, Ir, In and Cs are reported. Spectroscopic constants for RuO2+, OsO2+, Cs2 and InH are calculated and compared with experiment.

  8. Modeling direct band-to-band tunneling: From bulk to quantum-confined semiconductor devices

    SciTech Connect

    Carrillo-Nuñez, H.; Ziegler, A.; Luisier, M.; Schenk, A.

    2015-06-21

    A rigorous framework to study direct band-to-band tunneling (BTBT) in homo- and hetero-junction semiconductor nanodevices is introduced. An interaction Hamiltonian coupling conduction and valence bands (CVBs) is derived using a multiband envelope method. A general form of the BTBT probability is then obtained from the linear response to the “CVBs interaction” that drives the system out of equilibrium. Simple expressions in terms of the one-electron spectral function are developed to compute the BTBT current in two- and three-dimensional semiconductor structures. Additionally, a two-band envelope equation based on the Flietner model of imaginary dispersion is proposed for the same purpose. In order to characterize their accuracy and differences, both approaches are compared with full-band, atomistic quantum transport simulations of Ge, InAs, and InAs-Si Esaki diodes. As another numerical application, the BTBT current in InAs-Si nanowire tunnel field-effect transistors is computed. It is found that both approaches agree with high accuracy. The first one is considerably easier to conceive and could be implemented straightforwardly in existing quantum transport tools based on the effective mass approximation to account for BTBT in nanodevices.

  9. Nucleon and pion distribution functions in the valence region

    NASA Astrophysics Data System (ADS)

    Holt, Roy J.; Roberts, Craig D.

    2010-10-01

    An experimental and theoretical perspective is provided on the behavior of unpolarized distribution functions for the nucleon and pion on the valence-quark domain, namely, Bjorken x≳0.4 . This domain is a key to much of hadron physics; e.g., a hadron is defined by its flavor content and that is a valence-quark property. Furthermore, its accurate parametrization is crucial to the provision of reliable input for large collider experiments. The focus is on experimental extractions of distribution functions via electron and muon inelastic scattering, and from Drell-Yan interactions; and on theoretical treatments that emphasize an explanation of the distribution functions, providing an overview of major contemporary approaches and issues. Valence-quark physics is a compelling subject, which probes at the heart of our understanding of the standard model. There are numerous outstanding and unresolved challenges, which experiment and theory must confront. In connection with experiment, an explanation that an upgraded Jefferson Laboratory facility is well suited to provide new data on the nucleon is provided, while a future electron-ion collider could provide essential new data for the mesons. There is also great potential in using Drell-Yan interactions, at FNAL, CERN, J-PARC, and GSI, to push into the large- x domain for both mesons and nucleons. Furthermore, it is argued that explanation, in contrast to modeling and parametrization, requires a widespread acceptance of the need to adapt theory: to the lessons learnt already from the methods of nonperturbative quantum-field theory and a fuller exploitation of those methods.

  10. Nucleon and pio distribution functions in the valence region.

    SciTech Connect

    Holt, R. J.; Roberts, C. D.

    2010-10-28

    An experimental and theoretical perspective is provided on the behavior of unpolarized distribution functions for the nucleon and pion on the valence-quark domain, namely, Bjorken x {ge} 0.4. This domain is a key to much of hadron physics; e.g., a hadron is defined by its flavor content and that is a valence-quark property. Furthermore, its accurate parametrization is crucial to the provision of reliable input for large collider experiments. The focus is on experimental extractions of distribution functions via electron and muon inelastic scattering, and from Drell-Yan interactions; and on theoretical treatments that emphasize an explanation of the distribution functions, providing an overview of major contemporary approaches and issues. Valence-quark physics is a compelling subject, which probes at the heart of our understanding of the standard model. There are numerous outstanding and unresolved challenges, which experiment and theory must confront. In connection with experiment, an explanation that an upgraded Jefferson Laboratory facility is well suited to provide new data on the nucleon is provided, while a future electron-ion collider could provide essential new data for the mesons. There is also great potential in using Drell-Yan interactions, at FNAL, CERN, J-PARC, and GSI, to push into the large-x domain for both mesons and nucleons. Furthermore, it is argued that explanation, in contrast to modeling and parametrization, requires a widespread acceptance of the need to adapt theory: to the lessons learnt already from the methods of nonperturbative quantum-field theory and a fuller exploitation of those methods.

  11. Neural correlates of valence generalization in an affective conditioning paradigm.

    PubMed

    Schick, Anita; Adam, Ruth; Vollmayr, Barbara; Kuehner, Christine; Kanske, Philipp; Wessa, Michèle

    2015-10-01

    In case of uncertainty, predictions that are based on prior, similar experiences guide our decision by processes of generalization. Over-generalization of negative information has been identified as an important feature of several psychopathologies, including anxiety disorders and depression, and might underlie biased interpretation of ambiguous information. Here, we investigated the neural correlates of valence generalization to ambiguous stimuli using a translational affective conditioning task during fMRI. Twenty-five healthy individuals participated in a conditioning procedure with (1) an initial acquisition phase, where participants learned the positive and negative valence of two different tones (reference tones) through their responses and subsequent feedback and (2) a test phase, where participants were presented with the previously learned reference tones and three additional tones with intermediate frequency to the learned reference tones. By recording the responses to these intermediate stimuli we were able to assess the participantsí interpretation of ambiguous tones as either positive or negative. Behavioral results revealed a graded response pattern to the three intermediate tones, which was mirrored on the neural level. More specifically, parametric analyses OF BOLD responses to all five tones revealed a linear effect in bilateral anterior insula and SMA with lowest activation to the negative reference tone and highest activation to the positive negative tone. In addition, a cluster in the SMA showed a reverse-quadratic response, i.e., the strongest response for the most ambiguous tone. These findings suggest overlapping regions in the salience network that mediate valence generalization and decision-making under ambiguity, potentially underlying biased ambiguous cue interpretation. PMID:26057359

  12. Pion and kaon valence-quark parton distribution functions

    SciTech Connect

    Nguyen, Trang; Bashir, Adnan; Roberts, Craig D.; Tandy, Peter C.

    2011-06-15

    A rainbow-ladder truncation of QCD's Dyson-Schwinger equations, constrained by existing applications to hadron physics, is employed to compute the valence-quark parton distribution functions of the pion and kaon. Comparison is made to {pi}-N Drell-Yan data for the pion's u-quark distribution and to Drell-Yan data for the ratio u{sub K}(x)/u{sub {pi}}(x): the environmental influence of this quantity is a parameter-free prediction, which agrees well with existing data. Our analysis unifies the computation of distribution functions with that of numerous other properties of pseudoscalar mesons.

  13. Pion and kaon valence-quark parton distribution functions.

    SciTech Connect

    Nguyen, T.; Bashir, A.; Roberts, C. D.; Tandy, P. C.

    2011-06-16

    A rainbow-ladder truncation of QCD's Dyson-Schwinger equations, constrained by existing applications to hadron physics, is employed to compute the valence-quark parton distribution functions of the pion and kaon. Comparison is made to {pi}-N Drell-Yan data for the pion's u-quark distribution and to Drell-Yan data for the ratio u{sub K}(x)/u{sub {pi}}(x): the environmental influence of this quantity is a parameter-free prediction, which agrees well with existing data. Our analysis unifies the computation of distribution functions with that of numerous other properties of pseudoscalar mesons.

  14. Aging and long-term memory for emotionally valenced events.

    PubMed

    Breslin, Carolyn W; Safer, Martin A

    2013-06-01

    In 2008, 1103 ardent Boston Red Sox fans answered questions about their team's 2003 loss and 2004 win in baseball championship games with archrival New York Yankees. Contrary to predictions based on socioemotional selectivity theory, there were no significant interactions of age and event valence for accuracy in remembering event details, or for self-reported subjective vividness and rehearsal of the memories. Fans 65 years and older tended to remember feeling only sad about the 2003 loss, whereas fans 25 years and under tended to remember feeling both sad and angry. Individuals may remember emotional feelings based on remembered goals about an event.

  15. Pion and kaon valence-quark parton distribution functions

    NASA Astrophysics Data System (ADS)

    Nguyen, Trang; Bashir, Adnan; Roberts, Craig D.; Tandy, Peter C.

    2011-06-01

    A rainbow-ladder truncation of QCD’s Dyson-Schwinger equations, constrained by existing applications to hadron physics, is employed to compute the valence-quark parton distribution functions of the pion and kaon. Comparison is made to π-N Drell-Yan data for the pion’s u-quark distribution and to Drell-Yan data for the ratio uK(x)/uπ(x): the environmental influence of this quantity is a parameter-free prediction, which agrees well with existing data. Our analysis unifies the computation of distribution functions with that of numerous other properties of pseudoscalar mesons.

  16. Heterojunction band offsets and dipole formation at BaTiO{sub 3}/SrTiO{sub 3} interfaces

    SciTech Connect

    Balaz, Snjezana; Zeng, Zhaoquan; Brillson, Leonard J.

    2013-11-14

    We used a complement of photoemission and cathodoluminescence techniques to measure formation of the BaTiO{sub 3} (BTO) on SrTiO{sub 3} (STO) heterojunction band offset grown monolayer by monolayer by molecular beam epitaxy. X-ray photoemission spectroscopy (XPS) provided core level and valence band edge energies to monitor the valence band offset in-situ as the first few crystalline BTO monolayers formed on the STO substrate. Ultraviolet photoemission spectroscopy (UPS) measured Fermi level positions within the band gap, work functions, and ionization potentials of the growing BTO film. Depth-resolved cathodoluminescence spectroscopy measured energies and densities of interface states at the buried heterojunction. Kraut-based XPS heterojunction band offsets provided evidence for STO/BTO heterojunction linearity, i.e., commutativity and transitivity. In contrast, UPS and XPS revealed a large dipole associated either with local charge transfer or strain-induced polarization within the BTO epilayer.

  17. 16O + 16O molecular structures of positive- and negative-parity superdeformed bands in 34S

    NASA Astrophysics Data System (ADS)

    Taniguchi, Yasutaka

    2016-05-01

    The structures of excited states in 34S are investigated using the antisymmetrized molecular dynamics and generator coordinate method(GCM). The GCM basis wave functions are calculated via energy variation with a constraint on the quadrupole deformation parameter β. By applying the GCM after parity and angular momentum projections, the coexistence of two positive- and one negative-parity super de formed(SD) bands are predicted, and low-lying states and other deformed bands are obtained. The SD bands have structures of 16O + 16O + two valence neutrons in molecular orbitals around the two 16O cores in a cluster picture. The configurations of the two valence neutrons are δ2 and π2 for the positive-parity SD bands and π1δ1 for the negative parity SD band.

  18. Constraints to the flat band potential of hematite photo-electrodes.

    PubMed

    Hankin, A; Alexander, J C; Kelsall, G H

    2014-08-14

    We revisit the fundamental constraints that apply to flat band potential values at semiconductor photo-electrodes. On the physical scale, the Fermi level energy of a non-degenerate semiconductor at the flat band condition, EF(FB), is constrained to a position between the conduction band, EC, and the valence band, EV,: |EC| < |EF(FB)| < |EV| throughout the depth of the semiconductor. The same constraint applies on the electrode potential scale, where the values are referenced against a common reference electrode: UC(FB) < UF(FB) < UV(FB). Some experimentally determined flat band potentials appear to lie outside these fundamental boundaries. In order to assess the validity of any determined flat band potential, the boundaries set by the conduction band and the valence band must be computed on both scales a priori, where possible. This is accomplished with the aid of an analytical reconstruction of the semiconductor|electrolyte interface in question. To illustrate this approach, we provide a case study based on synthetic hematite, α-Fe2O3. The analysis of this particular semiconductor is motivated by the large variance in the flat band potential values reported in the literature.

  19. Theoretical performance of solar cell based on mini-bands quantum dots

    SciTech Connect

    Aly, Abou El-Maaty M. E-mail: ashraf.nasr@gmail.com; Nasr, A. E-mail: ashraf.nasr@gmail.com

    2014-03-21

    The tremendous amount of research in solar energy is directed toward intermediate band solar cell for its advantages compared with the conventional solar cell. The latter has lower efficiency because the photons have lower energy than the bandgap energy and cannot excite mobile carriers from the valence band to the conduction band. On the other hand, if mini intermediate band is introduced between the valence and conduction bands, then the smaller energy photons can be used to promote charge carriers transfer to the conduction band and thereby the total current increases while maintaining a large open circuit voltage. In this article, the influence of the new band on the power conversion efficiency for structure of quantum dots intermediate band solar cell is theoretically investigated and studied. The time-independent Schrödinger equation is used to determine the optimum width and location of the intermediate band. Accordingly, achievement of a maximum efficiency by changing the width of quantum dots and barrier distances is studied. Theoretical determination of the power conversion efficiency under the two different ranges of QD width is presented. From the obtained results, the maximum power conversion efficiency is about 70.42%. It is carried out for simple cubic quantum dot crystal under fully concentrated light. It is strongly dependent on the width of quantum dots and barrier distances.

  20. Comparative studies on photonic band structures of diamond and hexagonal diamond using the multiple scattering method

    NASA Astrophysics Data System (ADS)

    Chen, Hui; Zhang, Weiyi; Wang, Zhenlin

    2004-02-01

    Photonic band structures are investigated for both diamond and hexagonal diamond crystals composed of dielectric spheres, and absolute photonic band gaps (PBGs) are found in both cases. In agreement with both Karathanos and Moroz's calculations, a large PBG occurs between the eighth and ninth bands in diamond crystal, but a PBG in hexagonal diamond crystal is found to occur between the sixteenth and seventeenth bands because of the doubling of dielectric spheres in the primitive cell. To explore the physical mechanism of how the photonic band gap might be broadened, we have compared the electric field distributions (|E|2) of the 'valence' and 'conduction' band edges. Results show that the field intensity for the 'conduction' band locates in the inner core of the sphere while that of the 'valence' band concentrates in the outer shell. With this motivation, double-layer spheres are designed to enhance the corresponding photonic band gaps; the PBG is increased by 35% for the diamond structure, and 14% for the hexagonal diamond structure.

  1. 8-band k·p modelling of mid-infrared intersubband absorption in Ge quantum wells

    NASA Astrophysics Data System (ADS)

    Paul, D. J.

    2016-07-01

    The 8-band k.p parameters which include the direct band coupling between the conduction and the valence bands are derived and used to model optical intersubband transitions in Ge quantum well heterostructure material grown on Si substrates. Whilst for Si rich quantum wells the coupling between the conduction bands and valence bands is not important for accurate modelling, the present work demonstrates that the inclusion of such coupling is essential to accurately determine intersubband transitions between hole states in Ge and Ge-rich Si1-xGex quantum wells. This is due to the direct bandgap being far smaller in energy in Ge compared to Si. Compositional bowing parameters for a range of the key modelling input parameters required for Ge/SiGe heterostructures, including the Kane matrix elements, the effective mass of the Γ 2 ' conduction band, and the Dresselhaus parameters for both 6- and 8-band k.p modelling, have been determined. These have been used to understand valence band intersubband transitions in a range of Ge quantum well intersubband photodetector devices in the mid-infrared wavelength range.

  2. Scandium Selenophosphates: Structure and Properties of K4Sc2(PSe4)2(P2Se6).

    PubMed

    Syrigos, Jonathan C; Kanatzidis, Mercouri G

    2016-05-01

    The new compound K4Sc2P4Se14 was synthesized via the polychalcogenide flux method. It crystallizes in the space group C2/c, and the structure is composed of (1)/∞[Sc2P4Se14(4-)] chains that are separated by K(+) cations. The structural motif features two [PSe4](3-) units and one [P2Se6](4-) unit bridging the Sc centers and has not been reported for any other compound. The (1)/∞[Sc2P4Se14(4-)] chains pack in a crosshatched pattern perpendicular to the c axis of the crystal, forming channels for half of the K(+) atoms while the other half occupy empty space between the chains. The orange-yellow crystals of K4Sc2P4Se14 are air-sensitive and gradually turn red over the course of a couple hours. The band gap of the phase is 2.25(2) eV, and Raman spectroscopy shows the symmetric stretches of the selenophosphate groups to be at 231 and 216 cm(-1) for the [PSe4](3-) and [P2Se6](4-) units, respectively. Solid-state (31)P MAS NMR of K4Sc2P4Se14 shows two prominent peaks at 11.31 and -23.07 ppm and one minor peak at -106.36 ppm, most likely due to degradation of the product or an unknown second phase. PMID:27078201

  3. Coupled-cluster based basis sets for valence correlation calculations

    NASA Astrophysics Data System (ADS)

    Claudino, Daniel; Gargano, Ricardo; Bartlett, Rodney J.

    2016-03-01

    Novel basis sets are generated that target the description of valence correlation in atoms H through Ar. The new contraction coefficients are obtained according to the Atomic Natural Orbital (ANO) procedure from CCSD(T) (coupled-cluster singles and doubles with perturbative triples correction) density matrices starting from the primitive functions of Dunning et al. [J. Chem. Phys. 90, 1007 (1989); ibid. 98, 1358 (1993); ibid. 100, 2975 (1993)] (correlation consistent polarized valence X-tuple zeta, cc-pVXZ). The exponents of the primitive Gaussian functions are subject to uniform scaling in order to ensure satisfaction of the virial theorem for the corresponding atoms. These new sets, named ANO-VT-XZ (Atomic Natural Orbital Virial Theorem X-tuple Zeta), have the same number of contracted functions as their cc-pVXZ counterparts in each subshell. The performance of these basis sets is assessed by the evaluation of the contraction errors in four distinct computations: correlation energies in atoms, probing the density in different regions of space via (-3 ≤ n ≤ 3) in atoms, correlation energies in diatomic molecules, and the quality of fitting potential energy curves as measured by spectroscopic constants. All energy calculations with ANO-VT-QZ have contraction errors within "chemical accuracy" of 1 kcal/mol, which is not true for cc-pVQZ, suggesting some improvement compared to the correlation consistent series of Dunning and co-workers.

  4. Coupled-cluster based basis sets for valence correlation calculations.

    PubMed

    Claudino, Daniel; Gargano, Ricardo; Bartlett, Rodney J

    2016-03-14

    Novel basis sets are generated that target the description of valence correlation in atoms H through Ar. The new contraction coefficients are obtained according to the Atomic Natural Orbital (ANO) procedure from CCSD(T) (coupled-cluster singles and doubles with perturbative triples correction) density matrices starting from the primitive functions of Dunning et al. [J. Chem. Phys. 90, 1007 (1989); ibid. 98, 1358 (1993); ibid. 100, 2975 (1993)] (correlation consistent polarized valence X-tuple zeta, cc-pVXZ). The exponents of the primitive Gaussian functions are subject to uniform scaling in order to ensure satisfaction of the virial theorem for the corresponding atoms. These new sets, named ANO-VT-XZ (Atomic Natural Orbital Virial Theorem X-tuple Zeta), have the same number of contracted functions as their cc-pVXZ counterparts in each subshell. The performance of these basis sets is assessed by the evaluation of the contraction errors in four distinct computations: correlation energies in atoms, probing the density in different regions of space via ⟨r(n)⟩ (-3 ≤ n ≤ 3) in atoms, correlation energies in diatomic molecules, and the quality of fitting potential energy curves as measured by spectroscopic constants. All energy calculations with ANO-VT-QZ have contraction errors within "chemical accuracy" of 1 kcal/mol, which is not true for cc-pVQZ, suggesting some improvement compared to the correlation consistent series of Dunning and co-workers.

  5. Intracranial markers of emotional valence processing and judgments in music.

    PubMed

    Omigie, Diana; Dellacherie, Delphine; Hasboun, Dominique; Clément, Sylvain; Baulac, Michel; Adam, Claude; Samson, Séverine

    2015-01-01

    The involvement of the amygdala and orbitofrontal cortex in the processing of valenced stimuli is well established. However, less is known about the extent to which activity in these regions reflects a stimulus' physical properties, the individual subjective experience it evokes, or both. We recorded cortical electrical activity from five epileptic patients implanted with depth electrodes for presurgical evaluation while they rated "consonant" and "dissonant" musical chords using a "pleasantness" scale. We compared the pattern of responses in the amygdala and orbitofrontal cortex when trials were sorted by pleasantness judgments relative to when they were sorted by the acoustic properties known to influence emotional reactions to musical chords. This revealed earlier differential activity in the amygdala in the physical properties-based, relative to in the judgment-based, analyses. Thus, our results demonstrate that the amygdala has, first and foremost, a high initial sensitivity to the physical properties of valenced stimuli. The finding that differentiations in the amygdala based on pleasantness ratings had a longer latency suggests that in this structure, mediation of emotional judgment follows accumulation of sensory information. This is in contrast to the orbitofrontal cortex where sensitivity to sensory information did not precede differentiation based on affective judgments. PMID:25496511

  6. Aggression proneness: Transdiagnostic processes involving negative valence and cognitive systems.

    PubMed

    Verona, Edelyn; Bresin, Konrad

    2015-11-01

    Aggressive behavior is observed in persons with various mental health problems and has been studied from the perspectives of neuroscience and psychophysiology. The present research reviews some of the extant experimental literature to help clarify the interplay between domains of functioning implicated in aggression proneness. We then convey a process-oriented model that elucidates how the interplay of the Negative Valence and Cognitive System domains of NIMH's Research Domain Criteria (RDoC) helps explain aggression proneness, particularly reactive aggression. Finally, we report on a study involving event-related potential (ERP) indices of emotional and inhibitory control processing during an emotional-linguistic go/no-go task among 67 individuals with histories of violence and criminal offending (30% female, 44% African-American) who reported on their aggressive tendencies using the Buss-Perry Aggression Questionnaire. Results provide evidence that tendencies toward angry and aggressive behavior relate to reduced inhibitory control processing (no-go P3) specifically during relevant threat-word blocks, suggesting deterioration of cognitive control by acute or sustained threat sensitivity. These findings highlight the value of ERP methodologies for clarifying the interplay of Negative Valence and Cognitive System processes in aggression proneness.

  7. Valence-bond quantum Monte Carlo algorithms defined on trees.

    PubMed

    Deschner, Andreas; Sørensen, Erik S

    2014-09-01

    We present a class of algorithms for performing valence-bond quantum Monte Carlo of quantum spin models. Valence-bond quantum Monte Carlo is a projective T=0 Monte Carlo method based on sampling of a set of operator strings that can be viewed as forming a treelike structure. The algorithms presented here utilize the notion of a worm that moves up and down this tree and changes the associated operator string. In quite general terms, we derive a set of equations whose solutions correspond to a whole class of algorithms. As specific examples of this class of algorithms, we focus on two cases. The bouncing worm algorithm, for which updates are always accepted by allowing the worm to bounce up and down the tree, and the driven worm algorithm, where a single parameter controls how far up the tree the worm reaches before turning around. The latter algorithm involves only a single bounce where the worm turns from going up the tree to going down. The presence of the control parameter necessitates the introduction of an acceptance probability for the update. PMID:25314561

  8. Coupled-cluster based basis sets for valence correlation calculations.

    PubMed

    Claudino, Daniel; Gargano, Ricardo; Bartlett, Rodney J

    2016-03-14

    Novel basis sets are generated that target the description of valence correlation in atoms H through Ar. The new contraction coefficients are obtained according to the Atomic Natural Orbital (ANO) procedure from CCSD(T) (coupled-cluster singles and doubles with perturbative triples correction) density matrices starting from the primitive functions of Dunning et al. [J. Chem. Phys. 90, 1007 (1989); ibid. 98, 1358 (1993); ibid. 100, 2975 (1993)] (correlation consistent polarized valence X-tuple zeta, cc-pVXZ). The exponents of the primitive Gaussian functions are subject to uniform scaling in order to ensure satisfaction of the virial theorem for the corresponding atoms. These new sets, named ANO-VT-XZ (Atomic Natural Orbital Virial Theorem X-tuple Zeta), have the same number of contracted functions as their cc-pVXZ counterparts in each subshell. The performance of these basis sets is assessed by the evaluation of the contraction errors in four distinct computations: correlation energies in atoms, probing the density in different regions of space via ⟨r(n)⟩ (-3 ≤ n ≤ 3) in atoms, correlation energies in diatomic molecules, and the quality of fitting potential energy curves as measured by spectroscopic constants. All energy calculations with ANO-VT-QZ have contraction errors within "chemical accuracy" of 1 kcal/mol, which is not true for cc-pVQZ, suggesting some improvement compared to the correlation consistent series of Dunning and co-workers. PMID:26979680

  9. +2 Valence Metal Concentrations in Lion Creek, Oakland, California

    NASA Astrophysics Data System (ADS)

    Vazquez, P.; Zedd, T.; Chagolla, R.; Dutton-Starbuck, M.; Negrete, A.; Jinham, M.; Lapota, M.

    2012-12-01

    Seven major creeks exist within the City of Oakland, California. These creeks all flow in the southwest direction from forested hills down through densely populated streets where they become susceptible to urban runoff. Lion Creek has been diverted to engineered channels and underground culverts and runs directly under our school (Roots International) before flowing into the San Leandro Bay. One branch of the creek begins near an abandoned sulfur mine. Previous studies have shown that extremely high levels of lead, arsenic and iron exist in this portion of the creek due to acid mine drainage. In this study +2 valence heavy metals concentration data was obtained from samples collected from a segment of the creek located approximately 2.8 miles downstream from the mine. Concentrations in samples collected at three different sites along this segment ranged between 50 ppb and 100 ppb. We hypothesize that these levels are related to the high concentration of +2 valence heavy metals at the mining site. To test this hypothesis, we have obtained samples from various locations along the roughly 3.75 miles of Lion Creek that are used to assess changes in heavy metals concentration levels from the mining site to the San Leandro Bay.

  10. Valence-state reflectometry of complex oxide heterointerfaces

    DOE PAGES

    Hamann-Borrero, Jorge E.; Macke, Sebastian; Choi, Woo Seok; Sutarto, Ronny; He, Feizhou; Radi, Abdullah; Elfimov, Ilya; Green, Robert J.; Haverkort, Maurits W.; Zabolotnyy, Volodymyr B.; et al

    2016-09-16

    Emergent phenomena in transition-metal-oxide heterostructures such as interface superconductivity and magnetism have been attributed to electronic reconstruction, which, however, is difficult to detect and characterise. Here we overcome the associated difficulties to simultaneously address the electronic degrees of freedom and distinguish interface from bulk effects by implementing a novel approach to resonant X-ray reflectivity (RXR). Our RXR study of the chemical and valance profiles along the polar (001) direction of a LaCoO3 film on NdGaO3 reveals a pronounced valence-state reconstruction from Co3+ in the bulk to Co2+ at the surface, with an areal density close to 0.5 Co2+ ions permore » unit cell. An identical film capped with polar (001) LaAlO3 maintains the Co3+ valence over its entire thickness. As a result, we interpret this as evidence for electronic reconstruction in the uncapped film, involving the transfer of 0.5e– per unit cell to the subsurface CoO2 layer at its LaO-terminated polar surface.« less

  11. Valence-bond quantum Monte Carlo algorithms defined on trees.

    PubMed

    Deschner, Andreas; Sørensen, Erik S

    2014-09-01

    We present a class of algorithms for performing valence-bond quantum Monte Carlo of quantum spin models. Valence-bond quantum Monte Carlo is a projective T=0 Monte Carlo method based on sampling of a set of operator strings that can be viewed as forming a treelike structure. The algorithms presented here utilize the notion of a worm that moves up and down this tree and changes the associated operator string. In quite general terms, we derive a set of equations whose solutions correspond to a whole class of algorithms. As specific examples of this class of algorithms, we focus on two cases. The bouncing worm algorithm, for which updates are always accepted by allowing the worm to bounce up and down the tree, and the driven worm algorithm, where a single parameter controls how far up the tree the worm reaches before turning around. The latter algorithm involves only a single bounce where the worm turns from going up the tree to going down. The presence of the control parameter necessitates the introduction of an acceptance probability for the update.

  12. The role of valence quarks in proton fragmentation

    NASA Astrophysics Data System (ADS)

    van Hove, L.

    1981-06-01

    Following earlier theoretical and experimental work (Kalinowski et al. [6], Bourquin et al. [7]), baryon production by fragmentation of incident protons in high energy hadron collisions is re-investigated in terms of a fragmentation-recombination mechanism similar to a model proposed by Fukuda and Iso [4]. The multiplicities n f (B) for the various types of baryons B produced in proton fragmentation are expressed in terms of the probabilities a i for i=0, ..., 3 valence quarks of the incident proton to emerge in the baryon B and 3- i to emerge in mesons (following [7] we suppose that antibaryon production is mostly due to baryon-antibaryon pair production by a mechanism of non-fragmentation type, and this is taken into account in deducing n f (B) from baryon and antibaryon multiplicity data). The positivity of the a i is found to impose remarkably narrow constraints on the n f (B) for (meta)stable B, and we find the data to satisfy these constraints. We show furthermore that the data are compatible with uncorrelated behaviour of the valence quarks of the incident proton, each of them having a probability ≃ 0.6 to emerge in the fragmentation baryon B, and a probability ≃ 0.4 to emerge in a meson. We also briefly discuss the relation of our analysis to previous work on the recombination model of proton fragmentation and its possible extension to meson fragmentation.

  13. Ignoring real faces: effects of valence, threat, and salience.

    PubMed

    Blagrove, Elisabeth; Watson, Derrick G

    2014-04-01

    Facial stimuli have been shown to accrue a special status within visual processing, particularly when attention is prioritized to one face over another on the basis of affective content. This has been examined in relation to the ability of faces to guide or hold attention, or to resist attentional suppression. Previous work has shown that schematic faces can only be partially ignored and that the emotional valence of to-be-ignored faces has little effect. Given recent debates concerning the use of schematic faces, here we examined the ease with which photorealistic faces could be ignored. Although we found evidence of a partial preview benefit for these stimuli, the findings were complex, with stimulus salience, valence, and threat content interacting to affect both the strength of the benefit and target detection efficiency (Exps. 1-3). Experiment 4 then clarified the effects of physical salience and perceived stimulus similarity in the previous experiments, demonstrating that a combination of these factors is likely to account for the search patterns observed.

  14. Nitrogen valence electronic structure in the strong chemisorption limit: Molecular adsorption on Cr(110) and O/Cr(110)

    NASA Astrophysics Data System (ADS)

    Shinn, Neal D.

    1990-05-01

    Nitrogen adsorption and dissociation on clean and oxygen-dosed Cr(110) surfaces have been studied with angle-integrated synchrotron-radiation ultraviolet photoelectron spectroscopy (UPS) and work-function measurements. At 90 K, nitrogen adsorbs molecularly via a mobile precursor state and exhibits UPS valence-orbital peaks at binding energies of 12.7 (weak), 8.4, and 7.1 eV with respect to the Fermi level; these positions and separations suggest an unusual N2(ads) valence electronic structure similar to that of ``π-bonded'' N2 on Fe(111). Thermal dissociation of N2(ads) commences at 100 K but remains incomplete until ~265 K. Chemisorbed N2 increases the work function Φ by 0.1+/-0.1 eV, whereas annealing the adlayer to 300 K subsequently reduces Φ by 0.7 eV due to dissociation. At 300 K, only dissociative chemisorption is observed but with a reduced sticking probability and a lower saturation coverage compared with thermally dissociating a molecular adlayer. A surface-sensitive Cr valence-band feature is identified which (i) shifts to increasing binding energy with N2 adsorption, but (ii) exhibits different coverage-dependent behavior for isoelectronic N2(ads) and CO(ads). Low coverages of chemisorbed oxygen do not inhibit N2 adsorption but co-adsorption effects are observed when a N2(ads) saturated surface is exposed to large oxygen doses. Consideration of these results in comparison with other nitrogen chemisorption studies shows that the bonding of nitrogen to Cr(110) is not well described by the usual σ-donation and π-backbonding concepts. A bonding geometry with both nitrogen atoms coordinated to chromium atoms is proposed in spite of the absence of surface hollow sites usually invoked to account for such a species.

  15. A Time-Based Account of the Perception of Odor Objects and Valences

    PubMed Central

    Olofsson, Jonas K.; Bowman, Nicholas E.; Khatibi, Katherine; Gottfried, Jay A.

    2013-01-01

    Is human odor perception guided by memory or emotion? Object-centered accounts predict that recognition of unique odor qualities precedes valence decoding. Valence-centered accounts predict the opposite: that stimulus-driven valence responses precede and guide identification. In a speeded response time study, participants smelled paired odors, presented sequentially, and indicated whether the second odor in each pair belonged to the same category as the first (object evaluation task) or whether the second odor was more pleasant than the first (valence evaluation task). Object evaluation was faster and more accurate than valence evaluation. In a complementary experiment, participants performed an identification task, in which they indicated whether an odor matched the previously presented word label. Responses were quicker for odors preceded by semantically matching, rather than nonmatching, word labels, but results showed no evidence of interference from valence on nonmatching trials. These results are in accordance with object-centered accounts of odor perception. PMID:22961773

  16. Three-Electron Bond Valence-Bond Structures for the Ditetracyanoethylene Dianion.

    PubMed

    Harcourt, Richard D

    2015-05-12

    Using valence-bond structures of the types Ȧ · Ḃ and A∴B or A-̇B to represent diatomic three-electron bonds, two types of valence-bond structures are constructed for the cyclic 6-electron 4-center bonding unit that is present in the ditetracyanoethylene dianion. These latter valence-bond structures, which are obtained by singlet spin-pairing the antibonding electrons of two three-electron bonds, are examples of increased-valence structures. It is shown that increased-valence structures that use the Ȧ · Ḃ three-electron bond structure, which relate easily to their component Lewis structures, should be preferred to those that involve the A∴B or A-̇B three-electron bond structures. STO-6G weights are reported for the two 6-electron 4-center increased-valence structures for the [C2]2(2-) component of the ditetracyanoethylene dianion.

  17. Expertise in video game playing is associated with reduced valence-concordant emotional expressivity.

    PubMed

    Weinreich, André; Strobach, Tilo; Schubert, Torsten

    2015-01-01

    In carefully selected groups of video game playing (VGP) experts and nonexperts, we examined valence-concordant emotional expressivity. We measured electromyographic (EMG) activity over the corrugator supercilii muscle while participants viewed pleasant, neutral, and unpleasant pictures. Potential group differences concerning valence-concordant expressivity may arise from differences concerning the participants' emotional reactivity. To control for such differences, we concomitantly measured skin conductance response (SCR) and, in a separate affect misattribution procedure (AMP), valence transfer from the same set of stimuli. Importantly, we found attenuated valence-concordant EMG activity over the corrugator supercilii muscle in VGP experts compared to nonexperts, but no differences were evident concerning SCR or valence transfer in the AMP. The findings suggest that expertise in VGP is particularly associated with reduced valence-concordant emotional expressivity.

  18. Synchrotron studies of narrow band materials

    SciTech Connect

    Allen, J.W.

    1993-01-01

    Objective was to determine the single-particle electronic structure of selected narrow band materials in order to understand the relation between their electronic structures and novel low energy properties, such as mixed valence, heavy Fermions, Kondo effect, insulator-metal transitions, non-Fermi liquid behavior, and high-temperature superconductivity. This program supports photoemission spectroscopy (PES) at various synchrotrons. The progress is reported under the following section titles: ZSA (Zaanen-Sawatzky-Allen) systematics and I-M transitions in 3d transition metal oxides, insulator-metal transitions in superconducting cuprates, Fermi liquid and non-Fermi liquid behavior in angular resolved PES lineshapes, heavy-Fermion and non-Fermi liquid 5f electron systems, and Kondo insulators.

  19. Photonic band gap materials

    SciTech Connect

    Soukoulis, C.M. |

    1993-12-31

    An overview of the theoretical and experimental efforts in obtaining a photonic band gap, a frequency band in three-dimensional dielectric structures in which electromagnetic waves are forbidden, is presented.

  20. Bonds, bands and elasticity of smithsonite rock

    NASA Astrophysics Data System (ADS)

    Bouibes, A.; Zaoui, A.; Tunega, D.

    2013-07-01

    The objective here is to spread out in detail the various fundamental state properties of smithsonite rock (ZnCO3) for which the most intrinsic quantities remain still unknown. First-principles electronic structure calculations based on the density functional theory with the pseudopotential method were performed using diverse functionals. A number of mechanical quantities were evaluated such as bulk modulus, elastic constants, Young's and shear moduli, and transversal and longitudinal sound velocities (VS and VP). Fitting the compression data of smithsonite to the third-order Birch-Murnaghan equation of state gives a bulk modulus of 124.17 GPa, which reflects an important rigidity compared to the other carbonates. The analysis of the band structure reveals a band-gap energy of 3.36 eV that is close enough to some semiconductors rather than insulators. Finally the chemical bonding was analyzed through the electronic charge density of the total contributions of the valence bands. A pronounced charge transfer was observed towards the carbonate ion, indicating thereby the ionic character of ZnCO3.

  1. Influence of chemical bonds on the lifetime of the molecular-field-split 2p levels in H{sub 2}S

    SciTech Connect

    Bueno, Andre Machado; Brito, Arnaldo Naves de; Fink, Reinhold F.; Baessler, Margit; Bjoerneholm, Olle; Burmeister, Florian; Feifel, Raimund; Miron, Catalin; Sorensen, Stacey L.; Wang Honghong; Svensson, Svante

    2003-02-01

    Different lifetime broadenings in molecular-field-split 2p core levels in H{sub 2}S are predicted theoretically and are identified in an experimental investigation of the S 2p Auger electron spectrum. The measurements were performed for the transition to the vibrationally resolved X{sup 1}A{sub 1} ground state of H{sub 2}S{sup 2+}. The lifetimes of the 3e{sub 1/2} and 5e{sub 1/2} levels of the 2p ionized molecule are found to be 64 and 74 meV, respectively. This unambiguous determination of the lifetime difference of 10{+-}1 meV is only possible as the 4e{sub 1/2}{yields}X{sup 1}A{sub 1}(2b{sub 1}{sup -2}) decay channel that overlaps the 5e{sub 1/2}{yields}X{sup 1}A{sub 1}(2b{sub 1}{sup -2}) channel is practically suppressed in Auger decay in H{sub 2}S. The lifetime difference is confirmed by ab initio calculations. A theoretical analysis shows that it results from the mutual orientation of the core hole in the intermediate states and the valence electron density in the sulfur 3p orbitals. Both are strongly influenced by the chemical bond. Thus the observed effect is the direct result of a fundamental property of molecular electronic structure.

  2. Spot detection from MODIS imagery using 2P-CFAR

    NASA Astrophysics Data System (ADS)

    Ding, Xianwen; Li, Xiaofeng

    2015-12-01

    Oil spills are one of the major environmental concerns, especially in the coastal zones of the ocean. Satellite remote sensing imagery has proved to be a useful tool for monitoring oil spills in the marine environment. With its two daily acquisitions and the possibility to obtain near-real-time data free of charge, the Moderate Resolution Imaging Spectroradiometer (MODIS) shows interesting potential as such a cost-effective supplementary tool. Several researches on oil spill detection in MODIS imagery has been carried out for the past few years. Basically, oil spills were manually detected from MODIS imagery [1,2]. The disadvantage of the manual detection method is inefficient and subjective. Shi et al. proposed an oil spill detection method from MODIS imagery by using fuzzy cluster and texture feature extraction [3]. It works in an automatic manner and does not require any priori knowledge of occurrence or the spectral attributes of spills. But its efficiency in very near shore regions is limited. Chen and Zhao detected oil spills from the oil-water contrast ratio image by using a thresholding method [4].They found that the oil-water contrast ratio can be enhanced by replacing the original image with the ratio image of two different band ones in 400-800 nm. To obtain the oil-water contrast ratio image from the MODIS imagery, they selected the oil spill area and the background sea area and then calculated the mean radiance or emissivity value in those areas. By doing so, the automation and the accuracy of the method were reduced. Adamo et al. [5] and Kudryavtsev et al. [6] proposed physical methods for oil spill detection from MODIS imagery acquired in sunglint conditions. These two methods take imaging geometry into consideration and have the aid of other models or functions such as the Cox and Munk (1954) model [7],the CMOD4 model [8,9], the ECMWF (European Centre for Medium-Range Weather Forecasts) atmospheric model, and the transfer function, which increase the

  3. Applying a rigid band model to the XYB14 crystal family

    NASA Astrophysics Data System (ADS)

    Wan, Liwen F.; Beckman, Scott P.

    2011-10-01

    The compounds AlMgB14, AlLiB14 and MgMgB14 belong to the same space group, Imma, and share similar structural properties. It is predicted that the rigid band model accurately describes the electronic states of these orthorhombic borides. The position of the Fermi level within the states depends on the metal site constituency. In this work the electronic properties of each compound are studied in detail by ab initio methods. Löwdin population analysis is conducted to examine the local charge distribution, and the projected density of states is calculated. It is found that the valence band edge is strongly dominated by the "Binter" and "Bconnector" atoms. This indicates that moving the Fermi level into the valence band will result in changes to the local bonding between the icosahedra and the inter-icosahedra B atoms.

  4. Investigation of crystalline and electronic band alignment properties of GaP/Ge(111) heterostructure

    SciTech Connect

    Dixit, V. K.; Kumar, Shailendra; Singh, S. D.; Khamari, S. K.; Kumar, R.; Tiwari, Pragya; Sharma, T. K.; Oak, S. M.; Phase, D. M.

    2014-03-03

    Gallium phosphide (GaP) epitaxial layer and nanostructures are grown on n-Ge(111) substrates using metal organic vapour phase epitaxy. It is confirmed by high resolution x-ray diffraction measurements that the layer is highly crystalline and oriented with the coexistence of two domains, i.e., GaP(111)A and GaP(111)B, with an angle of 60° between them due to the formation of a wurtzite monolayer at the interface. The valence band offset between GaP and Ge is 0.7 ± 0.1 eV as determined from the valence band onsets and from Kraut's method. A band alignment diagram for GaP/Ge/GeOx is also constructed which can be used to design monolithic optoelectronic integrated circuits.

  5. Modulation of K2P2.1 and K2P10.1 K+ channel sensitivity to carvedilol by alternative mRNA translation initiation

    PubMed Central

    Kisselbach, J; Seyler, C; Schweizer, P A; Gerstberger, R; Becker, R; Katus, H A; Thomas, D

    2014-01-01

    Background and Purpose The β-receptor antagonist carvedilol blocks a range of ion channels. K2P2.1 (TREK1) and K2P10.1 (TREK2) channels are expressed in the heart and regulated by alternative translation initiation (ATI) of their mRNA, producing functionally distinct channel variants. The first objective was to investigate acute effects of carvedilol on human K2P2.1 and K2P10.1 channels. Second, we sought to study ATI-dependent modulation of K2P K+ current sensitivity to carvedilol. Experimental Approach Using standard electrophysiological techniques, we recorded currents from wild-type and mutant K2P2.1 and K2P10.1 channels in Xenopus oocytes and HEK 293 cells. Key Results Carvedilol concentration-dependently inhibited K2P2.1 channels (IC50,oocytes = 20.3 μM; IC50,HEK = 1.6 μM) and this inhibition was frequency-independent. When K2P2.1 isoforms generated by ATI were studied separately in oocytes, the IC50 value for carvedilol inhibition of full-length channels (16.5 μM) was almost 5-fold less than that for the truncated channel variant (IC50 = 79.0 μM). Similarly, the related K2P10.1 channels were blocked by carvedilol (IC50,oocytes = 24.0 μM; IC50,HEK = 7.6 μM) and subject to ATI-dependent modulation of drug sensitivity. Conclusions and Implications Carvedilol targets K2P2.1 and K2P10.1 K+ channels. This previously unrecognized mechanism supports a general role of cardiac K2P channels as antiarrhythmic drug targets. Furthermore, the work reveals that the sensitivity of the cardiac ion channels K2P2.1 and K2P10.1 to block was modulated by alternative mRNA translation initiation. PMID:25168769

  6. Mixed valence Creutz-Taube ion analogues incorporating thiacrowns: synthesis, structure, physical properties, and computational studies.

    PubMed

    Adams, Harry; Costa, Paulo J; Newell, Mike; Vickers, Steven J; Ward, Michael D; Félix, Vítor; Thomas, Jim A

    2008-12-15

    A series of nine new complexes incorporating [Ru(II)Cl([n]aneS(3))] (n = 12, 14, 16) metal centers bridged by three ditopic ligands containing two monodentate sites (pyrazine, 4,4'-bipyridine, and 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine) have been synthesized and fully characterized. The solid-state structures of three of the complexes have been further characterized by X-ray crystallography studies. Intermetallic interactions within the new systems have been probed using electrochemistry and optical spectroscopy. Cyclic voltammetry reveals that the three pyrazine bridged systems display two separate Ru(III)/(II) redox couples. Using spectroelectrochemistry, we have investigated the optical properties of these mixed valence, Creutz-Taube ion analogues. An analysis of the intervalence charge transfer bands for the complexes revealed that, despite possessing the same donor sets, the electronic delocalization within these systems is modulated by the nature of the coordinated thiacrown. Computational modeling using density function theory offers further evidence of interaction between metal centers and provides insights into how these interactions are mediated. PMID:19012395

  7. Metal–insulator transition of valence-controlled VO2 thin film prepared by RF magnetron sputtering using oxygen radical

    NASA Astrophysics Data System (ADS)

    Suetsugu, Takaaki; Shimazu, Yuichi; Tsuchiya, Takashi; Kobayashi, Masaki; Minohara, Makoto; Sakai, Enju; Horiba, Koji; Kumigashira, Hiroshi; Higuchi, Tohru

    2016-06-01

    We have prepared b-axis-oriented VO2 thin films by RF magnetron sputtering using oxygen radicals as the reactive gas. The VO2 thin films consist of a mixed-valence V3+/V4+ state formed by oxygen vacancies. The V3+ ratio strongly depends on the film thickness and the oxygen partial pressure of the radical gun during deposition. The lattice constant of the b-axis increases and the metal–insulator transition (MIT) temperature decreases with decreasing V3+ ratio, although the VO2 thin films with a high V3+ ratio of 42% do not exhibit MIT. The bandwidths and spectral weights of V 3d a1g and \\text{e}\\text{g}σ bands at around the Fermi level, which correspond to the insulating phase at 300 K, are smaller in the VO2 thin films with a low V3+ ratio. These results indicate that the control of the mixed-valence V3+/V4+ state is important for the MIT of b-axis-oriented VO2 thin films.

  8. Metal-insulator transition of valence-controlled VO2 thin film prepared by RF magnetron sputtering using oxygen radical

    NASA Astrophysics Data System (ADS)

    Suetsugu, Takaaki; Shimazu, Yuichi; Tsuchiya, Takashi; Kobayashi, Masaki; Minohara, Makoto; Sakai, Enju; Horiba, Koji; Kumigashira, Hiroshi; Higuchi, Tohru

    2016-06-01

    We have prepared b-axis-oriented VO2 thin films by RF magnetron sputtering using oxygen radicals as the reactive gas. The VO2 thin films consist of a mixed-valence V3+/V4+ state formed by oxygen vacancies. The V3+ ratio strongly depends on the film thickness and the oxygen partial pressure of the radical gun during deposition. The lattice constant of the b-axis increases and the metal-insulator transition (MIT) temperature decreases with decreasing V3+ ratio, although the VO2 thin films with a high V3+ ratio of 42% do not exhibit MIT. The bandwidths and spectral weights of V 3d a1g and \\text{e}\\text{g}σ bands at around the Fermi level, which correspond to the insulating phase at 300 K, are smaller in the VO2 thin films with a low V3+ ratio. These results indicate that the control of the mixed-valence V3+/V4+ state is important for the MIT of b-axis-oriented VO2 thin films.

  9. Extreme-Ultraviolet-Initated High-Order Harmonic Generation: Driving Inner-Valence Electrons Using Below-Threshold-Energy Extreme-Ultraviolet Light.

    PubMed

    Brown, A C; van der Hart, H W

    2016-08-26

    We propose a novel scheme for resolving the contribution of inner- and outer-valence electrons in extreme-ultraviolet (XUV)-initiated high-harmonic generation in neon. By probing the atom with a low-energy (below the 2s ionization threshold) ultrashort XUV pulse, the 2p electron is steered away from the core, while the 2s electron is enabled to describe recollision trajectories. By selectively suppressing the 2p recollision trajectories, we can resolve the contribution of the 2s electron to the high-harmonic spectrum. We apply the classical trajectory model to account for the contribution of the 2s electron, which allows for an intuitive understanding of the process.

  10. Extreme-Ultraviolet-Initated High-Order Harmonic Generation: Driving Inner-Valence Electrons Using Below-Threshold-Energy Extreme-Ultraviolet Light.

    PubMed

    Brown, A C; van der Hart, H W

    2016-08-26

    We propose a novel scheme for resolving the contribution of inner- and outer-valence electrons in extreme-ultraviolet (XUV)-initiated high-harmonic generation in neon. By probing the atom with a low-energy (below the 2s ionization threshold) ultrashort XUV pulse, the 2p electron is steered away from the core, while the 2s electron is enabled to describe recollision trajectories. By selectively suppressing the 2p recollision trajectories, we can resolve the contribution of the 2s electron to the high-harmonic spectrum. We apply the classical trajectory model to account for the contribution of the 2s electron, which allows for an intuitive understanding of the process. PMID:27610852

  11. Extreme-Ultraviolet-Initated High-Order Harmonic Generation: Driving Inner-Valence Electrons Using Below-Threshold-Energy Extreme-Ultraviolet Light

    NASA Astrophysics Data System (ADS)

    Brown, A. C.; van der Hart, H. W.

    2016-08-01

    We propose a novel scheme for resolving the contribution of inner- and outer-valence electrons in extreme-ultraviolet (XUV)-initiated high-harmonic generation in neon. By probing the atom with a low-energy (below the 2 s ionization threshold) ultrashort XUV pulse, the 2 p electron is steered away from the core, while the 2 s electron is enabled to describe recollision trajectories. By selectively suppressing the 2 p recollision trajectories, we can resolve the contribution of the 2 s electron to the high-harmonic spectrum. We apply the classical trajectory model to account for the contribution of the 2 s electron, which allows for an intuitive understanding of the process.

  12. Band-engineered SrTiO{sub 3} nanowires for visible light photocatalysis

    SciTech Connect

    Fu, Q.; He, T.; Li, J. L.; Yang, G. W.

    2012-11-15

    We have theoretically investigated the structural, electronic, and optical properties of perovskite SrTiO{sub 3} nanowires for use in visible light photocatalytic applications using pseudopotential density-functional theory calculations. The electronic structure calculations show that the band gap is modified in the SrTiO{sub 3} nanowires compared with that of the bulk. For TiO{sub 2}-terminated nanowires, the mid-band states induced by the combination of oxygen and strontium atoms on the surface lead to a shift in the valence band toward the conduction band without interference from the edge of the conduction band, which reduces the band gap. On the contrary, the electronic states induced by the combination of oxygen and strontium atoms on the surface of SrO-terminated nanowires lead to a shift in the conduction band toward the valence band. The calculated optical results indicate that the absorption edge of the nanowires shift towards the red-light region. These theoretical results suggest that perovskite SrTiO{sub 3} nanowires are promising candidates for use in visible light photocatalytic processes such as solar-assisted water splitting reactions.

  13. Band Alignment Engineering at Cu2O/ZnO Heterointerfaces.

    PubMed

    Siol, Sebastian; Hellmann, Jan C; Tilley, S David; Graetzel, Michael; Morasch, Jan; Deuermeier, Jonas; Jaegermann, Wolfram; Klein, Andreas

    2016-08-24

    Energy band alignments at heterointerfaces play a crucial role in defining the functionality of semiconductor devices, yet the search for material combinations with suitable band alignments remains a challenge for numerous applications. In this work, we demonstrate how changes in deposition conditions can dramatically influence the functional properties of an interface, even within the same material system. The energy band alignment at the heterointerface between Cu2O and ZnO was studied using photoelectron spectroscopy with stepwise deposition of ZnO onto Cu2O and vice versa. A large variation of energy band alignment depending on the deposition conditions of the substrate and the film is observed, with valence band offsets in the range ΔEVB = 1.45-2.7 eV. The variation of band alignment is accompanied by the occurrence or absence of band bending in either material. It can therefore be ascribed to a pinning of the Fermi level in ZnO and Cu2O, which can be traced back to oxygen vacancies in ZnO and to metallic precipitates in Cu2O. The intrinsic valence band offset for the interface, which is not modified by Fermi level pinning, is derived as ΔEVB ≈ 1.5 eV, being favorable for solar cell applications. PMID:27452037

  14. The splitting and oscillator strengths for the 2S/2/S-2p/2/P/0/ doublet in lithium-like sulfur. [during Skylab observed solar flares

    NASA Technical Reports Server (NTRS)

    Pegg, D. J.; Forester, J. P.; Elston, S. B.; Griffin, P. M.; Peterson, R. S.; Thoe, R. S.; Vane, C. R.; Sellin, I. A.; Groeneveld, K.-O.

    1977-01-01

    The beam-foil technique has been used to study the 2S(2)S-2p(2)P(0) doublet in S XIV. The results confirm the doublet splitting measured aboard Skylab during solar flare events. In addition, the oscillator strengths for the resonance transitions comprising this doublet have been measured and found to agree well with recent relativistic f-value calculations.

  15. Band structure of core-shell semiconductor nanowires

    NASA Astrophysics Data System (ADS)

    Pistol, Mats-Erik; Pryor, Craig

    2009-03-01

    We present band structures of strained core-shell nanowires composed of zincblende III-V (binary) semiconductors. We consider all combinations of AlN, GaN, InN, and all combinations of AlP, GaP, AlAs, GaAs, InP, InAs, AlSb, GaSb, and InSb. We compute the γ- and X-conduction band minima as well as the valence band maximum, all as functions of the core and shell radii. The calculations were performed using continuum elasticity theory for the strain, eight-band strain-dependent k.p theory for the γ-point energies, and single band approximation for the X-point conduction minima. We identify structures with type-I, type-II and type-III band alignment, as well as systems in which one material becomes metallic due to a negative band-gap. We identify structures that may support exciton crystals with and without photoexcitation. We have also computed the effective masses, from which the confinement energy may be estimated. All the results [Pistol and Pryor, Phys. Rev. B 78, 115319] are available in graphical and tabular form at www.semiconductor.physics.uiowa.edu

  16. Band-gap and band-edge engineering of multicomponent garnet scintillators from first principles

    SciTech Connect

    Yadav, Satyesh K.; Uberuaga, Blas P.; Nikl, Martin; Jiang, Chao; Stanek, Christopher R.

    2015-11-24

    Complex doping schemes in R3Al5O12 (where R is the rare-earth element) garnet compounds have recently led to pronounced improvements in scintillator performance. Specifically, by admixing lutetium and yttrium aluminate garnets with gallium and gadolinium, the band gap is altered in a manner that facilitates the removal of deleterious electron trapping associated with cation antisite defects. Here, we expand upon this initial work to systematically investigate the effect of substitutional admixing on the energy levels of band edges. Density-functional theory and hybrid density-functional theory (HDFT) are used to survey potential admixing candidates that modify either the conduction-band minimum (CBM) or valence-band maximum (VBM). We consider two sets of compositions based on Lu3B5O12 where B is Al, Ga, In, As, and Sb, and R3Al5O12, where R is Lu, Gd, Dy, and Er. We find that admixing with various R cations does not appreciably affect the band gap or band edges. In contrast, substituting Al with cations of dissimilar ionic radii has a profound impact on the band structure. We further show that certain dopants can be used to selectively modify only the CBM or the VBM. Specifically, Ga and In decrease the band gap by lowering the CBM, while As and Sb decrease the band gap by raising the VBM, the relative change in band gap is quantitatively validated by HDFT. These results demonstrate a powerful approach to quickly screen the impact of dopants on the electronic structure of scintillator compounds, identifying those dopants which alter the band edges in very specific ways to eliminate both electron and hole traps responsible for performance limitations. Furthermore, this approach should be broadly applicable for the optimization of electronic and optical performance for a wide range of compounds by tuning the VBM and CBM.

  17. Effect of low-temperature annealing on the electronic- and band-structures of (Ga,Mn)As epitaxial layers

    SciTech Connect

    Yastrubchak, O. Gluba, L.; Żuk, J.; Wosinski, T. Andrearczyk, T.; Domagala, J. Z.; Sadowski, J.

    2014-01-07

    The effect of outdiffusion of Mn interstitials from (Ga,Mn)As epitaxial layers, caused by post-growth low-temperature annealing, on their electronic- and band-structure properties has been investigated by modulation photoreflectance (PR) spectroscopy. The annealing-induced changes in structural and magnetic properties of the layers were examined with high-resolution X-ray diffractometry and superconducting quantum interference device magnetometry, respectively. They confirmed an outdiffusion of Mn interstitials from the layers and an enhancement in their hole concentration, which were more efficient for the layer covered with a Sb cap acting as a sink for diffusing Mn interstitials. The PR results demonstrating a decrease in the band-gap-transition energy in the as-grown (Ga,Mn)As layers, with respect to that in the reference GaAs one, are interpreted by assuming a merging of the Mn-related impurity band with the GaAs valence band. Whereas an increase in the band-gap-transition energy caused by the annealing treatment of the (Ga,Mn)As layers is interpreted as a result of annealing-induced enhancement of the free-hole concentration and the Fermi level location within the valence band. The experimental results are consistent with the valence-band origin of itinerant holes mediating ferromagnetic ordering in (Ga,Mn)As, in agreement with the Zener model for ferromagnetic semiconductors.

  18. Band alignment of ultra-thin hetero-structure ZnO/TiO{sub 2} junction

    SciTech Connect

    Shen, Kai; Wu, Kunjie; Wang, Deliang

    2014-03-01

    Graphical abstract: - Highlights: • Band alignment at the ZnO/TiO{sub 2} hetero-structural interface with different ZnO coating thickness was studied. • The valence band offset was decreased with increased ZnO coating layer thickness. • The interface dipole was responsible for the decreased band offset. - Abstract: The band alignment at the ZnO/TiO{sub 2} hetero-structure interface was measured by high resolution X-ray photoelectron spectroscopy. The valence band offset (E{sub ZnO}−E{sub TiO{sub 2}}){sub Valence} was linearly changed from 0.27 to 0.01 eV at the interface with increased ZnO coating thickness from 0.7 to 7 nm. The interface dipole presented at the ZnO/TiO{sub 2} interface was responsible for the decreased band offset. The band alignment of the ZnO/TiO{sub 2} heterojunction is a type II alignment.

  19. Chiral Bands in Odd-Odd Triaxially Deformed Nuclei

    NASA Astrophysics Data System (ADS)

    Starosta, K.

    2001-10-01

    In rotational bands built on high-j single-particle orbitals in odd-odd nuclei having triaxial shapes, the angular momenta of the valence proton, the valence neutron, and the collective rotation tend to align along the perpendicular axes of the triaxial core. This occurs when the Fermi level is low within the proton (neutron) subshell, but high within the neutron (proton) subshell resulting in their angular momenta oriented along the short and long axes, respectively. The core angular momentum is oriented along the intermediate axis because it has the largest moment of inertia according to the model of irrotational flow. These three mutually perpendicular vectors can be arranged to form two systems which differ by intrinsic chirality, a left- and a right-handed system; the two systems cannot be transformed into each other by rotation or space inversion, but are related by an operator, which involves time reversal. Chirality resulting from orthogonal coupling of angular momenta is unique to rotational bands in atomic nuclei since these are the only systems where a significant part of the total spin results from single-particle contributions. In relation to time reversal, chirality is a novel example of spontaneous symmetry breaking, on the same level as octupole deformation in relation to space inversion. The main experimental fingerprint of chirality in nuclear rotation is the doubling of states in rotational bands. Δ I=1 doublet-band structures with remarkably similar experimental characteristics, recently observed for N=75 and N=73 isotones in the A ~130 region, have been interpreted as chiral-band partners built on the πh_11/2νh_11/2 configuration. Additional transition rate information is being investigated both experimentally and theoretically. The description of the chiral partner bands based on the microscopic Tilted Axis Cranking approach in the intrinsic, body-fixed reference frame and phenomenological core-particle coupling in the laboratory reference

  20. The use of bulk states to accelerate the band edge statecalculation of a semiconductor quantum dot

    SciTech Connect

    Vomel, Christof; Tomov, Stanimire Z.; Wang, Lin-Wang; Marques,Osni A.; Dongarra, Jack J.

    2006-05-10

    We present a new technique to accelerate the convergence of the folded spectrum method in empirical pseudopotential band edge state calculations for colloidal quantum dots. We use bulk band states of the materials constituent of the quantum dot to construct initial vectors and a preconditioner. We apply these to accelerate the convergence of the folded spectrum method for the interior states at the top of the valence and the bottom of the conduction band. For large CdSe quantum dots, the number of iteration steps until convergence decreases by about a factor of 4 compared to previous calculations.

  1. Effect of variable valence impurities on the formation of bismuth-related optical centres in a silicate glass

    SciTech Connect

    Galagan, B I; Denker, B I; Lili Hu; Sverchkov, S E; Shulman, I L; Dianov, Evgenii M

    2012-10-31

    We have studied the effect of variable valence impurities (cerium and iron) on the formation of bismuth-related IR luminescence centres and the optical loss between 1000 and 1300 nm in a magnesium aluminosilicate glass. The results demonstrate that additional doping of the glass with ceria leads to effective bleaching in a wide spectral range, including the luminescence range of the bismuth centres. At the same time, ceria reduces the concentration of luminescence centres. Gamma irradiation of the glass bleached by cerium restores the luminescence centres but leads to a background loss in a wide spectral range. Iron is shown to be a very harmful impurity in bismuth-doped active media: even trace levels of iron prevent the formation of bismuth-related active centres in the glass and produce a strong, broad absorption band centred near 1 {mu}m. (luminescence of glasses)

  2. Vibrational effects on valence electron momentum distributions of ethylene.

    PubMed

    Watanabe, Noboru; Yamazaki, Masakazu; Takahashi, Masahiko

    2012-09-21

    We report an electron momentum spectroscopy study of vibrational effects on the electron momentum distributions for the outer valence orbitals of ethylene (C(2)H(4)). The symmetric noncoplanar (e,2e) experiment has been conducted at an impact energy of 1.2 keV. Furthermore, a theoretical method of calculating electron momentum distributions for polyatomic molecules has been developed with vibrational effects being involved. It is shown from comparisons between experiment and theory that taking into account effects of the CH(2) asymmetric stretching and CH(2) rocking vibrational modes of C(2)H(4) is essential for a proper understanding of the electron momentum distribution of the 1b(3g) molecular orbital.

  3. The application of cholesky decomposition in valence bond calculation.

    PubMed

    Gong, Xiping; Chen, Zhenhua; Wu, Wei

    2016-09-01

    The Cholesky decomposition (CD) technique, used to approximate the two-electron repulsion integrals (ERIs), is applied to the valence bond self-consistent field (VBSCF) method. Test calculations on ethylene, C2 n H2 n +2 , and C2 n H4 n -2 molecules (n = 1-7) show that the performance of the VBSCF method is much improved using the CD technique, and thus, the integral transformation from basis functions to VB orbitals is no longer the bottleneck in VBSCF calculations. The errors of the CD-based ERIs and of the total energy are controlled by the CD threshold, for which a value of 10(-6) ensures to control the total energy error within 10(-6) Hartree. © 2016 Wiley Periodicals, Inc. PMID:27377531

  4. The valence-fluctuating ground state of plutonium

    PubMed Central

    Janoschek, Marc; Das, Pinaki; Chakrabarti, Bismayan; Abernathy, Douglas L.; Lumsden, Mark D.; Lawrence, John M.; Thompson, Joe D.; Lander, Gerard H.; Mitchell, Jeremy N.; Richmond, Scott; Ramos, Mike; Trouw, Frans; Zhu, Jian-Xin; Haule, Kristjan; Kotliar, Gabriel; Bauer, Eric D.

    2015-01-01

    A central issue in material science is to obtain understanding of the electronic correlations that control complex materials. Such electronic correlations frequently arise because of the competition of localized and itinerant electronic degrees of freedom. Although the respective limits of well-localized or entirely itinerant ground states are well understood, the intermediate regime that controls the functional properties of complex materials continues to challenge theoretical understanding. We have used neutron spectroscopy to investigate plutonium, which is a prototypical material at the brink between bonding and nonbonding configurations. Our study reveals that the ground state of plutonium is governed by valence fluctuations, that is, a quantum mechanical superposition of localized and itinerant electronic configurations as recently predicted by dynamical mean field theory. Our results not only resolve the long-standing controversy between experiment and theory on plutonium’s magnetism but also suggest an improved understanding of the effects of such electronic dichotomy in complex materials. PMID:26601219

  5. Theory of Valence-Fluctuating Tm Impurities. I

    NASA Astrophysics Data System (ADS)

    Saso, Tetsuro

    1989-11-01

    A new formalism is presented for describing mixed valent Tm impurities fluctuating between two magnetic configurations. Based on the self-consistent perturbation scheme, the present formalism incorporates not only the valence fluctuation between 4f12 and 4f13, but also the multiscattering process of 4f13 and a conduction electron, yielding a singlet bound state. Thus the ground state is a Kondo singlet, which however is different from the ordinary Kondo state and conceptually new in that the length of the local moment of the impurity is fluctuating between the two values j{=}6 and J{=}7/2. Numerical calculations are presented for the spectral distribution function of these states. Systematic study of the Kondo temperature TK yields that TK is substantially low when the number of f electrons is close to 12. Contribution of the above scattering processes to the f-electron spectral function and the magnetic susceptibility is also disscussed.

  6. Incautiously Optimistic: Positively-Valenced Cognitive Avoidance in Adult ADHD

    PubMed Central

    Knouse, Laura E.; Mitchell, John T.

    2015-01-01

    Clinicians who conduct cognitive-behavioral therapy (CBT) targeting attention-deficit/hyperactivity disorder (ADHD) in adulthood have noted that their patients sometimes verbalize overly positive automatic thoughts and set overly optimistic goals. These cognitions are frequently related to failure to engage in compensatory behavioral strategies emphasized in CBT. In this paper, we offer a functional analysis of this problematic pattern, positively-valenced cognitive avoidance, and suggest methods for addressing it within CBT for adult ADHD. We propose that maladaptive positive cognitions function to relieve aversive emotions in the short-term and are therefore negatively reinforced but that, in the long-term, they are associated with decreased likelihood of active coping and increased patterns of behavioral avoidance. Drawing on techniques from Behavioral Activation (BA), we offer a case example to illustrate these concepts and describe step-by-step methods for clinicians to help patients recognize avoidant patterns and engage in more active coping. PMID:25908901

  7. Resonating Valence Bond states for low dimensional S=1 antiferromagnets

    NASA Astrophysics Data System (ADS)

    Liu, Zheng-Xin; Zhou, Yi; Ng, Tai-Kai

    2014-03-01

    We study S = 1 spin liquid states in low dimensions. We show that the resonating-valence-bond (RVB) picture of S = 1 / 2 spin liquid state can be generalized to S = 1 case. For S = 1 system, a many-body singlet (with even site number) can be decomposed into superposition of products of two-body singlets. In other words, the product states of two-body singlets, called the singlet pair states (SPSs), are over complete to span the Hilbert space of many-body singlets. Furthermore, we generalized fermionic representation and the corresponding mean field theory and Gutzwiller projected stats to S = 1 models. We applied our theory to study 1D anti-ferromagnetic bilinear-biquadratic model and show that both the ground states (including the phase transition point) and the excited states can be understood excellently well within the framework. Our method can be applied to 2D S = 1 antiferromagnets.

  8. Plaquette valence bond theory of high-temperature superconductivity

    NASA Astrophysics Data System (ADS)

    Harland, Malte; Katsnelson, Mikhail I.; Lichtenstein, Alexander I.

    2016-09-01

    We present a strong-coupling approach to the theory of high-temperature superconductivity based on the observation of a quantum critical point in the plaquette within the t ,t' Hubbard model. The crossing of ground-state energies in the N =2 -4 sectors occurs for parameters close to the optimal doping. The theory predicts the maximum of the dx2-y2-wave order parameter at the border between localized and itinerant electron behaviors and gives a natural explanation for the pseudogap formation via the soft-fermion mode related to local singlet states of the plaquette in the environment. Our approach follows the general line of resonating valence-bond theory stressing a crucial role of singlets in the physics of high-Tc superconductors but focuses on the formation of local singlets, similar to phenomena observed in frustrated one-dimensional quantum spin models.

  9. The valence-fluctuating ground state of plutonium

    SciTech Connect

    Janoschek, Marc; Das, Pinaki; Chakrabarti, Bismayan; Abernathy, Douglas L.; Lumsden, Mark D.; Lawrence, John M.; Thompson, Joe D.; Lander, Gerard H.; Mitchell, Jeremy N.; Richmond, Scott; Ramos, Mike; Trouw, Frans; Zhu, Jian -Xin; Haule, Kristjan; Kotliar, Gabriel; Bauer, Eric D.

    2015-07-10

    A central issue in material science is to obtain understanding of the electronic correlations that control complex materials. Such electronic correlations frequently arise because of the competition of localized and itinerant electronic degrees of freedom. Although the respective limits of well-localized or entirely itinerant ground states are well understood, the intermediate regime that controls the functional properties of complex materials continues to challenge theoretical understanding. We have used neutron spectroscopy to investigate plutonium, which is a prototypical material at the brink between bonding and nonbonding configurations. In addition, our study reveals that the ground state of plutonium is governed by valence fluctuations, that is, a quantum mechanical superposition of localized and itinerant electronic configurations as recently predicted by dynamical mean field theory. Our results not only resolve the long-standing controversy between experiment and theory on plutonium’s magnetism but also suggest an improved understanding of the effects of such electronic dichotomy in complex materials.

  10. Overlap populations, bond orders and valences for 'fuzzy' atoms

    NASA Astrophysics Data System (ADS)

    Mayer, I.; Salvador, P.

    2004-01-01

    Proper definitions are proposed to calculate interatomic overlap populations, bond order (multiplicity) indices and actual atomic valences from the results of ab initio quantum chemical calculations, in terms of 'fuzzy' atoms, i.e., such divisions of the three-dimensional physical space into atomic regions in which the regions assigned to the individual atoms have no sharp boundaries but exhibit a continuous transition from one to another. The results of test calculations are in agreement with the classical chemical notions, exhibit unexpectedly small basis sensitivity and do not depend too much on the selection of the weight function defining the actual division of the space into 'fuzzy' atomic regions. The scheme is applicable on both SCF and correlated levels of theory. A free program is available.

  11. Valence bond cluster studies of alkali metal/semiconductor bonding

    NASA Astrophysics Data System (ADS)

    Tatar, Robert C.; Messmer, Richard P.

    1986-12-01

    We present results of cluster studies of alkali metal/semiconductor bonding. Using the Generalized Valence Bond (GVB) method, we find a remarkable consistency in the behavoir of bonding orbitals for a variety of systems, including: LiH, CLi4, LiH4 and several hypervalent systems, such as SiH3Li2, SiH4Li2. Our results show that the metal-semiconductor bonding in these systems can be understood in terms of a pairing between McAdon-Goddard type metallic bonding orbitals and a set of equivalent orbitals of the non-metallic species. We propose that the results are relevant to the initial stages of alkali overlayer growth on semiconductor surfaces and lead to a simple picture of the bonding including the transition from a non-conducting to a conducting layer. We have considered numerous proposed hypervalent structures in light of the above results and find that they can be understood.

  12. Negativity in the generalized Valence Bond Solid state

    NASA Astrophysics Data System (ADS)

    Santos, Raul A.; Korepin, V.

    2016-08-01

    Using a graphical presentation of the spin S one-dimensional Valence Bond Solid (VBS) state, based on the representation theory of the SU(2) Lie algebra of spins, we compute the spectrum of a mixed-state reduced density matrix. This mixed state of two blocks of spins A and B is obtained by tracing out the spins outside A and B, in the pure VBS state density matrix. We find in particular that the negativity of the mixed state is nonzero only for adjacent subsystems. The method introduced here can be generalized to the computation of entanglement properties in Levin-Wen models, that possess a similar algebraic structure to the VBS state in the ground state.

  13. Mesoscopic resonating valence bond system on a triple dot.

    PubMed

    Le Hur, Karyn; Recher, Patrik; Dupont, Emilie; Loss, Daniel

    2006-03-17

    We theoretically introduce a mesoscopic pendulum from a triple dot. The pendulum is fastened through a singly occupied dot (spin qubit). Two other strongly capacitively coupled islands form a double-dot charge qubit with one electron in excess oscillating between the two low-energy charge states (1,0) and (0,1). The triple dot is placed between two superconducting leads. Under realistic conditions, the main proximity effect stems from the injection of resonating singlet (valence) bonds on the triple dot. This gives rise to a Josephson current that is charge- and spin-dependent and, as a consequence, exhibits a distinct resonance as a function of the superconducting phase difference. PMID:16605773

  14. A density functional for core-valence correlation energy.

    PubMed

    Ranasinghe, Duminda S; Frisch, Michael J; Petersson, George A

    2015-12-01

    A density functional, εCV-DFT(ρc, ρv), describing the core-valence correlation energy has been constructed as a linear combination of εLY P (corr)(ρc), εV WN5 (corr)(ρc, ρv), εPBE (corr)(ρc, ρv), εSlater (ex)(ρc, ρv), εHCTH (ex)(ρc, ρv), εHF (ex)(ρc, ρv), and FCV-DFTNi,Zi, a function of the nuclear charges. This functional, with 6 adjustable parameters, reproduces (±0.27 kcal/mol rms error) a benchmark set of 194 chemical energy changes including 9 electron affinities, 18 ionization potentials, and 167 total atomization energies covering the first- and second-rows of the periodic table. This is almost twice the rms error (±0.16 kcal/mol) obtained with CCSD(T)/MTsmall calculations, but less than half the rms error (±0.65 kcal/mol) obtained with MP2/GTlargeXP calculations, and somewhat smaller than the rms error (±0.39 kcal/mol) obtained with CCSD/MTsmall calculations. The largest positive and negative errors from εCV-DFT(ρc, ρv) were 0.88 and -0.75 kcal/mol with the set of 194 core-valence energy changes ranging from +3.76 kcal/mol for the total atomization energy of propyne to -9.05 kcal/mol for the double ionization of Mg. Evaluation of the εCV-DFT(ρc, ρv) functional requires less time than a single SCF iteration, and the accuracy is adequate for any model chemistry based on the CCSD(T) level of theory. PMID:26646873

  15. Ab initio valence-space theory for exotic nuclei

    NASA Astrophysics Data System (ADS)

    Holt, Jason

    2015-10-01

    Recent advances in ab initio nuclear structure theory have led to groundbreaking predictions in the exotic medium-mass region, from the location of the neutron dripline to the emergence of new magic numbers far from stability. Playing a key role in this progress has been the development of sophisticated many-body techniques and chiral effective field theory, which provides a systematic basis for consistent many-nucleon forces and electroweak currents. Within the context of valence-space Hamiltonians derived from the nonperturbative in-medium similarity renormalization group (IM-SRG) approach, I will discuss the importance of 3N forces in understanding and making new discoveries in the exotic sd -shell region. Beginning in oxygen, we find that the effects of 3N forces are decisive in explaining why 24O is the last bound oxygen isotope, validating first predictions of this phenomenon from several years ago. Furthermore, 3N forces play a key role in reproducing spectroscopy, including signatures of doubly magic 22,24O, and physics beyond the dripline. Similar improvements are obtained in new spectroscopic predictions for exotic fluorine and neon isotopes, where agreement with recent experimental data is competitive with state-of-the-art phenomenology. Finally, I will discuss first applications of the IM-SRG to effective valence-space operators, such as radii and E 0 transitions, as well as extensions to general operators crucial for our future understanding of electroweak processes, such as neutrinoless double-beta decay. This work was supported by NSERC and the NRC Canada.

  16. A density functional for core-valence correlation energy

    NASA Astrophysics Data System (ADS)

    Ranasinghe, Duminda S.; Frisch, Michael J.; Petersson, George A.

    2015-12-01

    A density functional, ɛCV-DFT(ρc, ρv), describing the core-valence correlation energy has been constructed as a linear combination of ɛLY Pcorr(ρc), ɛV WN5corr(ρc, ρv), ɛPBEcorr(ρc, ρv), ɛSlaterex(ρc, ρv), ɛHCTHex(ρc, ρv), ɛHFex(ρc, ρv), and F CV -DFT (" separators=" N i , Z i ) , a function of the nuclear charges. This functional, with 6 adjustable parameters, reproduces (±0.27 kcal/mol rms error) a benchmark set of 194 chemical energy changes including 9 electron affinities, 18 ionization potentials, and 167 total atomization energies covering the first- and second-rows of the periodic table. This is almost twice the rms error (±0.16 kcal/mol) obtained with CCSD(T)/MTsmall calculations, but less than half the rms error (±0.65 kcal/mol) obtained with MP2/GTlargeXP calculations, and somewhat smaller than the rms error (±0.39 kcal/mol) obtained with CCSD/MTsmall calculations. The largest positive and negative errors from ɛCV-DFT(ρc, ρv) were 0.88 and -0.75 kcal/mol with the set of 194 core-valence energy changes ranging from +3.76 kcal/mol for the total atomization energy of propyne to -9.05 kcal/mol for the double ionization of Mg. Evaluation of the ɛCV-DFT(ρc, ρv) functional requires less time than a single SCF iteration, and the accuracy is adequate for any model chemistry based on the CCSD(T) level of theory.

  17. Skin-depth lattice strain, core-level trap depression and valence charge polarization of Al surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Bo, Maolin; Liu, Yonghui; Guo, Yongling; Wang, Haibin; Yue, Jian; Huang, Yongli

    2016-01-01

    Clarifying the origin for surface core-level shift (SCLS) and gaining quantitative information regarding the coordination-resolved local strain, binding energy (BE) shift and cohesive energy change have been a challenge. Here, we show that a combination of the bond order-length-strength (BOLS) premise, X-ray photoelectron spectroscopy (XPS) and the ab initio density functional theory (DFT) calculations of aluminum (Al) 2p3/2 energy shift of Al surfaces has enabled us to derive such information, namely, (i) the 2p3/2 energy of an isolated Al atom (72.146 ± 0.003eV) and its bulk shift (0.499 eV); (ii) the skin lattice contracts by up to 12.5% and the BE density increases by 70%; and (iii) the cohesive energy drops up to 38%. It is affirmed that the shorter and stronger bonds between under-coordinated atoms provide a perturbation to the Hamiltonian and hence lead to the local strain, quantum entrapment and valence charge polarization. Findings should help in understanding the phenomena of surface pre-melting and skin-high elasticity, in general.

  18. Interfacial chemical bonding state and band alignment of CaF{sub 2}/hydrogen-terminated diamond heterojunction

    SciTech Connect

    Liu, J. W.; Liao, M. Y.; Cheng, S. H.; Imura, M.; Koide, Y.

    2013-03-28

    CaF{sub 2} films are deposited on hydrogen-terminated diamond (H-diamond) by a radio-frequency sputter-deposition technique at room temperature. Interfacial chemical bonding state and band alignment of CaF{sub 2}/H-diamond heterojunction are investigated by X-ray photoelectron spectroscopy. It is confirmed that there are only C-Ca bonds at the CaF{sub 2}/H-diamond heterointerface. Valence and conductance band offsets of the CaF{sub 2}/H-diamond heterojunciton are determined to be 3.7 {+-} 0.2 and 0.3 {+-} 0.2 eV, respectively. It shows a type I straddling band configuration. The large valence band offset suggests advantage of the CaF{sub 2}/H-diamond heterojunciton for the development of high power and high frequency field effect transistors.

  19. Band offsets for biaxially and uniaxially stressed silicon-germanium layers with arbitrary substrate and channel orientations

    NASA Astrophysics Data System (ADS)

    Eneman, Geert; Roussel, Philippe; Brunco, David Paul; Collaert, Nadine; Mocuta, Anda; Thean, Aaron

    2016-08-01

    The conduction and valence band offsets between a strained silicon-germanium layer and a silicon-germanium substrate are reported for arbitrary substrate and channel crystal orientations. The offsets are calculated both for the case of biaxial stress, corresponding approximately to the stress state of a thin strained channel in a planar field-effect transistor (FET), and for uniaxial stress, which is the approximate stress state for strained channels in a FinFET configuration. Significant orientation dependence is found for the conduction band offset, overall leading to the strongest electron quantum confinement in biaxial-tensile stressed channels on {100}-oriented substrates, and uniaxial-tensile stressed channels in the ⟨100⟩ and ⟨110⟩ directions. For biaxially stressed layers on {111} substrates, the conduction band offset is significantly smaller than for {100} or {110} directions. For the valence band offset, the dependence on crystal orientation is found to be small.

  20. Impact of field-enhanced band-traps-band tunneling on the dark current generation in germanium p-i-n photodetector

    NASA Astrophysics Data System (ADS)

    Ang, Kah-Wee; Ng, Joseph Weisheng; Lo, Guo-Qiang; Kwong, Dim-Lee

    2009-06-01

    This letter investigates the impact of field-enhanced band-traps-band tunneling on the dark current generation in germanium (Ge) p-i-n photodetector. We show that the existence of defect-induced traps within the forbidden gap forms the underlying leakage mechanism. Enhancing the electric field intensity is found to reduce the activation energy that governs the leakage generation rates. In the presence of enlarged band-bending, the dark current generation is further aggravated by the enhancement in electrons and holes tunneling from the resulting deep levels into the conduction and valence bands, respectively. Such field-enhanced band tunneling effect becomes increasingly prominent with a downsizing of the detector's depletion width, which imposes a design trade-off between leakage generation and bandwidth enhancement.

  1. Observation of the Forbidden Magnetic Dipole Transition 6{sup 2}P{sub ½} --> 7{sup 2}P{sub ½} in Atomic Thallium

    DOE R&D Accomplishments Database

    Chu, S.

    1976-10-01

    A measurement of the 6{sup 2}P{sub ½} --> 7{sup 2}P{sub ½} forbidden magnetic dipole matrix element in atomic thallium is described. A pulsed, linearly polarized dye laser tuned to the transition frequency is used to excite the thallium vapor from the 6{sup 2}P{sub ½} ground state to the 7{sup 2}P{sub ½} excited state. Interference between the magnetic dipole M1 amplitude and a static electric field induced E1 amplitude results in an atomic polarization of the 7{sup 2}P{sub ½} state, and the subsequent circular polarization of 535 nm fluorescence. The circular polarization is seen to be proportional to / as expected, and measured for several transitions between hyperfine levels of the 6{sup 2}P{sub ½} and 7{sup 2}P{sub ½} states. The result is = -(2.11 +- 0.30) x 10{sup -5} parallel bar e parallel bar dirac constant/2mc, in agreement with theory.

  2. New superhindered polydentate polyphosphine ligands P(CH2CH2P(t)Bu2)3, PhP(CH2CH2P(t)Bu2)2, P(CH2CH2CH2P(t)Bu2)3, and their ruthenium(II) chloride complexes.

    PubMed

    Gilbert-Wilson, Ryan; Field, Leslie D; Bhadbhade, Mohan M

    2012-03-01

    The synthesis and characterization of the extremely hindered phosphine ligands, P(CH(2)CH(2)P(t)Bu(2))(3) (P(2)P(3)(tBu), 1), PhP(CH(2)CH(2)P(t)Bu(2))(2) (PhP(2)P(2)(tBu), 2), and P(CH(2)CH(2)CH(2)P(t)Bu(2))(3) (P(3)P(3)(tBu), 3) are reported, along with the synthesis and characterization of ruthenium chloro complexes RuCl(2)(P(2)P(3)(tBu)) (4), RuCl(2)(PhP(2)P(2)(tBu)) (5), and RuCl(2)(P(3)P(3)(tBu)) (6). The bulky P(2)P(3)(tBu) (1) and P(3)P(3)(tBu) (3) ligands are the most sterically encumbered PP(3)-type ligands so far synthesized, and in all cases, only three phosphorus donors are able to bind to the metal center. Complexes RuCl(2)(PhP(2)P(2)(tBu)) (5) and RuCl(2)(P(3)P(3)(tBu)) (6) were characterized by crystallography. Low temperature solution and solid state (31)P{(1)H} NMR were used to demonstrate that the structure of RuCl(2)(P(2)P(3)(tBu)) (4) is probably analogous to that of RuCl(2)(PhP(2)P(2)(tBu)) (5) which had been structurally characterized.

  3. Dissociable Modulation of Overt Visual Attention in Valence and Arousal Revealed by Topology of Scan Path

    PubMed Central

    Ni, Jianguang; Jiang, Huihui; Jin, Yixiang; Chen, Nanhui; Wang, Jianhong; Wang, Zhengbo; Luo, Yuejia; Ma, Yuanye; Hu, Xintian

    2011-01-01

    Emotional stimuli have evolutionary significance for the survival of organisms; therefore, they are attention-grabbing and are processed preferentially. The neural underpinnings of two principle emotional dimensions in affective space, valence (degree of pleasantness) and arousal (intensity of evoked emotion), have been shown to be dissociable in the olfactory, gustatory and memory systems. However, the separable roles of valence and arousal in scene perception are poorly understood. In this study, we asked how these two emotional dimensions modulate overt visual attention. Twenty-two healthy volunteers freely viewed images from the International Affective Picture System (IAPS) that were graded for affective levels of valence and arousal (high, medium, and low). Subjects' heads were immobilized and eye movements were recorded by camera to track overt shifts of visual attention. Algebraic graph-based approaches were introduced to model scan paths as weighted undirected path graphs, generating global topology metrics that characterize the algebraic connectivity of scan paths. Our data suggest that human subjects show different scanning patterns to stimuli with different affective ratings. Valence salient stimuli (with neutral arousal) elicited faster and larger shifts of attention, while arousal salient stimuli (with neutral valence) elicited local scanning, dense attention allocation and deep processing. Furthermore, our model revealed that the modulatory effect of valence was linearly related to the valence level, whereas the relation between the modulatory effect and the level of arousal was nonlinear. Hence, visual attention seems to be modulated by mechanisms that are separate for valence and arousal. PMID:21494331

  4. Electron-pair density decomposition for core-valence separable systems.

    PubMed

    Wang, Jian; Wang, Yu; Ugalde, Jesus M

    2012-10-30

    The electron pair density of a core-valence separable system can be decomposed into three parts: core-core, core-valence, and valence-valence. The core-core part has a Hartree-Fock like structure. The core-valence part can be written as Γ(cv) (1,2) = γ(c) (1,1)γ(v) (2,2) - γ(c) (1,2)γ(v) (2,1) + γ(c) (2,2)γ(v) (1,1) - γ(c) (2,1)γ(v) (1,2), where only the 1-matrices from the core and valence orbitals contribute. The valence-valence part is left to be determined from the reduced frozen-core type wave function, which often contains the essential information on the electron correlation and the chemical bond. We demonstrate the analysis to the ground state of negative ion Li(-) and 2(1)Σ(u)(+) excited state of the Li(2) molecule.

  5. Age influences the relation between subjective valence ratings and emotional word use during autobiographical memory retrieval.

    PubMed

    Ford, Jaclyn H; DiGirolamo, Marissa A; Kensinger, Elizabeth A

    2016-09-01

    Recent research reveals an age-related increase in positive autobiographical memory retrieval using a number of positivity measures, including valence ratings and positive word use. It is currently unclear whether the positivity shift in each of these measures co-occurs, or if age uniquely influences multiple components of autobiographical memory retrieval. The current study examined the correspondence between valence ratings and emotional word use in young and older adults' autobiographical memories. Positive word use in narratives was associated with valence ratings only in young adults' narratives. Older adults' narratives contained a consistent level of positive word use regardless of valence rating, suggesting that positive words and concepts may be chronically accessible to older adults during memory retrieval, regardless of subjective valence. Although a relation between negative word use in narratives and negative valence ratings was apparent in both young and older adults, it was stronger in older adults' narratives. These findings confirm that older adults do vary their word use in accordance with subjective valence, but they do so in a way that is different from young adults. The results also point to a potential dissociation between age-related changes in subjective valence and in positive word use. PMID:26274398

  6. Effects of Emotional Valence and Arousal on Recollective and Nonrecollective Recall

    ERIC Educational Resources Information Center

    Gomes, Carlos F. A.; Brainerd, Charles J.; Stein, Lilian M.

    2013-01-01

    The authors investigated the effects of valence and arousal on memory using a dual-process model that quantifies recollective and nonrecollective components of recall without relying on metacognitive judgments to separate them. The results showed that valenced words increased reconstruction (a component of nonrecollective retrieval) relative to…

  7. Group Motivation and Group Task Performance: The Expectancy-Valence Theory Approach.

    ERIC Educational Resources Information Center

    Nakanishi, Masayuki

    1988-01-01

    Investigated effects of group motivation on group task performance. Created two levels of valence, expectancy and instrumentality. Valence variable reflected on group productivity on unstructured and task persistence measures. Expectancy variable's effect was on task persistence measure. Instrumentality affected group productivity on structured…

  8. Identifying Facial Emotions: Valence Specific Effects and an Exploration of the Effects of Viewer Gender

    ERIC Educational Resources Information Center

    Jansari, Ashok; Rodway, Paul; Goncalves, Salvador

    2011-01-01

    The valence hypothesis suggests that the right hemisphere is specialised for negative emotions and the left hemisphere is specialised for positive emotions (Silberman & Weingartner, 1986). It is unclear to what extent valence-specific effects in facial emotion perception depend upon the gender of the perceiver. To explore this question 46…

  9. 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)

  10. Synchrotron Studies of Narrow Band and Low-Dimensional Materials. Final Report for July 1, 1990---December 31, 2002

    SciTech Connect

    Allen, J. W.

    2003-05-13

    This report summarizes a 12-year program of various kinds of synchrotron spectroscopies directed at the electronic structures of narrow band and low-dimensional materials that display correlated electron behaviors such as metal-insulator transitions, mixed valence, superconductivity, Kondo moment quenching, heavy Fermions, and non-Fermi liquid properties.

  11. Classical trajectory study of alignment effects in the capture process: He 2+-Li ∗(2pΣ,2pΠ) collisions

    NASA Astrophysics Data System (ADS)

    Perumal, A. N.; Tripathi, D. N.

    1998-08-01

    A simulation method (CTMC) has been used to investigate the selectivity and alignment effects on the capture process in He 2+-Li ∗(2pΣ,2pΠ) collisions. The anomalous results of the experiment (∼ 50% error) as well as the AO calculation of Gieler et al. in case of capture into He II ( n = 4) from the initial Li ∗ (2pΣ) state are not found in the present work. Relative velocity and spatial overlap together mainly control the capture process in ion-atom collisions. The n-distribution of the final capture state is also presented.

  12. Study of energy band discontinuity in NiZnO/ZnO heterostructure using X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Dewan, Sheetal; Tomar, Monika; Goyal, Anshu; Kapoor, A. K.; Tandon, R. P.; Gupta, Vinay

    2016-05-01

    A heterostructure based on ZnO and Ni doped ZnO (NiZnO) thin films has been prepared on c-plane sapphire substrate by pulsed laser deposition technique. X-ray photo electron spectroscopy has been utilized to study the energy band discontinuities, i.e., valence band offset ( Δ E v ) and conduction band offset ( Δ E c ) at the interface of NiZnO and ZnO thin films. A type-II band alignment is identified at the interface of prepared heterostructure from the computed data, which is attractive for the realization of efficient optoelectronic devices.

  13. Band Structure Asymmetry of Bilayer Graphene Revealed by Infrared Spectroscopy

    SciTech Connect

    Li, Z.Q.; Henriksen, E.A.; Jiang, Z.; Hao, Zhao; Martin, Michael C.; Kim, P.; Stormer, H.L.; Basov, Dimitri N.

    2008-12-10

    We report on infrared spectroscopy of bilayer graphene integrated in gated structures. We observe a significant asymmetry in the optical conductivity upon electrostatic doping of electrons and holes. We show that this finding arises from a marked asymmetry between the valence and conduction bands, which is mainly due to the inequivalence of the two sublattices within the graphene layer and the next-nearest-neighbor interlayer coupling. From the conductivity data, the energy difference of the two sublattices and the interlayer coupling energy are directly determined.

  14. Evolutionary divergence of Ure2pA glutathione transferases in wood degrading fungi.

    PubMed

    Roret, Thomas; Thuillier, Anne; Favier, Frédérique; Gelhaye, Eric; Didierjean, Claude; Morel-Rouhier, Mélanie

    2015-10-01

    The intracellular systems of detoxification are crucial for the survival of wood degrading fungi. Within these systems, glutathione transferases could play a major role since this family of enzymes is specifically extended in lignolytic fungi. In particular the Ure2p class represents one third of the total GST number in Phanerochaete chrysosporium. These proteins have been phylogenetically split into two subclasses called Ure2pA and Ure2pB. Ure2pB can be classified as Nu GSTs because of shared structural and functional features with previously characterized bacterial isoforms. Ure2pA can rather be qualified as Nu-like GSTs since they exhibit a number of differences. Ure2pA possess a classical transferase activity, a more divergent catalytic site and a higher structural flexibility for some of them, compared to Nu GSTs. The characterization of four members of this Ure2pA subclass (PcUre2pA4, PcUre2pA5, PcUre2pA6 and PcUre2pA8) revealed specific functional and structural features, suggesting that these enzymes have rapidly evolved and differentiated, probably to adapt to the complex chemical environment associated with wood decomposition.

  15. Valence fluctuations of europium in the boride Eu4Pd(29+x)B8.

    PubMed

    Gumeniuk, Roman; Schnelle, Walter; Ahmida, Mahmoud A; Abd-Elmeguid, Mohsen M; Kvashnina, Kristina O; Tsirlin, Alexander A; Leithe-Jasper, Andreas; Geibel, Christoph

    2016-03-23

    We synthesized a high-quality sample of the boride Eu4Pd(29+x)B8 (x  =  0.76) and studied its structural and physical properties. Its tetragonal structure was solved by direct methods and confirmed to belong to the Eu4Pd29B8 type. All studied physical properties indicate a valence fluctuating Eu state, with a valence decreasing continuously from about 2.9 at 5 K to 2.7 at 300 K. Maxima in the T dependence of the susceptibility and thermopower at around 135 K and 120 K, respectively, indicate a valence fluctuation energy scale on the order of 300 K. Analysis of the magnetic susceptibility evidences some inconsistencies when using the ionic interconfigurational fluctuation (ICF) model, thus suggesting a stronger relevance of hybridization between 4f and valence electrons compared to standard valence-fluctuating Eu systems.

  16. Examining the role of emotional valence of mind wandering: All mind wandering is not equal.

    PubMed

    Banks, Jonathan B; Welhaf, Matthew S; Hood, Audrey V B; Boals, Adriel; Tartar, Jaime L

    2016-07-01

    To evaluate the role of emotional valence on the impact of mind wandering on working memory (WM) and sustained attention, we reanalyzed data from three independently conducted studies that examined the impact of stress on WM (Banks & Boals, 2016; Banks, Welhaf, & Srour, 2015) and sustained attention (Banks, Tartar, & Welhaf, 2014). Across all studies, participants reported the content of their thoughts at random intervals during the WM or sustained attention task. Thought probes in all studies included a core set of response options for task-unrelated thoughts (TUTs) that were negatively, positively, or neutrally emotionally valenced. In line with theories of emotional valenced stimuli on capture of attention, results suggest negatively valenced TUTs, but not positively valenced TUTs, were related to poorer WM and sustained attention in two studies. Neutral TUTs were related to poorer WM but not sustained attention performance. Implications for models of mind wandering are discussed.

  17. Valence fluctuations of europium in the boride Eu4Pd29+x B8

    NASA Astrophysics Data System (ADS)

    Gumeniuk, Roman; Schnelle, Walter; Ahmida, Mahmoud A.; Abd-Elmeguid, Mohsen M.; Kvashnina, Kristina O.; Tsirlin, Alexander A.; Leithe-Jasper, Andreas; Geibel, Christoph

    2016-03-01

    We synthesized a high-quality sample of the boride Eu4Pd29+x B8 (x  =  0.76) and studied its structural and physical properties. Its tetragonal structure was solved by direct methods and confirmed to belong to the Eu4Pd29B8 type. All studied physical properties indicate a valence fluctuating Eu state, with a valence decreasing continuously from about 2.9 at 5 K to 2.7 at 300 K. Maxima in the T dependence of the susceptibility and thermopower at around 135 K and 120 K, respectively, indicate a valence fluctuation energy scale on the order of 300 K. Analysis of the magnetic susceptibility evidences some inconsistencies when using the ionic interconfigurational fluctuation (ICF) model, thus suggesting a stronger relevance of hybridization between 4f and valence electrons compared to standard valence-fluctuating Eu systems.

  18. Identifying words that emerge into consciousness: Effects of word valence and unconscious previewing.

    PubMed

    Prioli, Simone C; Kahan, Todd A

    2015-09-01

    Words with negative valence capture attention and this increase in attentional resources typically enhances perceptual processing. Recently, data using continuous flash suppression (CFS) appear to contradict this. In prior research when Chinese words were unconsciously presented in CFS and contrast was raised until the word was identified, RTs to identify words with negative valence were slower than RTs to words with neutral valence. This result might be limited to situations where a logographic writing system is used and could reflect a type of cognitive aftereffect where previewing the word causes habituation. Data (N=60) indicate that results generalize from a logographic (Chinese) to an orthographic writing system (English). In addition, when words were previewed in CFS RTs were slowed for words with negative valence relative to words with neutral valence and this was reversed when words were shown binocularly. Implications for theories of unconscious word processing and cognitive aftereffects are discussed.

  19. Emotions and language about motion: Differentiating affective dominance with syntax from valence with semantics.

    PubMed

    Freddi, Sébastien; Esteban, José; Dru, Vincent

    2015-12-15

    Motion as encoded in linguistic cues is used to differentiate affective valence and dominance. Participants were invited to rate their affective responses to different words along valence and dominance scales. The words were nouns describing static cues and verbs describing motion, connected to DOWN/UP and Avoidance/Approach cues. The results of three studies showed that valence and dominance could be differentiated through syntax and semantics of motion. On one hand, dominance feelings, compared to valence ones, are particularly influenced by motion encoded in syntactic classes (verbs vs. nouns). On the other hand, valence feelings, compared to dominance ones, are influenced by a semantics of motion through DOWN/UP and Avoidance/Approach cues, considered as polarities. A polarity correspondence effect is proposed to explain these results.

  20. Examining the role of emotional valence of mind wandering: All mind wandering is not equal.

    PubMed

    Banks, Jonathan B; Welhaf, Matthew S; Hood, Audrey V B; Boals, Adriel; Tartar, Jaime L

    2016-07-01

    To evaluate the role of emotional valence on the impact of mind wandering on working memory (WM) and sustained attention, we reanalyzed data from three independently conducted studies that examined the impact of stress on WM (Banks & Boals, 2016; Banks, Welhaf, & Srour, 2015) and sustained attention (Banks, Tartar, & Welhaf, 2014). Across all studies, participants reported the content of their thoughts at random intervals during the WM or sustained attention task. Thought probes in all studies included a core set of response options for task-unrelated thoughts (TUTs) that were negatively, positively, or neutrally emotionally valenced. In line with theories of emotional valenced stimuli on capture of attention, results suggest negatively valenced TUTs, but not positively valenced TUTs, were related to poorer WM and sustained attention in two studies. Neutral TUTs were related to poorer WM but not sustained attention performance. Implications for models of mind wandering are discussed. PMID:27310109

  1. Valence fluctuations of europium in the boride Eu4Pd(29+x)B8.

    PubMed

    Gumeniuk, Roman; Schnelle, Walter; Ahmida, Mahmoud A; Abd-Elmeguid, Mohsen M; Kvashnina, Kristina O; Tsirlin, Alexander A; Leithe-Jasper, Andreas; Geibel, Christoph

    2016-03-23

    We synthesized a high-quality sample of the boride Eu4Pd(29+x)B8 (x  =  0.76) and studied its structural and physical properties. Its tetragonal structure was solved by direct methods and confirmed to belong to the Eu4Pd29B8 type. All studied physical properties indicate a valence fluctuating Eu state, with a valence decreasing continuously from about 2.9 at 5 K to 2.7 at 300 K. Maxima in the T dependence of the susceptibility and thermopower at around 135 K and 120 K, respectively, indicate a valence fluctuation energy scale on the order of 300 K. Analysis of the magnetic susceptibility evidences some inconsistencies when using the ionic interconfigurational fluctuation (ICF) model, thus suggesting a stronger relevance of hybridization between 4f and valence electrons compared to standard valence-fluctuating Eu systems. PMID:26895077

  2. Madelung and Hubbard interactions in polaron band model of doped organic semiconductors.

    PubMed

    Png, Rui-Qi; Ang, Mervin C Y; Teo, Meng-How; Choo, Kim-Kian; Tang, Cindy Guanyu; Belaineh, Dagmawi; Chua, Lay-Lay; Ho, Peter K H

    2016-01-01

    The standard polaron band model of doped organic semiconductors predicts that density-of-states shift into the π-π* gap to give a partially filled polaron band that pins the Fermi level. This picture neglects both Madelung and Hubbard interactions. Here we show using ultrahigh workfunction hole-doped model triarylamine-fluorene copolymers that Hubbard interaction strongly splits the singly-occupied molecular orbital from its empty counterpart, while Madelung (Coulomb) interactions with counter-anions and other carriers markedly shift energies of the frontier orbitals. These interactions lower the singly-occupied molecular orbital band below the valence band edge and give rise to an empty low-lying counterpart band. The Fermi level, and hence workfunction, is determined by conjunction of the bottom edge of this empty band and the top edge of the valence band. Calculations are consistent with the observed Fermi-level downshift with counter-anion size and the observed dependence of workfunction on doping level in the strongly doped regime. PMID:27582355

  3. First principles scheme to evaluate band edge positions in potential transition metal oxide photocatalysts and photoelectrodes.

    PubMed

    Toroker, Maytal Caspary; Kanan, Dalal K; Alidoust, Nima; Isseroff, Leah Y; Liao, Peilin; Carter, Emily A

    2011-10-01

    The positions of electronic band edges are one important metric for determining a material's capability to function in a solar energy conversion device that produces fuels from sunlight. In particular, the position of the valence band maximum (conduction band minimum) must lie lower (higher) in energy than the oxidation (reduction) reaction free energy in order for these reactions to be thermodynamically favorable. We present first principles quantum mechanics calculations of the band edge positions in five transition metal oxides and discuss the feasibility of using these materials in photoelectrochemical cells that produce fuels, including hydrogen, methane, methanol, and formic acid. The band gap center is determined within the framework of DFT+U theory. The valence band maximum (conduction band minimum) is found by subtracting (adding) half of the quasiparticle gap obtained from a non-self-consistent GW calculation. The calculations are validated against experimental data where possible; results for several materials including manganese(ii) oxide, iron(ii) oxide, iron(iii) oxide, copper(i) oxide and nickel(ii) oxide are presented.

  4. Band offsets at the crystalline / hydrogenated amorphous silicon interface from first-principles

    NASA Astrophysics Data System (ADS)

    Hazrati, Ebrahim; Jarolimek, Karol; de Wijs, Gilles A.; InstituteMolecules; Materials Team

    2015-03-01

    The heterojunction formed between crystalline silicon (c-Si) and hydrogenated amorphous silicon (a-Si:H) is a key component of a new type of high-efficiency silicon solar cell. Since a-Si:H has a larger band gap than c-Si, band offsets are formed at the interface. A band offset at the minority carrier band will mitigate recombination and lead to an increased efficiency. Experimental values of band offsets scatter in a broad range. However, a recent meta-analysis of the results (W. van Sark et al.pp. 405, Springer 2012) gives a larger valence offset (0.40 eV) than the conduction offset (0.15 eV). In light of the conflicting reports our goal is to calculate the band offsets at the c-Si/a-Si:H interface from first-principles. We have prepared several atomistic models of the interface. The crystalline part is terminated with (111) surfaces on both sides. The amorphous structure is generated by simulating an annealing process at 1100 K, with DFT molecular dynamics. Once the atomistic is ready it can be used to calculate the electronic structure of the interface. Our preliminary results show that the valence offset is larger than the conduction band offset.

  5. Madelung and Hubbard interactions in polaron band model of doped organic semiconductors

    NASA Astrophysics Data System (ADS)

    Png, Rui-Qi; Ang, Mervin C. Y.; Teo, Meng-How; Choo, Kim-Kian; Tang, Cindy Guanyu; Belaineh, Dagmawi; Chua, Lay-Lay; Ho, Peter K. H.

    2016-09-01

    The standard polaron band model of doped organic semiconductors predicts that density-of-states shift into the π-π* gap to give a partially filled polaron band that pins the Fermi level. This picture neglects both Madelung and Hubbard interactions. Here we show using ultrahigh workfunction hole-doped model triarylamine-fluorene copolymers that Hubbard interaction strongly splits the singly-occupied molecular orbital from its empty counterpart, while Madelung (Coulomb) interactions with counter-anions and other carriers markedly shift energies of the frontier orbitals. These interactions lower the singly-occupied molecular orbital band below the valence band edge and give rise to an empty low-lying counterpart band. The Fermi level, and hence workfunction, is determined by conjunction of the bottom edge of this empty band and the top edge of the valence band. Calculations are consistent with the observed Fermi-level downshift with counter-anion size and the observed dependence of workfunction on doping level in the strongly doped regime.

  6. Madelung and Hubbard interactions in polaron band model of doped organic semiconductors

    PubMed Central

    Png, Rui-Qi; Ang, Mervin C.Y.; Teo, Meng-How; Choo, Kim-Kian; Tang, Cindy Guanyu; Belaineh, Dagmawi; Chua, Lay-Lay; Ho, Peter K.H.

    2016-01-01

    The standard polaron band model of doped organic semiconductors predicts that density-of-states shift into the π–π* gap to give a partially filled polaron band that pins the Fermi level. This picture neglects both Madelung and Hubbard interactions. Here we show using ultrahigh workfunction hole-doped model triarylamine–fluorene copolymers that Hubbard interaction strongly splits the singly-occupied molecular orbital from its empty counterpart, while Madelung (Coulomb) interactions with counter-anions and other carriers markedly shift energies of the frontier orbitals. These interactions lower the singly-occupied molecular orbital band below the valence band edge and give rise to an empty low-lying counterpart band. The Fermi level, and hence workfunction, is determined by conjunction of the bottom edge of this empty band and the top edge of the valence band. Calculations are consistent with the observed Fermi-level downshift with counter-anion size and the observed dependence of workfunction on doping level in the strongly doped regime. PMID:27582355

  7. Madelung and Hubbard interactions in polaron band model of doped organic semiconductors.

    PubMed

    Png, Rui-Qi; Ang, Mervin C Y; Teo, Meng-How; Choo, Kim-Kian; Tang, Cindy Guanyu; Belaineh, Dagmawi; Chua, Lay-Lay; Ho, Peter K H

    2016-09-01

    The standard polaron band model of doped organic semiconductors predicts that density-of-states shift into the π-π* gap to give a partially filled polaron band that pins the Fermi level. This picture neglects both Madelung and Hubbard interactions. Here we show using ultrahigh workfunction hole-doped model triarylamine-fluorene copolymers that Hubbard interaction strongly splits the singly-occupied molecular orbital from its empty counterpart, while Madelung (Coulomb) interactions with counter-anions and other carriers markedly shift energies of the frontier orbitals. These interactions lower the singly-occupied molecular orbital band below the valence band edge and give rise to an empty low-lying counterpart band. The Fermi level, and hence workfunction, is determined by conjunction of the bottom edge of this empty band and the top edge of the valence band. Calculations are consistent with the observed Fermi-level downshift with counter-anion size and the observed dependence of workfunction on doping level in the strongly doped regime.

  8. Band alignment of atomic layer deposited (HfZrO{sub 4}){sub 1−x}(SiO{sub 2}){sub x} gate dielectrics on Si (100)

    SciTech Connect

    Heo, Sung; Tahir, Dahlang; Chung, Jae Gwan; Lee, Jae Cheol; Kim, KiHong; Lee, Junho; Lee, Hyung-Ik; Park, Gyeong Su; Oh, Suhk Kun; Kang, Hee Jae; Choi, Pyungho; Choi, Byoung-Deog

    2015-11-02

    The band alignment of atomic layer deposited (HfZrO{sub 4}){sub 1−x}(SiO{sub 2}){sub x} (x = 0, 0.10, 0.15, and 0.20) gate dielectric thin films grown on Si (100) was obtained by using X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. The band gap, valence band offset, and conduction band offset values for HfZrO{sub 4} silicate increased from 5.4 eV to 5.8 eV, from 2.5 eV to 2.75 eV, and from 1.78 eV to 1.93 eV, respectively, as the mole fraction (x) of SiO{sub 2} increased from 0.1 to 0.2. This increase in the conduction band and valence band offsets, as a function of increasing SiO{sub 2} mole fraction, decreased the gate leakage current density. As a result, HfZrO{sub 4} silicate thin films were found to be better for advanced gate stack applications because they had adequate band gaps to ensure sufficient conduction band offsets and valence band offsets to Si.

  9. Direct measurement of band offset at the interface between CdS and Cu2ZnSnS4 using hard X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Tajima, Shin; Kataoka, Keita; Takahashi, Naoko; Kimoto, Yasuji; Fukano, Tatsuo; Hasegawa, Masaki; Hazama, Hirofumi

    2013-12-01

    We directly and non-destructively measured the valence band offset at the interface between CdS and Cu2ZnSnS4 (CZTS) using hard X-ray photoelectron spectroscopy (HAXPES), which can measure the electron state of the buried interface because of its large analysis depth. These measurements were made using the following real devices; CZTS(t = 700 nm), CdS(t = 100 nm)/CZTS(t = 700 nm), and CdS(t = 5 nm)/CZTS(t = 700 nm) films formed on Mo coated glass. The valence band spectra were measured by HAXPES using an X-ray photon energy of 8 keV. The value of the valence band offset at the interface between CdS and CZTS was estimated as 1.0 eV by fitting the spectra. The conduction band offset could be deduced as 0.0 eV from the obtained valence band offset and the band gap energies of CdS and CZTS.

  10. Interband interaction between bulk and surface resonance bands of a Pb-adsorbed Ge(001) surface

    NASA Astrophysics Data System (ADS)

    Sakata, Tomohiro; Takeda, Sakura N.; Kitagawa, Kosuke; Daimon, Hiroshi

    2016-08-01

    We investigated the valence band structure of a Pb-adsorbed Ge(001) surface by angle-resolved photoelectron spectroscopy. Three Ge bands, G1, G2, and G3, were observed in a Ge(001) 2 × 1 clean surface. In addition to these three bands, a fourth band (R band) is found on the surface with 2 ML of Pb. The R band continuously appeared even when the surface superstructure was changed. The position of the R band does not depend on Pb coverage. These results indicate that the R band derives from Ge subsurface states, known as surface resonance states. Furthermore, the effective mass of G3 is significantly reduced when the R band exists. We found that this reduction of G3 effective mass was explained by the interaction of the G3 and R bands. Consequently, the surface resonance band is considered to penetrate into the Ge subsurface region affecting the Ge bulk states. We determine the hybridization energy to be 0.068 eV by fitting the observed bands.

  11. First-principle natural band alignment of GaN / dilute-As GaNAs alloy

    SciTech Connect

    Tan, Chee-Keong Tansu, Nelson

    2015-01-15

    Density functional theory (DFT) calculations with the local density approximation (LDA) functional are employed to investigate the band alignment of dilute-As GaNAs alloys with respect to the GaN alloy. Conduction and valence band positions of dilute-As GaNAs alloy with respect to the GaN alloy on an absolute energy scale are determined from the combination of bulk and surface DFT calculations. The resulting GaN / GaNAs conduction to valence band offset ratio is found as approximately 5:95. Our theoretical finding is in good agreement with experimental observation, indicating the upward movements of valence band at low-As content dilute-As GaNAs are mainly responsible for the drastic reduction of the GaN energy band gap. In addition, type-I band alignment of GaN / GaNAs is suggested as a reasonable approach for future device implementation with dilute-As GaNAs quantum well, and possible type-II quantum well active region can be formed by using InGaN / dilute-As GaNAs heterostructure.

  12. Control of sigma virus multiplication by the ref(2)P gene of Drosophila melanogaster: an in vivo study of the PB1 domain of Ref(2)P.

    PubMed

    Carré-Mlouka, A; Gaumer, S; Gay, P; Petitjean, A M; Coulondre, C; Dru, P; Bras, F; Dezélée, S; Contamine, D

    2007-05-01

    Ref(2)P has been described as one of the Drosophila proteins that interacts with the sigma virus cycle. We generated alleles to identify critical residues involved in the restrictive (inhibiting viral multiplication) or permissive (allowing viral multiplication) character of Ref(2)P. We demonstrate that permissive alleles increase the ability of the sigma virus to infect Drosophila when compared to null alleles and we confirm that restrictive alleles decrease this capacity. Moreover, we have created alleles unfunctional in viral cycling while functional for Ref(2)P fly functions. This type of allele had never been observed before and shows that fly- and virus-related activities of Ref(2)P are separable. The viral status of Ref(2)P variants is determined by the amino-terminal PB1 domain polymorphism. In addition, an isolated PB1 domain mimics virus-related functions even if it is similar to a loss of function toward fly-related activities. The evolutionary tree of the Ref(2)P PB1 domain that we could build on the basis of the natural allele sequences is in agreement with an evolution of PB1 domain due to successive transient selection waves.

  13. Stretch Band Exercise Program

    ERIC Educational Resources Information Center

    Skirka, Nicholas; Hume, Donald

    2007-01-01

    This article discusses how to use stretch bands for improving total body fitness and quality of life. A stretch band exercise program offers a versatile and inexpensive option to motivate participants to exercise. The authors suggest practical exercises that can be used in physical education to improve or maintain muscular strength and endurance,…

  14. Rubber Band Science

    ERIC Educational Resources Information Center

    Cowens, John

    2005-01-01

    Not only are rubber bands great for binding objects together, but they can be used in a simple science experiment that involves predicting, problem solving, measuring, graphing, and experimenting. In this article, the author describes how rubber bands can be used to teach the force of mass.

  15. Singing with the Band

    ERIC Educational Resources Information Center

    Altman, Timothy Meyer; Wright, Gary K.

    2012-01-01

    Usually band, orchestra, and choir directors work independently. However, the authors--one a choral director, the other a band director--have learned that making music together makes friends. Not only can ensemble directors get along, but joint concerts may be just the way to help students see how music can reach the heart. Combined instrumental…

  16. Progressive Band Selection

    NASA Technical Reports Server (NTRS)

    Fisher, Kevin; Chang, Chein-I

    2009-01-01

    Progressive band selection (PBS) reduces spectral redundancy without significant loss of information, thereby reducing hyperspectral image data volume and processing time. Used onboard a spacecraft, it can also reduce image downlink time. PBS prioritizes an image's spectral bands according to priority scores that measure their significance to a specific application. Then it uses one of three methods to select an appropriate number of the most useful bands. Key challenges for PBS include selecting an appropriate criterion to generate band priority scores, and determining how many bands should be retained in the reduced image. The image's Virtual Dimensionality (VD), once computed, is a reasonable estimate of the latter. We describe the major design details of PBS and test PBS in a land classification experiment.

  17. Valence atom with bohmian quantum potential: the golden ratio approach

    PubMed Central

    2012-01-01

    Background The alternative quantum mechanical description of total energy given by Bohmian theory was merged with the concept of the golden ratio and its appearance as the Heisenberg imbalance to provide a new density-based description of the valence atomic state and reactivity charge with the aim of clarifying their features with respect to the so-called DFT ground state and critical charge, respectively. Results The results, based on the so-called double variational algorithm for chemical spaces of reactivity, are fundamental and, among other issues regarding chemical bonding, solve the existing paradox of using a cubic parabola to describe a quadratic charge dependency. Conclusions Overall, the paper provides a qualitative-quantitative explanation of chemical reactivity based on more than half of an electronic pair in bonding, and provide new, more realistic values for the so-called “universal” electronegativity and chemical hardness of atomic systems engaged in reactivity (analogous to the atoms-in-molecules framework). PMID:23146157

  18. Oxytocin specifically enhances valence-dependent parasympathetic responses.

    PubMed

    Gamer, Matthias; Büchel, Christian

    2012-01-01

    The evolutionarily highly conserved neuropeptide oxytocin seems to be involved in the regulation of complex forms of social behavior. It enhances the processing of positive social stimuli, reduces behavioral and neuroendocrine stress responses and modulates amygdala activity in humans. Moreover, it has been proposed that oxytocin dampens sympathetic nervous system activity. This hypothesis was tested in a double-blind, placebo-controlled study with 38 men either receiving 24 IU oxytocin intranasally or a placebo spray. While accomplishing an emotion classification task, electrodermal responses were measured as an index of sympathetic activity. Moreover, heart rate changes were recorded that are additionally mediated by the parasympathetic nervous system. Oxytocin enhanced differential heart rate responses to facial expressions as a function of the emotional valence, but had no effect on electrodermal activity or tonic measures of physiological arousal. These results indicate that oxytocin specifically modulates phasic activity of the parasympathetic nervous system which potentially reflects an increased motivational value of facial expressions following oxytocin treatment. Findings suggest that anxiolytic effects of oxytocin are not reflected in short-term sympathetic responses and may even be a consequence of rather than a prerequisite for improved social information processing. PMID:21641726

  19. Resonating valence bond wave functions and classical interacting dimer models.

    PubMed

    Damle, Kedar; Dhar, Deepak; Ramola, Kabir

    2012-06-15

    We relate properties of nearest-neighbor resonating valence-bond (NNRVB) wave functions for SU(g) spin systems on two-dimensional bipartite lattices to those of fully packed interacting classical dimer models on the same lattice. The interaction energy can be expressed as a sum of n-body potentials V(n), which are recursively determined from the NNRVB wave function on finite subgraphs of the original lattice. The magnitude of the n-body interaction V(n) (n>1) is of order O(g(-(n-1))) for small g(-1). The leading term is a two-body nearest-neighbor interaction V2(g) favoring two parallel dimers on elementary plaquettes. For SU(2) spins, using our calculated value of V2(g=2), we find that the long-distance behavior of the bond-energy correlation function is dominated by an oscillatory term that decays as 1/|r|α with α≈1.22. This result is in remarkable quantitative agreement with earlier direct numerical studies of the corresponding wave function, which give α≈1.20. PMID:23004328

  20. Electrochemical modification of Surface valence - Cr precipitates on LSCF surfaces

    NASA Astrophysics Data System (ADS)

    Finsterbusch, Martin; Schaefer, J. A.; Eigenbrodt, B. C.; Walker, R. A.; Lussier, A.; Idzerda, Y. U.

    2010-10-01

    Interactions of gaseous Cr contaminants with the perovskite material LSCF (La0.6Sr0.4Co0.2Fe0.8O3) commonly used as cathode for Solid Oxide Fuel Cells (SOFC) were investigated by means of X-ray absorption Spectroscopy (XAS) and Raman Spectroscopy. The setup consisted of a model cell with a GDC (Gd0.1Ce0.9O2) electrolyte pellet with a LSCF cathode on both sides in a Cr containing sample holder. The chemical structure and valency of the precipitate were found to depend on the electrochemical conditions of the surface, particularly on the bias voltage and not the total current density present in the cell. Cr^6+ spinels were found to form under high bias voltage, while under low bias voltage mostly Cr2O3 was formed. The influence of the contact material (Au vs. Ag) and the effect of quenching were investigated by Raman Spectroscopy under operating conditions (800 C in air). XAS unlike EDS, XRD or XPS is a precise and valuable tool for the direct measurement of the oxidation state of transition metals in compounds if the concentration is low (contamination) and the substrate is porous.