Outer-valence Electron Spectra of Prototypical Aromatic Heterocycles from an Optimally Tuned Range-Separated Hybrid Functional

PubMed Central

2014-01-01

Density functional theory with optimally tuned range-separated hybrid (OT-RSH) functionals has been recently suggested [Refaely-Abramson et al. Phys. Rev. Lett.2012, 109, 226405] as a nonempirical approach to predict the outer-valence electronic structure of molecules with the same accuracy as many-body perturbation theory. Here, we provide a quantitative evaluation of the OT-RSH approach by examining its performance in predicting the outer-valence electron spectra of several prototypical gas-phase molecules, from aromatic rings (benzene, pyridine, and pyrimidine) to more complex organic systems (terpyrimidinethiol and copper phthalocyanine). For a range up to several electronvolts away from the frontier orbital energies, we find that the outer-valence electronic structure obtained from the OT-RSH method agrees very well (typically within ∼0.1–0.2 eV) with both experimental photoemission and theoretical many-body perturbation theory data in the GW approximation. In particular, we find that with new strategies for an optimal choice of the short-range fraction of Fock exchange, the OT-RSH approach offers a balanced description of localized and delocalized states. We discuss in detail the sole exception found—a high-symmetry orbital, particular to small aromatic rings, which is relatively deep inside the valence state manifold. Overall, the OT-RSH method is an accurate DFT-based method for outer-valence electronic structure prediction for such systems and is of essentially the same level of accuracy as contemporary GW approaches, at a reduced computational cost. PMID:24839410

Valence ionized states of iron pentacarbonyl and eta5-cyclopentadienyl cobalt dicarbonyl studied by symmetry-adapted cluster-configuration interaction calculation and collision-energy resolved Penning ionization electron spectroscopy.

PubMed

Fukuda, Ryoichi; Ehara, Masahiro; Nakatsuji, Hiroshi; Kishimoto, Naoki; Ohno, Koichi

2010-02-28

Valence ionized states of iron pentacarbonyl Fe(CO)(5) and eta(5)-cyclopentadienyl cobalt dicarbonyl Co(eta(5)-C(5)H(5))(CO)(2) have been studied by ultraviolet photoelectron spectroscopy, two-dimensional Penning ionization electron spectroscopy (2D-PIES), and symmetry-adapted cluster-configuration interaction calculations. Theory provided reliable assignments for the complex ionization spectra of these molecules, which have metal-carbonyl bonds. Theoretical ionization energies agreed well with experimental observations and the calculated wave functions could explain the relative intensities of PIES spectra. The collision-energy dependence of partial ionization cross sections (CEDPICS) was obtained by 2D-PIES. To interpret these CEDPICS, the interaction potentials between the molecules and a Li atom were examined in several coordinates by calculations. The relation between the slope of the CEDPICS and the electronic structure of the ionized states, such as molecular symmetry and the spatial distribution of ionizing orbitals, was analyzed. In Fe(CO)(5), an attractive interaction was obtained for the equatorial CO, while the interaction for the axial CO direction was repulsive. For Co(eta(5)-C(5)H(5))(CO)(2), the interaction potential in the direction of both Co-C-O and Co-Cp ring was attractive. These anisotropic interactions and ionizing orbital distributions consistently explain the relative slopes of the CEDPICS.

Direct Visualization of Valence Electron Motion Using Strong-Field Photoelectron Holography

NASA Astrophysics Data System (ADS)

He, Mingrui; Li, Yang; Zhou, Yueming; Li, Min; Cao, Wei; Lu, Peixiang

2018-03-01

Watching the valence electron move in molecules on its intrinsic timescale has been one of the central goals of attosecond science and it requires measurements with subatomic spatial and attosecond temporal resolutions. The time-resolved photoelectron holography in strong-field tunneling ionization holds the promise to access this realm. However, it remains to be a challenging task hitherto. Here we reveal how the information of valence electron motion is encoded in the hologram of the photoelectron momentum distribution (PEMD) and develop a novel approach of retrieval. As a demonstration, applying it to the PEMDs obtained by solving the time-dependent Schrödinger equation for the prototypical molecule H2+ , the attosecond charge migration is directly visualized with picometer spatial and attosecond temporal resolutions. Our method represents a general approach for monitoring attosecond charge migration in more complex polyatomic and biological molecules, which is one of the central tasks in the newly emerging attosecond chemistry.

Direct Visualization of Valence Electron Motion Using Strong-Field Photoelectron Holography.

PubMed

He, Mingrui; Li, Yang; Zhou, Yueming; Li, Min; Cao, Wei; Lu, Peixiang

2018-03-30

Watching the valence electron move in molecules on its intrinsic timescale has been one of the central goals of attosecond science and it requires measurements with subatomic spatial and attosecond temporal resolutions. The time-resolved photoelectron holography in strong-field tunneling ionization holds the promise to access this realm. However, it remains to be a challenging task hitherto. Here we reveal how the information of valence electron motion is encoded in the hologram of the photoelectron momentum distribution (PEMD) and develop a novel approach of retrieval. As a demonstration, applying it to the PEMDs obtained by solving the time-dependent Schrödinger equation for the prototypical molecule H_{2}^{+}, the attosecond charge migration is directly visualized with picometer spatial and attosecond temporal resolutions. Our method represents a general approach for monitoring attosecond charge migration in more complex polyatomic and biological molecules, which is one of the central tasks in the newly emerging attosecond chemistry.

Multireference configuration interaction study of the mixed Valence-Rydberg character of the C2H4 1(π,π*) V state

NASA Astrophysics Data System (ADS)

Krebs, Stefan; Buenker, Robert J.

1997-05-01

The spatial extension of the C2H41(π,π*) V state is investigated by means of low selection threshold multireference configuration interaction (CI) calculations employing two atomic orbital (AO) basis sets with different numbers of polarization and Rydberg functions. The results are shown to be nearly independent of the choice of one-electron basis (ground N, triplet T, and singlet V self-consistent field molecular orbitals (SCF MOs)) in forming the many-electron basis for the configuration interaction indicating that the AO basis limit has been closely approached in each case. The calculations indicate that the value for the <ΨV|Σxi2|ΨV>≡V matrix element falls in the 18±1 a02 range, 50% larger than the corresponding values computed for N and T, respectively, for the corresponding N and T states. This result is interpreted to be a consequence of the mixing of diabatic 1(π,π*) valence and 1(π,dπ) Rydberg states in the Franck-Condon region of the V-N transition. The corresponding excitation energy is computed to lie in the 7.90-7.95 eV range, indicating that there is a distinct nonverticality in the measured absorption spectrum which is caused in part by nonadiabatic interactions between the V and 1(π,3py) Rydberg states as a result of torsional motion of the C2H4 molecule.

Theory for electron transfer from a mixed-valence dimer with paramagnetic sites to a mononuclear acceptor

NASA Astrophysics Data System (ADS)

Bominaar, E. L.; Achim, C.; Borshch, S. A.

1999-06-01

Polynuclear transition-metal complexes, such as Fe-S clusters, are the prosthetic groups in a large number of metalloproteins and serve as temporary electron storage units in a number of important redox-based biological processes. Polynuclearity distinguishes clusters from mononuclear centers and confers upon them unique properties, such as spin ordering and the presence of thermally accessible excited spin states in clusters with paramagnetic sites, and fractional valencies in clusters of the mixed-valence type. In an earlier study we presented an effective-mode (EM) analysis of electron transfer from a binuclear mixed-valence donor with paramagnetic sites to a mononuclear acceptor which revealed that the cluster-specific attributes have an important impact on the kinetics of long-range electron transfer. In the present study, the validity of these results is tested in the framework of more detailed theories which we have termed the multimode semiclassical (SC) model and the quantum-mechanical (QM) model. It is found that the qualitative trends in the rate constant are the same in all treatments and that the semiclassical models provide a good approximation of the more rigorous quantum-mechanical description of electron transfer under physiologically relevant conditions. In particular, the present results corroborate the importance of electron transfer via excited spin states in reactions with a low driving force and justify the use of semiclassical theory in cases in which the QM model is computationally too demanding. We consider cases in which either one or two donor sites of a dimer are electronically coupled to the acceptor. In the case of multiconnectivity, the rate constant for electron transfer from a valence-delocalized (class-III) donor is nonadditive with respect to transfer from individual metal sites of the donor and undergoes an order-of-magnitude change by reversing the sign of the intradimer metal-metal resonance parameter (β). In the case of

A revised MRCI-algorithm. I. Efficient combination of spin adaptation with individual configuration selection coupled to an effective valence-shell Hamiltonian

NASA Astrophysics Data System (ADS)

Strodel, Paul; Tavan, Paul

2002-09-01

We present a revised multi-reference configuration interaction (MRCI) algorithm for balanced and efficient calculation of electronic excitations in molecules. The revision takes up an earlier method, which had been designed for flexible, state-specific, and individual selection (IS) of MRCI expansions, included perturbational corrections (PERT), and used the spin-coupled hole-particle formalism of Tavan and Schulten (1980) for matrix-element evaluation. It removes the deficiencies of this method by introducing tree structures, which code the CI bases and allow us to efficiently exploit the sparseness of the Hamiltonian matrices. The algorithmic complexity is shown to be optimal for IS/MRCI applications. The revised IS/MRCI/PERT module is combined with the effective valence shell Hamiltonian OM2 suggested by Weber and Thiel (2000). This coupling serves the purpose of making excited state surfaces of organic dye molecules accessible to relatively cheap and sufficiently precise descriptions.

On the valence fluctuation in the early actinide metals

DOE PAGES

Soderlind, P.; Landa, A.; Tobin, J. G.; ...

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 f 3 and f 4 configurations, respectively, with only minor contributions from other configurations. For plutonium (both αmore » 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 f 6 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

One-electron oxidation of electronically diverse manganese(III) and nickel(II) salen complexes: transition from localized to delocalized mixed-valence ligand radicals.

PubMed

Kurahashi, Takuya; Fujii, Hiroshi

2011-06-01

Ligand radicals from salen complexes are unique mixed-valence compounds in which a phenoxyl radical is electronically linked to a remote phenolate via a neighboring redox-active metal ion, providing an opportunity to study electron transfer from a phenolate to a phenoxyl radical mediated by a redox-active metal ion as a bridge. We herein synthesize one-electron-oxidized products from electronically diverse manganese(III) salen complexes in which the locus of oxidation is shown to be ligand-centered, not metal-centered, affording manganese(III)-phenoxyl radical species. The key point in the present study is an unambiguous assignment of intervalence charge transfer bands by using nonsymmetrical salen complexes, which enables us to obtain otherwise inaccessible insight into the mixed-valence property. A d(4) high-spin manganese(III) ion forms a Robin-Day class II mixed-valence system, in which electron transfer is occurring between the localized phenoxyl radical and the phenolate. This is in clear contrast to a d(8) low-spin nickel(II) ion with the same salen ligand, which induces a delocalized radical (Robin-Day class III) over the two phenolate rings, as previously reported by others. The present findings point to a fascinating possibility that electron transfer could be drastically modulated by exchanging the metal ion that bridges the two redox centers. © 2011 American Chemical Society

Effective on-site Coulomb interaction and electron configurations in transition-metal complexes from constraint density functional theory

NASA Astrophysics Data System (ADS)

Nawa, Kenji; Nakamura, Kohji; Akiyama, Toru; Ito, Tomonori; Weinert, Michael

Effective on-site Coulomb interactions (Ueff) and electron configurations in the localized d and f orbitals of metal complexes in transition-metal oxides and organometallic molecules, play a key role in the first-principles search for the true ground-state. However, wide ranges of values in the Ueff parameter of a material, even in the same ionic state, are often reported. Here, we revisit this issue from constraint density functional theory (DFT) by using the full-potential linearized augmented plane wave method. The Ueff parameters for prototypical transition-metal oxides, TMO (TM =Mn, Fe, Co, Ni), were calculated by the second derivative of the total energy functional with respect to the d occupation numbers inside the muffin-tin (MT) spheres as a function of the sphere radius. We find that the calculated Ueff values depend significantly on the MT radius, with a variation of more than 3 eV when the MT radius changes from 2.0 to 2.7 a.u., but importantly an identical valence band structure can be produced in all the cases, with an approximate scaling of Ueff. This indicates that a simple transferability of the Ueff value among different calculation methods is not allowed. We further extend the constraint DFT to treat various electron configurations of the localized d-orbitals in organometallic molecules, TMCp2 (TM =Cr, Mn, Fe, Co, Ni), and find that the calculated Ueff values can reproduce the experimentally determined ground-state electron configurations.

Norbornane: An investigation into its valence electronic structure using electron momentum spectroscopy, and density functional and Green's function theories

NASA Astrophysics Data System (ADS)

Knippenberg, S.; Nixon, K. L.; Brunger, M. J.; Maddern, T.; Campbell, L.; Trout, N.; Wang, F.; Newell, W. R.; Deleuze, M. S.; Francois, J.-P.; Winkler, D. A.

2004-12-01

We report on the results of an exhaustive study of the valence electronic structure of norbornane (C7H12), up to binding energies of 29 eV. Experimental electron momentum spectroscopy and theoretical Green's function and density functional theory approaches were all utilized in this investigation. A stringent comparison between the electron momentum spectroscopy and theoretical orbital momentum distributions found that, among all the tested models, the combination of the Becke-Perdew functional and a polarized valence basis set of triple-ζ quality provides the best representation of the electron momentum distributions for all of the 20 valence orbitals of norbornane. This experimentally validated quantum chemistry model was then used to extract some chemically important properties of norbornane. When these calculated properties are compared to corresponding results from other independent measurements, generally good agreement is found. Green's function calculations with the aid of the third-order algebraic diagrammatic construction scheme indicate that the orbital picture of ionization breaks down at binding energies larger than 22.5 eV. Despite this complication, they enable insights within 0.2 eV accuracy into the available ultraviolet photoemission and newly presented (e,2e) ionization spectra, except for the band associated with the 1a2-1 one-hole state, which is probably subject to rather significant vibronic coupling effects, and a band at ˜25 eV characterized by a momentum distribution of "s-type" symmetry, which Green's function calculations fail to reproduce. We note the vicinity of the vertical double ionization threshold at ˜26 eV.

Influence of polyhedron distortions on calculated bond-valence sums for cations with one lone electron pair.

PubMed

Wang, X; Liebau, F

2007-04-01

In the present bond-valence model (BVM), the bond-valence parameters r(0) and b are, in general, supposed to be constant for each A-X pair and equal to 0.37 A for all A-X pairs, respectively. For [A(i)(X(j))(n)] coordination polyhedra that do not deviate strongly from regularity, these suppositions are well fulfilled and calculated values for the bond-valence sums (BVS)(i) are nearly equal to the whole-number values of the stoichiometric valence. However, application of the BVM to 2591 [L(i)(X(j))(n)] polyhedra, where L are p-block cations, i.e. cations of the 13th to 17th group of the periodic system of elements, with one lone electron pair and X = O(-II), S(-II) and Se(-II), shows that r(0i) values of individual [LX(n)] polyhedra are correlated with the absolute value /Phi(i)/ of an eccentricity parameter, Phi(i), which is higher for more distorted [LX(n)] polyhedra. As a consequence, calculated (BVS)(i) values for these polyhedra are also correlated with /Phi(i)/, rather than being numerically equal to the stoichiometric valence of L. This is interpreted as the stereochemical influence of the lone electron pair of L. It is shown that the values of the correlation parameters and the R(2) values of the correlation equations depend on the position of the L cation in the periodic system of elements, if the correlations are assumed to be linear. This observation suggests that (BVS)(L) describes a chemical quantity that is different from the stoichiometric valence of L.

In search for an optimal methodology to calculate the valence electron affinities of temporary anions.

PubMed

Puiatti, Marcelo; Vera, D Mariano A; Pierini, Adriana B

2009-10-28

Recently, we have proposed an approach for finding the valence anion ground state, based on the stabilization exerted by a polar solvent; the methodology used standard DFT methods and relatively inexpensive basis sets and yielded correct electron affinity (EA) values by gradually decreasing the dielectric constant of the medium. In order to address the overall performance of the new methodology, to find the best conditions for stabilizing the valence state and to evaluate its scope and limitations, we gathered a pool of 60 molecules, 25 of them bearing the conventional valence state as the ground anion and 35 for which the lowest anion state found holds the extra electron in a diffuse orbital around the molecule (non valence state). The results obtained by testing this representative set suggest a very good performance for most species having an experimental EA less negative than -3.0 eV; the correlation at the B3LYP/6-311+G(2df,p) level being y = 1.01x + 0.06, with a correlation index of 0.985. As an alternative, the time dependent DFT (TD-DFT) approach was also tested with both B3LYP and PBE0 functionals. The methodology we proposed shows a comparable or better accuracy with respect to TD-DFT, although the TD-DFT approach with the PBE0 functional is suggested as a suitable estimate for species with the most negative EAs (ca.-2.5 to -3.5 eV), for which stabilization strategies can hardly reach the valence state. As an application, a pool of 8 compounds of key biological interest with EAs which remain unknown or unclear were predicted using the new methodology.

Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals.

PubMed

Sayfutyarova, Elvira R; Sun, Qiming; Chan, Garnet Kin-Lic; Knizia, Gerald

2017-09-12

We introduce the atomic valence active space (AVAS), a simple and well-defined automated technique for constructing active orbital spaces for use in multiconfiguration and multireference (MR) electronic structure calculations. Concretely, the technique constructs active molecular orbitals capable of describing all relevant electronic configurations emerging from a targeted set of atomic valence orbitals (e.g., the metal d orbitals in a coordination complex). This is achieved via a linear transformation of the occupied and unoccupied orbital spaces from an easily obtainable single-reference wave function (such as from a Hartree-Fock or Kohn-Sham calculations) based on projectors to targeted atomic valence orbitals. We discuss the premises, theory, and implementation of the idea, and several of its variations are tested. To investigate the performance and accuracy, we calculate the excitation energies for various transition-metal complexes in typical application scenarios. Additionally, we follow the homolytic bond breaking process of a Fenton reaction along its reaction coordinate. While the described AVAS technique is not a universal solution to the active space problem, its premises are fulfilled in many application scenarios of transition-metal chemistry and bond dissociation processes. In these cases the technique makes MR calculations easier to execute, easier to reproduce by any user, and simplifies the determination of the appropriate size of the active space required for accurate results.

Housing Electrons: Relating Quantum Numbers, Energy Levels, and Electron Configurations.

ERIC Educational Resources Information Center

Garofalo, Anthony

1997-01-01

Presents an activity that combines the concepts of quantum numbers and probability locations, energy levels, and electron configurations in a concrete, hands-on way. Uses model houses constructed out of foam board and colored beads to represent electrons. (JRH)

On the correlations between the polyhedron eccentricity parameters and the bond-valence sums for the cations with one lone electron pair.

PubMed

Sidey, Vasyl

2008-08-01

Applicability of the Wang-Liebau polyhedron eccentricity parameter in the bond-valence model [Wang & Liebau (2007). Acta Cryst. B63, 216-228] has been found to be doubtful: the correlations between the values of the polyhedron eccentricity parameters and the bond-valence sums calculated for the cations with one lone electron pair are probably an artifact of the poorly determined bond-valence parameters.

Molecular Electronic Terms and Molecular Orbital Configurations.

ERIC Educational Resources Information Center

Mazo, R. M.

1990-01-01

Discussed are the molecular electronic terms which can arise from a given electronic configuration. Considered are simple cases, molecular states, direct products, closed shells, and open shells. Two examples are provided. (CW)

An electron momentum spectroscopy and density functional theory study of the outer valence electronic structure of stella-2,6-dione

NASA Astrophysics Data System (ADS)

Nixon, K. L.; Wang, F.; Campbell, L.; Maddern, T.; Winkler, D.; Gleiter, R.; Loeb, P.; Weigold, E.; Brunger, M. J.

2003-07-01

We report on the first electron momentum spectroscopy (EMS) study into the outer valence electronic structure of the ground electronic state for the organic molecule stella-2,6-dione (C8H8O2). Experimentally measured binding-energy spectra are compared against a He(Ialpha) photoelectron spectroscopy result, while our derived momentum distributions (MDs) are compared against corresponding results from the plane wave impulse approximation (PWIA) level calculations. These computations employed density functional theory (DFT) basis states at the triple zeta valence polarization (TZVP) level, with a range of exchange-correlation (XC) functionals. A detailed comparison between the experimental and PWIA DFT-XC/TZVP calculated MDs enabled us to evaluate the accuracy of the various functionals, the Becke-Perdew (BP) XC functional being found to provide the most accurate description here. The importance of the through-bond interaction to the molecular orbitals (MOs) of stella-2,6-dione is demonstrated using the orbital imaging capability of EMS. Finally we show that the molecular geometry of this molecule, as derived from BP/TZVP, is in quite good agreement with corresponding independent experimental data.

Demystifying Introductory Chemistry. Part 1: Electron Configurations from Experiment.

ERIC Educational Resources Information Center

Gillespie, Ronald J.; And Others

1996-01-01

Presents suggestions for alternative presentations of some of the material that usually forms part of the introductory chemistry course. Emphasizes development of concepts from experimental results. Discusses electronic configurations and quantum numbers, experimental evidence for electron configurations, deducing the shell model from the periodic…

The valence bond glass phase

NASA Astrophysics Data System (ADS)

Tarzia, M.; Biroli, G.

2008-06-01

We show that a new glassy phase can emerge in the presence of strong magnetic frustration and quantum fluctuations. It is a valence bond glass (VBG). We study its properties solving the Hubbard-Heisenberg model on a Bethe lattice within the large-N limit introduced by Affleck and Marston. We work out the phase diagram that contains Fermi liquid, dimer and valence bond glass phases. This new glassy phase has no electronic or spin gap (although a pseudo-gap is observed), it is characterized by long-range critical valence bond correlations and is not related to any magnetic ordering. As a consequence, it is quite different from both valence bond crystals and spin glasses.

One Way to Design a Valence-Skip Compound.

PubMed

Hase, I; Yanagisawa, T; Kawashima, K

2017-12-01

Valence-skip compound is a good candidate with high T c and low anisotropy because it has a large attractive interaction at the site of valence-skip atom. However, it is not easy to synthesize such compound because of (i) the instability of the skipping valence state, (ii) the competing charge order, and (iii) that formal valence may not be true in some compounds. In the present study, we show several examples of the valence-skip compounds and discuss how we can design them by first principles calculations. Furthermore, we calculated the electronic structure of a promising candidate of valence skipping compound RbTlCl 3 from first principles. We confirmed that the charge-density wave (CDW) is formed in this compound, and the Tl atoms in two crystallographic different sites take the valence Tl 1+ and Tl 3+ . Structure optimization study reveals that this CDW is stable at the ambient pressure, while this CDW gap can be collapsed when we apply pressure with several gigapascals. In this metallic phase, we can expect a large charge fluctuation and a large electron-phonon interaction.

Electrochemical variational study of donor/acceptor orbital mixing and electronic coupling in cyanide-bridged mixed-valence complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Yuhuua; Hupp, J.T.

1992-07-08

Cyanide-bridged mixed-valence complexes are interesting examples of strongly covalently linked redox systems which, nevertheless, exist in valence-localized form. As mixed-valence species, they display fairly intense intervalence (or metal-to-metal) charge-transfer transitions ([epsilon] [approx] 3000 M[sup [minus]1] cm[sup [minus]1]), which tend to be shifted toward the visible region from the near-infrared on account of substantial redox asymmetry. The authors have recently succeeded in obtaining (by femtosecond transient absorbance spectroscopy) a direct measure of the thermal kinetics (k[sub ET]) of the highly exothermic back-electron-transfer reaction which follows intervalence excitation in one of these complexes, (H[sub 3]N)[sub 5]Ru-NC-Fe(CN)[sub 5][sup [minus

Electronic structure and thermoelectric properties of half-Heusler compounds with eight electron valence count—KScX (X = C and Ge)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ciftci, Yasemin O.; Mahanti, Subhendra D.

Electronic band structure and structural properties of two representative half-Heusler (HH) compounds with 8 electron valence count (VC), KScC and KScGe, have been studied using first principles methods within density functional theory and generalized gradient approximation. These systems differ from the well studied class of HH compounds like ZrNiSn and ZrCoSb which have VC = 18 because of the absence of d electrons of the transition metal atoms Ni and Co. Electronic transport properties such as Seebeck coefficient (S), electrical conductivity (σ), electronic thermal conductivity (κ{sub e}) (the latter two scaled by electronic relaxation time), and the power factor (S{sup 2}σ) havemore » been calculated using semi-classical Boltzmann transport theory within constant relaxation time approximation. Both the compounds are direct band gap semiconductors with band extrema at the X point. Their electronic structures show a mixture of heavy and light bands near the valance band maximum and highly anisotropic conduction and valence bands near the band extrema, desirable features of good thermoelectric. Optimal p- or n-type doping concentrations have been estimated based on thermopower and maximum power factors. The optimum room temperature values of S are ∼1.5 times larger than that of the best room temperature thermoelectric Bi{sub 2}Te{sub 3}. We also discuss the impact of the band structure on deviations from Weidemann-Franz law as one tunes the chemical potential across the band gap.« less

The electronic characterization of biphenylene—Experimental and theoretical insights from core and valence level spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lüder, Johann; Sanyal, Biplab; Eriksson, Olle

In this paper, we provide detailed insights into the electronic structure of the gas phase biphenylene molecule through core and valence spectroscopy. By comparing results of X-ray Photoelectron Spectroscopy (XPS) measurements with ΔSCF core-hole calculations in the framework of Density Functional Theory (DFT), we could decompose the characteristic contributions to the total spectra and assign them to non-equivalent carbon atoms. As a difference with similar molecules like biphenyl and naphthalene, an influence of the localized orbitals on the relative XPS shifts was found. The valence spectrum probed by photoelectron spectroscopy at a photon energy of 50 eV in conjunction withmore » hybrid DFT calculations revealed the effects of the localization on the electronic states. Using the transition potential approach to simulate the X-ray absorption spectroscopy measurements, similar contributions from the non-equivalent carbon atoms were determined from the total spectrum, for which the slightly shifted individual components can explain the observed asymmetric features.« less

Measurement of the background in Auger-Photoemission Spectra (APECS) associated with multi-electron and inelastic valence band photoemission processes

NASA Astrophysics Data System (ADS)

Joglekar, Prasad; Shastry, Karthik; Hulbert, Steven; Weiss, Alex

2014-03-01

Auger Photoelectron Coincidence Spectroscopy (APECS), in which the Auger spectra is measured in coincidence with the core level photoelectron, is capable of pulling difficult to observe low energy Auger peaks out of a large background due mostly to inelastically scattered valence band photoelectrons. However the APECS method alone cannot eliminate the background due to valence band VB photoemission processes in which the initial photon energy is shared by 2 or more electrons and one of the electrons is in the energy range of the core level photoemission peak. Here we describe an experimental method for estimating the contributions from these background processes in the case of an Ag N23VV Auger spectra obtained in coincidence with the 4p photoemission peak. A beam of 180eV photons was incident on a Ag sample and a series of coincidence measurements were made with one cylindrical mirror analyzer (CMA) set at a fixed energies between the core and the valence band and the other CMA scanned over a range corresponding to electrons leaving the surface between 0eV and the 70eV. The spectra obtained were then used to obtain an estimate of the background in the APECS spectra due to multi-electron and inelastic VB photoemission processes. NSF, Welch Foundation.

Development of fire resistant electronic configurations for use in oxygen enriched environments

NASA Technical Reports Server (NTRS)

Smith, F. J.

1975-01-01

Design concepts for electronic black boxes and modules were tested in oxygen enriched atmospheres, and it was found that various types of sealed configurations would generally eliminate any flammability hazard. The type of configuration and its construction was found to be of more importance in the elimination of flammability hazards in electronic configurations than the types of materials utilized in them. The design concepts developed for fire hazard free electronic configurations for use in manned space programs are applicable for the design of electronic hardware for any use or environment.

Oscillator strengths and integral cross sections for the valence-shell excitations of nitric oxide studied by fast electron impact.

PubMed

Xu, Xin; Xu, Long-Quan; Xiong, Tao; Chen, Tao; Liu, Ya-Wei; Zhu, Lin-Fan

2018-01-28

The generalized oscillator strengths for the valence-shell excitations of A 2 Σ + , C 2 Π, and D 2 Σ + electronic-states of nitric oxide have been determined at an incident electron energy of 1500 eV with an energy resolution of 70 meV. The optical oscillator strengths for these transitions have been obtained by extrapolating the generalized oscillator strengths to the limit that the squared momentum transfer approaches to zero, which give an independent cross-check to the previous experimental and theoretical results. The integral cross sections for the valence-shell excitations of nitric oxide have been determined systematically from the threshold to 2500 eV with the aid of the newly developed BE-scaling method for the first time. The present optical oscillator strengths and integral cross sections of the valence-shell excitations of nitric oxide play an important role in understanding many physics and chemistry of the Earth's upper atmosphere such as the radiative cooling, ozone destruction, day glow, aurora, and so on.

Electronic Structure in Pi Systems: Part I. Huckel Theory with Electron Repulsion.

ERIC Educational Resources Information Center

Fox, Marye Anne; Matsen, F. A.

1985-01-01

Pi-CI theory is a simple, semi-empirical procedure which (like Huckel theory) treats pi and pseudo-pi orbitals; in addition, electron repulsion is explicitly included and molecular configurations are mixed. Results obtained from application of pi-CI to ethylene are superior to either the Huckel molecular orbital or valence bond theories. (JN)

The Periodic Table as a Mnemonic Device for Writing Electronic Configurations

NASA Astrophysics Data System (ADS)

Mabrouk, Suzanne T.

2003-08-01

Lectures on electronic configurations often appear boring and intangible to many students. This topic can become engaging and interesting through the use of an interactive method based on the periodic table. Using a periodic table with shell and subshell designations in each square, students learn the patterns or the periodicity to the electronic configurations of the elements. Students are then encouraged to commit these patterns to memory through rehearsal in class. With the standard periodic table and the memorized patterns, students are shown that electronic configurations can be determined. Although students often appear mystified by the topic of electronic configurations, especially when its relevance to chemistry is absent, students' understanding can be improved easily by making connections and using analogy as the activity described here does.

Cluster molecular orbital description of the electronic structures of mixed-valence iron oxides and silicates

USGS Publications Warehouse

Sherman, David M.

1986-01-01

A molecular orbital description, based on spin-unrestricted X??-scattered wave calculations, is given for the electronic structures of mixed valence iron oxides and silicates. The cluster calculations show that electron hopping and optical intervalence charge-transger result from weak FeFe bonding across shared edges of FeO6 coordination polyhedra. In agreement with Zener's double exchange model, FeFe bonding is found to stabilize ferromagnetic coupling between Fe2+ and Fe3+ cations. ?? 1986.

Introducing Students to Inner Sphere Electron Transfer Concepts through Electrochemistry Studies in Diferrocene Mixed-Valence Systems

ERIC Educational Resources Information Center

Ventura, Karen; Smith, Mark B.; Prat, Jacob R.; Echegoyen, Lourdes E.; Villagran´, Dino

2017-01-01

We have designed a 4 h physical chemistry laboratory to introduce upper division students to electrochemistry concepts, including mixed valency and electron transfer (ET), using cyclic and differential pulse voltammetries. In this laboratory practice, students use a ferrocene dimer consisting of two ferrocene centers covalently bonded through a…

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.

Imaging of the outer valence orbitals of CO by electron momentum spectroscopy — Comparison with high level MRSD-CI and DFT calculations

NASA Astrophysics Data System (ADS)

Fan, X. W.; Chen, X. J.; Zhou, S. J.; Zheng, Y.; Brion, C. E.; Frey, R.; Davidson, E. R.

1997-09-01

A newly constructed energy dispersive multichannel electron momentum spectrometer has been used to image the electron density of the outer valence orbitals of CO with high precision. Binding energy spectra are obtained at a coincidence energy resolution of 1.2 eV fwhm. The measured electron density profiles in momentum space for the outer valence orbitals of CO are compared with cross sections calculated using SCF wavefunctions with basis sets of varying complexity up to near-Hartree-Fock limit in quality. The effects of correlation and electronic relaxation on the calculated momentum profiles are investigated using large MRSD-CI calculations of the full ion-neutral overlap distributions, as well as large basis set DFT calculations with local and non-local (gradient corrected) functionals.

Charge and Spin-State Characterization of Cobalt Bis( o-dioxolene) Valence Tautomers Using Co Kβ X-ray Emission and L-Edge X-ray Absorption Spectroscopies

DOE PAGES

Liang, H. Winnie; Kroll, Thomas; Nordlund, Dennis; ...

2016-12-30

The valence tautomeric states of Co(phen)(3,5-DBQ) 2 and Co(tmeda)(3,5-DBQ) 2, where 3,5-DBQ is either the semiquinone (SQ –) or catecholate (Cat 2–) form of 3,5-di- tert-butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission spectroscopy (Kβ XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their Kβ XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described asmore » a low-spin Co III configuration and the high-temperature valence tautomer as a high-spin Co II configuration. This conclusion is further supported by Co L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature valence tautomers and ligand-field atomic-multiplet calculations of the Kβ XES and L-edge XAS spectra. In conclusion, the nature and strength of the magnetic exchange interaction between the cobalt center and SQ – in cobalt valence tautomers is discussed in view of the effective spin at the Co site from Kβ XES and the molecular spin moment from magnetic susceptibility measurements.« less

Charge and Spin-State Characterization of Cobalt Bis( o-dioxolene) Valence Tautomers Using Co Kβ X-ray Emission and L-Edge X-ray Absorption Spectroscopies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, H. Winnie; Kroll, Thomas; Nordlund, Dennis

The valence tautomeric states of Co(phen)(3,5-DBQ) 2 and Co(tmeda)(3,5-DBQ) 2, where 3,5-DBQ is either the semiquinone (SQ –) or catecholate (Cat 2–) form of 3,5-di- tert-butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission spectroscopy (Kβ XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their Kβ XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described asmore » a low-spin Co III configuration and the high-temperature valence tautomer as a high-spin Co II configuration. This conclusion is further supported by Co L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature valence tautomers and ligand-field atomic-multiplet calculations of the Kβ XES and L-edge XAS spectra. In conclusion, the nature and strength of the magnetic exchange interaction between the cobalt center and SQ – in cobalt valence tautomers is discussed in view of the effective spin at the Co site from Kβ XES and the molecular spin moment from magnetic susceptibility measurements.« less

Why Teach the Electron Configuration of the Elements as We Do?

ERIC Educational Resources Information Center

Millikan, Roger C.

1982-01-01

Discusses pros and cons of current methods of teaching electron configurations of elements. Offers alternative instructional strategies, suggesting that although tables of electron configurations are useful and in conjunction with periodic tables may help solve many problems, they should be included as reference material. (Author/JN)

Solvent dynamical control of ultrafast ground state electron transfer: implications for Class II-III mixed valency.

PubMed

Lear, Benjamin J; Glover, Starla D; Salsman, J Catherine; Londergan, Casey H; Kubiak, Clifford P

2007-10-24

We relate the solvent and temperature dependence of the rates of intramolecular electron transfer (ET) of mixed valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}-1, where L = pyridyl ligand and BL = pyrazine. Complexes were reduced chemically or electrochemically to obtain the mixed valence anions in seven solvents: acetonitrile, methylene chloride, dimethylformamide, tetrahydrofuran, dimethylsulfoxide, chloroform, and hexamethylphosphoramide. Rate constants for intramolecular ET were estimated by simulating the observed degree of nu(CO) IR band shape coalescence in the mixed valence state. Correlations between rate constants for ET and solvent properties including static dielectric constant, optical dielectric constant, the quantity 1/epsilonop - 1/epsilonS, microscopic solvent polarity, viscosity, cardinal rotational moments of inertia, and solvent relaxation times were examined. In the temperature study, the complexes displayed a sharp increase in the ket as the freezing points of the solvents methylene chloride and acetonitrile were approached. The solvent phase transition causes a localized-to-delocalized transition in the mixed valence ions and an acceleration in the rate of ET. This is explained in terms of decoupling the slower solvent motions involved in the frequency factor nuN which increases the value of nuN. The observed solvent and temperature dependence of the ket for these complexes is used in order to formulate a new definition for Robin-Day class II-III mixed valence compounds. Specifically, it is proposed that class II-III compounds are those for which thermodynamic properties of the solvent exert no control over ket, but the dynamic properties of the solvent still influence ket.

A valence bond study of three-center four-electron pi bonding: electronegativity vs electroneutrality.

PubMed

DeBlase, Andrew; Licata, Megan; Galbraith, John Morrison

2008-12-18

Three-center four-electron (3c4e) pi bonding systems analogous to that of the ozone molecule have been studied using modern valence bond theory. Molecules studied herein consist of combinations of first row atoms C, N, and O with the addition of H atoms where appropriate in order to preserve the 3c4e pi system. Breathing orbital valence bond (BOVB) calculations were preformed at the B3LYP/6-31G**-optimized geometries in order to determine structural weights, pi charge distributions, resonance energies, and pi bond energies. It is found that the most weighted VB structure depends on atomic electronegativity and charge distribution, with electronegativity as the dominant factor. By nature, these systems are delocalized, and therefore, resonance energy is the main contributor to pi bond energies. Molecules with a single dominant VB structure have low resonance energies and therefore low pi bond energies.

Valence electronic structure of cobalt phthalocyanine from an optimally tuned range-separated hybrid functional.

PubMed

Brumboiu, Iulia Emilia; Prokopiou, Georgia; Kronik, Leeor; Brena, Barbara

2017-07-28

We analyse the valence electronic structure of cobalt phthalocyanine (CoPc) by means of optimally tuning a range-separated hybrid functional. The tuning is performed by modifying both the amount of short-range exact exchange (α) included in the hybrid functional and the range-separation parameter (γ), with two strategies employed for finding the optimal γ for each α. The influence of these two parameters on the structural, electronic, and magnetic properties of CoPc is thoroughly investigated. The electronic structure is found to be very sensitive to the amount and range in which the exact exchange is included. The electronic structure obtained using the optimal parameters is compared to gas-phase photo-electron data and GW calculations, with the unoccupied states additionally compared with inverse photo-electron spectroscopy measurements. The calculated spectrum with tuned γ, determined for the optimal value of α = 0.1, yields a very good agreement with both experimental results and with GW calculations that well-reproduce the experimental data.

Hierarchy effect on electronic structure and core-to-valence transitions in bone tissue: perspectives in medical nanodiagnostics of mineralized bone

NASA Astrophysics Data System (ADS)

Samoilenko, Dmitrii O.; Avrunin, Alexander S.; Pavlychev, Andrey A.

2017-06-01

Electronic structure and core-to-valence transitions in bone tissue are examined in the framework of the morphological 3DSL model that takes into account (i) structural and functional organization of the skeleton in the normal and pathological conditions and (ii) peculiarities of electron wave propagation in a three-dimensional superlattice of "black-nanocrystallites-in-muddy-waters". Our focus is on the HAP-to-bone red shifts of core-to-valence transitions near Ca and P 2p and O 1s edges in single-crystal hydroxyapatite (HAP) Ca10(PO4)6(OH)2. The origin of the HAP-to-bone shift is discussed and the extended comparative analysis of the experimental data is performed. The detected spectral shift is assigned with the effect of hierarchical organization of bone tissue. This hierarchy effect on the core-to-valence transition energies is regarded as a promising tool for medical imaging and perspective pathway for nanodiagnostics of mineralized bone. Contribution to the Topical Issue "Dynamics of Systems at the Nanoscale", edited by Andrey Solov'yov and Andrei Korol.

Probability of Two-Step Photoexcitation of Electron from Valence Band to Conduction Band through Doping Level in TiO2.

PubMed

Nishikawa, Masami; Shiroishi, Wataru; Honghao, Hou; Suizu, Hiroshi; Nagai, Hideyuki; Saito, Nobuo

2017-08-17

For an Ir-doped TiO 2 (Ir:TiO 2 ) photocatalyst, we examined the most dominant electron-transfer path for the visible-light-driven photocatalytic performance. The Ir:TiO 2 photocatalyst showed a much higher photocatalytic activity under visible-light irradiation than nondoped TiO 2 after grafting with the cocatalyst of Fe 3+ . For the Ir:TiO 2 photocatalyst, the two-step photoexcitation of an electron from the valence band to the conduction band through the Ir doping level occurred upon visible-light irradiation, as observed by electron spin resonance spectroscopy. The two-step photoexcitation through the doping level was found to be a more stable process with a lower recombination rate of hole-electron pairs than the two-step photoexcitation process through an oxygen vacancy. Once electrons are photoexcited to the conduction band by the two-step excitation, the electrons can easily transfer to the surface because the conduction band is a continuous electron path, whereas the electrons photoexcited at only the doping level could not easily transfer to the surface because of the discontinuity of this path. The observed two-step photoexcitation from the valence band to the conduction band through the doping level significantly contributes to the enhancement of the photocatalytic performance.

Electronic and transport properties of Cobalt-based valence tautomeric molecules and polymers

NASA Astrophysics Data System (ADS)

Chen, Yifeng; Calzolari, Arrigo; Buongiorno Nardelli, Marco

2011-03-01

The advancement of molecular spintronics requires further understandings of the fundamental electronic structures and transport properties of prototypical spintronics molecules and polymers. Here we present a density functional based theoretical study of the electronic structures of Cobalt-based valence tautomeric molecules Co III (SQ)(Cat)L Co II (SQ)2 L and their polymers, where SQ refers to the semiquinone ligand, and Cat the catecholate ligand, while L is a redox innocent backbone ligand. The conversion from low-spin Co III ground state to high-spin Co II excited state is realized by imposing an on-site potential U on the Co atom and elongating the Co-N bond. Transport properties are subsequently calculated by extracting electronic Wannier functions from these systems and computing the charge transport in the ballistic regime using a Non-Equilibrium Green's Function (NEGF) approach. Our transport results show distinct charge transport properties between low-spin ground state and high-spin excited state, hence suggesting potential spintronics devices from these molecules and polymers such as spin valves.

Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy

DOE PAGES

March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina; ...

2017-01-17

Here we probe the dynamics of valence electrons in photoexcited [Fe(terpy) 2] 2+ in solution to gain deeper insight into the Fe-ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making it a powerful technique for molecular studies in a wide variety of environments. A picosecond-time-resolved measurement of the complete Is X-ray emission spectrum captures the transient photoinduced changes and includes the weak valence-to-core (vtc) emission lines that correspond to transitions from occupied valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitalsmore » directly involved in the light-driven dynamics; a change in the metal-ligand orbital overlap results in an intensity reduction and a blue energy shift in agreement with our theoretical calculations and more subtle features at the highest energies reflect changes in the frontier orbital populations.« less

Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina

Here we probe the dynamics of valence electrons in photoexcited [Fe(terpy) 2] 2+ in solution to gain deeper insight into the Fe-ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making it a powerful technique for molecular studies in a wide variety of environments. A picosecond-time-resolved measurement of the complete Is X-ray emission spectrum captures the transient photoinduced changes and includes the weak valence-to-core (vtc) emission lines that correspond to transitions from occupied valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitalsmore » directly involved in the light-driven dynamics; a change in the metal-ligand orbital overlap results in an intensity reduction and a blue energy shift in agreement with our theoretical calculations and more subtle features at the highest energies reflect changes in the frontier orbital populations.« less

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

Authentic Assessment Tool for the Measurement of Students' Understanding of the Valence Shell Electron Pair Repulsion Theory

ERIC Educational Resources Information Center

Wuttisela, Karntarat

2017-01-01

There are various types of instructional media related to Valence Shell Electron Pair Repulsion (VSEPR) but there is a lack of diversity of resources devoted to assessment. This research presents an assessment and comparison of students' understanding of VSEPR theory before and after tuition involving the use of the foam molecule model (FMM) and…

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

2015-05-08

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.

Correlation between valence electronic structure and magnetic properties in RCo5 (R = rare earth) intermetallic compound

NASA Astrophysics Data System (ADS)

Zhi-Qin, Xue; Yong-Quan, Guo

2016-06-01

The magnetisms of RCo5 (R = rare earth) intermetallics are systematically studied with the empirical electron theory of solids and molecules (EET). The theoretical moments and Curie temperatures agree well with experimental ones. The calculated results show strong correlations between the valence electronic structure and the magnetic properties in RCo5 intermetallic compounds. The moments of RCo5 intermetallics originate mainly from the 3d electrons of Co atoms and 4f electrons of rare earth, and the s electrons also affect the magnetic moments by the hybridization of d and s electrons. It is found that moment of Co atom at 2c site is higher than that at 3g site due to the fact that the bonding effect between R and Co is associated with an electron transformation from 3d electrons into covalence electrons. In the heavy rare-earth-based RCo5 intermetallics, the contribution to magnetic moment originates from the 3d and 4f electrons. The covalence electrons and lattice electrons also affect the Curie temperature, which is proportional to the average moment along the various bonds. Project supported by the National Natural Science Foundation of China (Grant No. 11274110).

Valence holes observed in nanodiamonds dispersed in water

NASA Astrophysics Data System (ADS)

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

2015-02-01

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 sp2-hybridized carbon disappear, and holes in the valence band are observed.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 sp2-hybridized carbon disappear, and holes in the valence band are observed. Electronic supplementary information (ESI) available: Experimental methods, details on XAS/XES normalization and background correction procedures. See DOI: 10.1039/c4nr06639a

Seniority Number in Valence Bond Theory.

PubMed

Chen, Zhenhua; Zhou, Chen; Wu, Wei

2015-09-08

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.

The Periodic Table as a Mnemonic Device for Writing Electronic Configurations.

ERIC Educational Resources Information Center

Mabrouk, Suzanne T.

2003-01-01

Presents an interactive method for using the periodic table as an effective mnemonic for writing electronic configurations. Discusses the intrinsic relevance of configurations to chemistry by building upon past analogies. Addresses pertinent background information, describes the hands-on method, and demonstrates its use. Transforms the traditional…

Electric Field Generation and Control of Bipartite Quantum Entanglement between Electronic Spins in Mixed Valence Polyoxovanadate [GeV14O40]8.

PubMed

Palii, Andrew; Aldoshin, Sergey; Tsukerblat, Boris; Borràs-Almenar, Juan José; Clemente-Juan, Juan Modesto; Cardona-Serra, Salvador; Coronado, Eugenio

2017-08-21

As part of the search for systems in which control of quantum entanglement can be achieved, here we consider the paramagnetic mixed valence polyoxometalate K 2 Na 6 [GeV 14 O 40 ]·10H 2 O in which two electrons are delocalized over the 14 vanadium ions. Applying a homogeneous electric field can induce an antiferromagnetic coupling between the two delocalized electronic spins that behave independently in the absence of the field. On the basis of the proposed theoretical model, we show that the external field can be used to generate controllable quantum entanglement between the two electronic spins traveling over a vanadium network of mixed valence polyoxoanion [GeV 14 O 40 ] 8- . Within a simplified two-level picture of the energy pattern of the electronic pair based on the previous ab initio analysis, we evaluate the temperature and field dependencies of concurrence and thus indicate that the entanglement can be controlled via the temperature, magnitude, and orientation of the electric field with respect to molecular axes of [GeV 14 O 40 ] 8- .

Photoelectron spectrum of valence anions of uracil and first-principles calculations of excess electron binding energies.

PubMed

Bachorz, Rafał A; Klopper, Wim; Gutowski, Maciej; Li, Xiang; Bowen, Kit H

2008-08-07

The photoelectron spectrum (PES) of the uracil anion is reported and discussed from the perspective of quantum chemical calculations of the vertical detachment energies (VDEs) of the anions of various tautomers of uracil. The PES peak maximum is found at an electron binding energy of 2.4 eV, and the width of the main feature suggests that the parent anions are in a valence rather than a dipole-bound state. The canonical tautomer as well as four tautomers that result from proton transfer from an NH group to a C atom were investigated computationally. At the Hartree-Fock and second-order Moller-Plesset perturbation theory levels, the adiabatic electron affinity (AEA) and the VDE have been converged to the limit of a complete basis set to within +/-1 meV. Post-MP2 electron-correlation effects have been determined at the coupled-cluster level of theory including single, double, and noniterative triple excitations. The quantum chemical calculations suggest that the most stable valence anion of uracil is the anion of a tautomer that results from a proton transfer from N1H to C5. It is characterized by an AEA of 135 meV and a VDE of 1.38 eV. The peak maximum is as much as 1 eV larger, however, and the photoelectron intensity is only very weak at 1.38 eV. The PES does not lend support either to the valence anion of the canonical tautomer, which is the second most stable anion, and whose VDE is computed at about 0.60 eV. Agreement between the peak maximum and the computed VDE is only found for the third most stable tautomer, which shows an AEA of approximately -0.1 eV and a VDE of 2.58 eV. This tautomer results from a proton transfer from N3H to C5. The results illustrate that the characteristics of biomolecular anions are highly dependent on their tautomeric form. If indeed the third most stable anion is observed in the experiment, then it remains an open question why and how this species is formed under the given conditions.

Role of valence electrons in phase transformation kinetics of thallium and its dilute alloys

NASA Technical Reports Server (NTRS)

Ahmed, R.; Ahmed, S.

1991-01-01

The kinetics of the phase transformation of thallium and its dilute alloys were investigated using XRD and calorimetry. Pure thallium exhibits a beta(bcc) to alpha(hcp) phase transformation on cooling at 508 K. With alloying additions, the crystal structure for each phase does not change, although the size of the unit cell increases. The enthalpy and the temperature of phase transformation of each alloy have been determined. The chemical free energy change associated with the phase transformation of each alloy was calculated. The valence electrons make an outstanding contribution to the chemical free energy change required for the phase change.

Evidence for a different electronic configuration as a primary effect during compression of orthorhombic perovskites: The case of Nd M3 +O3 (M =Cr ,Ga )

NASA Astrophysics Data System (ADS)

Ardit, M.; Dondi, M.; Merli, M.; Cruciani, G.

2018-02-01

(Mg ,Fe ) Si O3 perovskite is the most abundant mineral of the Earth's lower mantle, and compounds with the perovskite structure are perhaps the most widely employed ceramics. Hence, they attract both geophysicists and material scientists. Several investigations attempted to predict their structural evolution at high pressure, and recent advancements highlighted that perovskites having ions with the same formal valence at both polyhedral sites (i.e., 3 +:3 + ) define different compressional patterns when transition metal ions (TMI) are involved. In this study, in situ high-pressure synchrotron XRD measurements coupled with ab initio simulations of the electronic population of NdCr O3 perovskite are compared with the compressional feature of NdGa O3 . Almost identical from a steric point of view (C r3 + and G a3 + have almost the same ionic radius), the different electronic configuration of octahedrally coordinated ions - which leads to a redistribution of electrons at the 3 d orbitals for C r3 + - allows the crystal field stabilization energy (CFSE) to act as a vehicle of octahedral softening in NdCr O3 or it turns octahedra into rigid units when CFSE is null as in NdGa O3 . Besides to highlight that different electronic configurations can act as a primary effect during compression of perovskite compounds, our findings have a deep repercussion on the way the compressibility of perovskites have to be modeled.

Electronic spectroscopy of diatomic molecules

NASA Technical Reports Server (NTRS)

Partridge, Harry; Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.

1994-01-01

This article provides an overview of the principal computational approaches and their accuracy for the study of electronic spectroscopy of diatomic molecules. We include a number of examples from our work that illustrate the range of application. We show how full configuration interaction benchmark calculations were instrumental in improving the understanding of the computational requirements for obtaining accurate results for diatomic spectroscopy. With this understanding it is now possible to compute radiative lifetimes accurate to within 10% for systems involving first- and second-row atoms. We consider the determination of the infrared vibrational transition probabilities for the ground states of SiO and NO, based on a globally accurate dipole moment function. We show how we were able to assign the a(sup "5)II state of CO as the upper state in the recently observed emission bands of CO in an Ar matrix. We next discuss the assignment of the photoelectron detachment spectra of NO and the alkali oxide negative ions. We then present several examples illustrating the state-of-the-art in determining radiative lifetimes for valence-valence and valence-Rydberg transitions. We next compare the molecular spectroscopy of the valence isoelectronic B2, Al2, and AlB molecules. The final examples consider systems involving transition metal atoms, which illustrate the difficulty in describing states with different numbers of d electrons.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamaguchi, Hisato; Ogawa, Shuichi; Watanabe, Daiki

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

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

DOE PAGES

Yamaguchi, Hisato; Ogawa, Shuichi; Watanabe, Daiki; ...

2016-09-01

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

Fast mapping of the cobalt-valence state in Ba0.5Sr0.5Co0.8Fe0.2O3-d by electron energy loss spectroscopy.

PubMed

Müller, Philipp; Meffert, Matthias; Störmer, Heike; Gerthsen, Dagmar

2013-12-01

A fast method for determination of the Co-valence state by electron energy loss spectroscopy in a transmission electron microscope is presented. We suggest the distance between the Co-L3 and Co-L2 white-lines as a reliable property for the determination of Co-valence states between 2+ and 3+. The determination of the Co-L2,3 white-line distance can be automated and is therefore well suited for the evaluation of large data sets that are collected for line scans and mappings. Data with a low signal-to-noise due to short acquisition times can be processed by applying principal component analysis. The new technique was applied to study the Co-valence state of Ba0.5Sr0.5Co0.8Fe0.2O3-d (BSCF), which is hampered by the superposition of the Ba-M4,5 white-lines on the Co-L2,3 white-lines. The Co-valence state of the cubic BSCF phase was determined to be 2.2+ (±0.2) after annealing for 100 h at 650°C, compared to an increased valence state of 2.8+ (±0.2) for the hexagonal phase. These results support models that correlate the instability of the cubic BSCF phase with an increased Co-valence state at temperatures below 840°C.

Electronic properties and bonding in Zr Hx thin films investigated by valence-band x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Magnuson, Martin; Schmidt, Susann; Hultman, Lars; Högberg, Hans

2017-11-01

The electronic structure and chemical bonding in reactively magnetron sputtered Zr Hx (x =0.15 , 0.30, 1.16) thin films with oxygen content as low as 0.2 at.% are investigated by 4d valence band, shallow 4p core-level, and 3d core-level x-ray photoelectron spectroscopy. With increasing hydrogen content, we observe significant reduction of the 4d valence states close to the Fermi level as a result of redistribution of intensity toward the H 1s-Zr 4d hybridization region at ˜6 eV below the Fermi level. For low hydrogen content (x =0.15 , 0.30), the films consist of a superposition of hexagonal closest-packed metal (α phase) and understoichiometric δ -Zr Hx (Ca F2 -type structure) phases, while for x =1.16 , the films form single-phase Zr Hx that largely resembles that of stoichiometric δ -Zr H2 phase. We show that the cubic δ -Zr Hx phase is metastable as thin film up to x =1.16 , while for higher H contents the structure is predicted to be tetragonally distorted. For the investigated Zr H1.16 film, we find chemical shifts of 0.68 and 0.51 eV toward higher binding energies for the Zr 4 p3 /2 and 3 d5 /2 peak positions, respectively. Compared to the Zr metal binding energies of 27.26 and 178.87 eV, this signifies a charge transfer from Zr to H atoms. The change in the electronic structure, spectral line shapes, and chemical shifts as a function of hydrogen content is discussed in relation to the charge transfer from Zr to H that affects the conductivity by charge redistribution in the valence band.

Understanding valence-shell electron-pair repulsion (VSEPR) theory using origami molecular models

NASA Astrophysics Data System (ADS)

Endah Saraswati, Teguh; Saputro, Sulistyo; Ramli, Murni; Praseptiangga, Danar; Khasanah, Nurul; Marwati, Sri

2017-01-01

Valence-shell electron-pair repulsion (VSEPR) theory is conventionally used to predict molecular geometry. However, it is difficult to explore the full implications of this theory by simply drawing chemical structures. Here, we introduce origami modelling as a more accessible approach for exploration of the VSEPR theory. Our technique is simple, readily accessible and inexpensive compared with other sophisticated methods such as computer simulation or commercial three-dimensional modelling kits. This method can be implemented in chemistry education at both the high school and university levels. We discuss the example of a simple molecular structure prediction for ammonia (NH3). Using the origami model, both molecular shape and the scientific justification can be visualized easily. This ‘hands-on’ approach to building molecules will help promote understanding of VSEPR theory.

A revised MRCI-algorithm coupled to an effective valence-shell Hamiltonian. II. Application to the valence excitations of butadiene

NASA Astrophysics Data System (ADS)

Strodel, Paul; Tavan, Paul

2002-09-01

In Paper I of this work we have sketched an improved MRCI algorithm and its coupling to the effective valence-shell Hamiltonian OM2. To check the quality of the resulting OM2/MRCI approach, it is applied here to the excited valence states of all-trans butadiene. As is explained by a review of previous theoretical work, proper descriptions of these states posed severe problems within correlated ab initio treatments but seemed to be trivial within simple correlated pi-electron models. We now show that an extended MRCI treatment of the correlations among all valence electrons as described by OM2 closely reproduces the experimental evidence, placing the vertical 2 1Ag excitation by about 0.2 eV below the 1 1Bu excitation. By an analysis of sigma]-[pi interactions we explain the corresponding earlier success of correlated pi-electron theory. Exploiting the enhanced capabilities of the new approach we investigate the potential surfaces. Here, OM2/MRCI is shown to predict that the 2 1Ag state is energetically lowered about four times more strongly than the 1 1Bu state upon geometry relaxation constrained to the C2h symmetry. We conclude that OM2/MRCI should be well-suited for the study of excited state surfaces of organic dye molecules.

Theory and practice of uncommon molecular electronic configurations.

PubMed

Gryn'ova, Ganna; Coote, Michelle L; Corminboeuf, Clemence

2015-01-01

The electronic configuration of the molecule is the foundation of its structure and reactivity. The spin state is one of the key characteristics arising from the ordering of electrons within the molecule's set of orbitals. Organic molecules that have open-shell ground states and interesting physicochemical properties, particularly those influencing their spin alignment, are of immense interest within the up-and-coming field of molecular electronics. In this advanced review, we scrutinize various qualitative rules of orbital occupation and spin alignment, viz., the aufbau principle, Hund's multiplicity rule, and dynamic spin polarization concept, through the prism of quantum mechanics. While such rules hold in selected simple cases, in general the spin state of a system depends on a combination of electronic factors that include Coulomb and Pauli repulsion, nuclear attraction, kinetic energy, orbital relaxation, and static correlation. A number of fascinating chemical systems with spin states that fluctuate between triplet and open-shell singlet, and are responsive to irradiation, pH, and other external stimuli, are highlighted. In addition, we outline a range of organic molecules with intriguing non-aufbau orbital configurations. In such quasi-closed-shell systems, the singly occupied molecular orbital (SOMO) is energetically lower than one or more doubly occupied orbitals. As a result, the SOMO is not affected by electron attachment to or removal from the molecule, and the products of such redox processes are polyradicals. These peculiar species possess attractive conductive and magnetic properties, and a number of them that have already been developed into molecular electronics applications are highlighted in this review. WIREs Comput Mol Sci 2015, 5:440-459. doi: 10.1002/wcms.1233 For further resources related to this article, please visit the WIREs website.

Configuration-specific electronic structure of strongly interacting interfaces: TiOPc on Cu(110)

NASA Astrophysics Data System (ADS)

Maughan, Bret; Zahl, Percy; Sutter, Peter; Monti, Oliver L. A.

2017-12-01

We use low-temperature scanning tunneling microscopy in combination with angle-resolved ultraviolet and two-photon photoemission spectroscopy to investigate the interfacial electronic structure of titanyl phthalocyanine (TiOPc) on Cu(110). We show that the presence of two unique molecular adsorption configurations is crucial for a molecular-level analysis of the hybridized interfacial electronic structure. Specifically, thermally induced self-assembly exposes marked adsorbate-configuration-specific contributions to the interfacial electronic structure. The results of this work demonstrate an avenue towards understanding and controlling interfacial electronic structure in chemisorbed films even for the case of complex film structure.

Smooth Scaling of Valence Electronic Properties in Fullerenes: From One Carbon Atom, to C60, to Graphene

DTIC Science & Technology

2012-09-18

Smooth scaling of valence electronic properties in fullerenes: from one carbon atom , to C60, to graphene Greyson R. Lewis,1 William E. Bunting,1...pacitance scaling lines of the fullerenes. Lastly, it is found that points representing the carbon atom and the graphene limit lie on scaling lines for...icosahedral fullerenes, so their quantum capacitances and their detachment energies scale smoothly from one C atom , through C60, to graphene. I

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

Magnetic properties and core electron binding energies of liquid water

NASA Astrophysics Data System (ADS)

Galamba, N.; Cabral, Benedito J. C.

2018-01-01

The magnetic properties and the core and inner valence electron binding energies of liquid water are investigated. The adopted methodology relies on the combination of molecular dynamics and electronic structure calculations. Born-Oppenheimer molecular dynamics with the Becke and Lee-Yang-Parr functionals for exchange and correlation, respectively, and includes an empirical correction (BLYP-D3) functional and classical molecular dynamics with the TIP4P/2005-F model were carried out. The Keal-Tozer functional was applied for predicting magnetic shielding and spin-spin coupling constants. Core and inner valence electron binding energies in liquid water were calculated with symmetry adapted cluster-configuration interaction. The relationship between the magnetic shielding constant σ(17O), the role played by the oxygen atom as a proton acceptor and donor, and the tetrahedral organisation of liquid water are investigated. The results indicate that the deshielding of the oxygen atom in water is very dependent on the order parameter (q) describing the tetrahedral organisation of the hydrogen bond network. The strong sensitivity of magnetic properties on changes of the electronic density in the nuclei environment is illustrated by a correlation between σ(17O) and the energy gap between the 1a1[O1s] (core) and the 2a1 (inner valence) orbitals of water. Although several studies discussed the eventual connection between magnetic properties and core electron binding energies, such a correlation could not be clearly established. Here, we demonstrate that for liquid water this correlation exists although involving the gap between electron binding energies of core and inner valence orbitals.

A variational Monte Carlo study of different spin configurations of electron-hole bilayer

NASA Astrophysics Data System (ADS)

Sharma, Rajesh O.; Saini, L. K.; Bahuguna, Bhagwati Prasad

2018-05-01

We report quantum Monte Carlo results for mass-asymmetric electron-hole bilayer (EHBL) system with different-different spin configurations. Particularly, we apply a variational Monte Carlo method to estimate the ground-state energy, condensate fraction and pair-correlations function at fixed density rs = 5 and interlayer distance d = 1 a.u. We find that spin-configuration of EHBL system, which consists of only up-electrons in one layer and down-holes in other i.e. ferromagnetic arrangement within layers and anti-ferromagnetic across the layers, is more stable than the other spin-configurations considered in this study.

Quantitative analysis of valence photoemission spectra and quasiparticle excitations at chromophore-semiconductor interfaces.

PubMed

Patrick, Christopher E; Giustino, Feliciano

2012-09-14

Investigating quasiparticle excitations of molecules on surfaces through photoemission spectroscopy forms a major part of nanotechnology research. Resolving spectral features at these interfaces requires a comprehensive theory of electron removal and addition processes in molecules and solids which captures the complex interplay of image charges, thermal effects, and configurational disorder. Here, we develop such a theory and calculate the quasiparticle energy-level alignment and the valence photoemission spectrum for the prototype biomimetic solar cell interface between anatase TiO(2) and the N3 chromophore. By directly matching our calculated photoemission spectrum to experimental data, we clarify the atomistic origin of the chromophore peak at low binding energy. This case study sets a new standard in the interpretation of photoemission spectroscopy at complex chromophore-semiconductor interfaces.

Aluminum/vacuum multilayer configuration for spatial high-energy electron shielding via electron return effects induced by magnetic field.

PubMed

Chen, Tuo; Tang, Xiaobin; Chen, Feida; Ni, Minxuan; Huang, Hai; Zhang, Yun; Chen, Da

2017-06-26

Radiation shielding of high-energy electrons is critical for successful space missions. However, conventional passive shielding systems exhibit several limitations, such as heavy configuration, poor shielding ability, and strong secondary bremsstrahlung radiation. In this work, an aluminum/vacuum multilayer structure was proposed based on the electron return effects induced by magnetic field. The shielding property of several configurations was evaluated by using the Monte Carlo method. Results showed that multilayer systems presented improved shielding ability to electrons, and less secondary x-ray transmissions than those of conventional systems. Moreover, the influences of magnetic flux density and number of layers on the shielding property of multilayer systems were investigated using a female Chinese hybrid reference phantom based on cumulative dose. In the case of two aluminum layers, the cumulative dose in a phantom gradually decreased with increasing magnetic flux density. The maximum decline rate was found within 0.4-1 Tesla. With increasing layers of configuration, the cumulative dose decreased and the shielding ability improved. This research provides effective shielding measures for future space radiation protection in high-energy electron environments.

Design of materials configurations for enhanced phononic and electronic properties

NASA Astrophysics Data System (ADS)

Daraio, Chiara

The discovery of novel nonlinear dynamic and electronic phenomena is presented for the specific cases of granular materials and carbon nanotubes. This research was conducted for designing and constructing optimized macro-, micro- and nano-scale structural configurations of materials, and for studying their phononic and electronic behavior. Variation of composite arrangements of granular elements with different elastic properties in a linear chain-of-sphere, Y-junction or 3-D configurations led to a variety of novel phononic phenomena and interesting physical properties, which can be potentially useful for security, communications, mechanical and biomedical engineering applications. Mechanical and electronic properties of carbon nanotubes with different atomic arrangements and microstructures were also investigated. Electronic properties of Y-junction configured carbon nanotubes exhibit an exciting transistor switch behavior which is not seen in linear configuration nanotubes. Strongly nonlinear materials were designed and fabricated using novel and innovative concepts. Due to their unique strongly nonlinear and anisotropic nature, novel wave phenomena have been discovered. Specifically, violations of Snell's law were detected and a new mechanism of wave interaction with interfaces between NTPCs (Nonlinear Tunable Phononic Crystals) was established. Polymer-based systems were tested for the first time, and the tunability of the solitary waves speed was demonstrated. New materials with transformed signal propagation speed in the manageable range of 10-100 m/s and signal amplitude typical for audible speech have been developed. The enhancing of the mitigation of solitary and shock waves in 1-D chains were demonstrated and a new protective medium was designed for practical applications. 1-D, 2-D and 3-D strongly nonlinear system have been investigated providing a broad impact on the whole area of strongly nonlinear wave dynamics and creating experimental basis for new

Non-linear valence electron dynamics in metallic clusters

NASA Astrophysics Data System (ADS)

Calvayrac, F.

This work deals with the response of the valence electrons of simple metal clusters to various excitations, in a purely dynamical context. It is related to various recent experiments where the methods based on linear response fail. The electronic motion is solved in direct time, the wavefunctions being discretized on an evenly spaced grid. The theoretical framework is the time dependent density functional theory, restricted to a version local in time and space (LSDA). The other parts of the clusters are either a jellium or an explicit ionic background exerting local or non-local pseudopotentials. The ionic dynamics is discussed, as well as the relevance of various observables. The corresponding numerical techniques are given: either a selfconsistent Crank-Nicholson method is used, approximated by an alternate propagation in every space direction, or a method alternating between direct and Fourier space. The equations suggest a parallel treatment. Several examples of application are given. The case of Na9+ is thoroughly discussed, then the less simple case of Na11+. Spectra obtained for sodium clusters deposited on sodium chlorine surfaces are shown. An example of a simulation with a moving ionic background is handled: the transfer to the ionic degrees of freedom of the energy deposited in a twelve sodium atoms cluster by a femtosecond laser pulse is discussed. The electronic resonance spectrum for a linear carbon cluster C5 is then given. In the conclusion, the work is discussed as well as possible improvements and developments from the theoretical or numerical point of view. Ce travail aborde la réponse des électrons de valence d'agrégats de métaux simples à diverses excitations, dans un contexte purement dynamique, en relation avec diverses expériences récentes que les méthodes fondées sur la réponse linéaire sont incapables d'aborder. Le mouvement de ces électrons est résolu directement en temps, leurs fonctions d'onde étant discrétisées sur une

Mixed valency and site-preference chemistry for cerium and its compounds: A predictive density-functional theory study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alam, Aftab; Johnson, Duane D.

Cerium and its technologically relevant compounds are examples of anomalous mixed valency, originating from two competing oxidation states—itinerant Ce4+ and localized Ce3+. Under applied stress, anomalous transitions are observed but not well understood. Here we treat mixed valency as an “alloy” problem involving two valences with competing and numerous site-occupancy configurations. We use density-functional theory with Hubbard U (i.e., DFT+U) to evaluate the effective valence and predict properties, including controlling the valence by pseudoternary alloying. For Ce and its compounds, such as (Ce,La)2(Fe,Co)14B permanent magnets, we find a stable mixed-valent α state near the spectroscopic value of νs=3.53. Ce valencymore » in compounds depends on its steric volume and local chemistry. For La doping, Ce valency shifts towards γ-like Ce3+, as expected from steric volume; for Co doping, valency depends on local Ce-site chemistry and steric volume. Our approach captures the key origins of anomalous valency and site-preference chemistry in complex compounds.« less

Porous electronic current collector bodies for electrochemical cell configurations

DOEpatents

Pollack, William; Reichner, Philip

1989-01-01

A high-temperature, solid electrolyte electrochemical cell configuration is made comprising a plurality of elongated electrochemical cells 1, having inner electrodes 3, outer electrodes 6 and solid electrolyte 4 therebetween, the cells being electronically connected in series and parallel by flexible, porous, fibrous strips 7, where the strips contain flexible, electronically conductive fibers bonded together and coated with a refractory oxide, and where the oxide coating is effective to prevent additional bonding of fibers during electrochemical cell operation at high temperatures.

Variation of sigma-hole magnitude with M valence electron population in MX(n)Y(4-n) molecules (n = 1-4; M = C, Si, Ge; X, Y = F, Cl, Br).

PubMed

McDowell, Sean A C; Joseph, Jerelle A

2014-01-14

Sigma holes are described as electron-deficient regions on atoms, particularly along the extension of covalent bonds, due to non-uniform electron density distribution on the surface of these atoms. A computational study of MX(n)Y(4-n) molecules (n = 1-4; M = C, Si, Ge; X, Y = F, Cl, Br) was undertaken and it is shown that the relative sigma hole potentials on M due to X-M and Y-M can be adequately explained in terms of the variation in the valence electron population of the central M atom. A model is proposed for the depletion of the M valence electron population which explains the trends in sigma hole strengths, especially those that cannot be accounted for solely on the basis of relative electronegativities.

Valence-Band Electronic Structures of High-Pressure-Phase PdF2-type Platinum-Group Metal Dioxides MO2 (M = Ru, Rh, Ir, and Pt)

NASA Astrophysics Data System (ADS)

Soda, Kazuo; Kobayashi, Daichi; Mizui, Tatsuya; Kato, Masahiko; Shirako, Yuichi; Niwa, Ken; Hasegawa, Masashi; Akaogi, Masaki; Kojitani, Hiroshi; Ikenaga, Eiji; Muro, Takayuki

2018-04-01

The valence-band electronic structures of high-pressure-phase PdF2-type (HP-PdF2-type) platinum-group metal dioxides MO2 (M = Ru, Rh, Ir, and Pt) were studied by synchrotron radiation photoelectron spectroscopy and first-principles calculations. The obtained photoelectron spectra for HP-PdF2-type RuO2, RhO2, and IrO2 agree well with the calculated valence-band densities of states (DOSs) for these compounds, indicating their metallic properties, whereas the DOS of HP-PdF2-type PtO2 (calculated in the presence and absence of spin-orbit interactions) predicts that this material may be metallic or semimetallic, which is inconsistent with the electric conductivity reported to date and the charging effect observed in current photoelectron measurements. Compared with the calculated results, the valence-band spectrum of PtO2 appears to have shifted toward the high-binding-energy side and reveals a gradual intensity decrease toward the Fermi energy EF, implying a semiconductor-like electronic structure. Spin-dependent calculations predict a ferromagnetic ground state with a magnetization of 0.475 μB per formula unit for HP-PdF2-type RhO2.

Valence-state reflectometry of complex oxide heterointerfaces

DOE PAGES

Hamann-Borrero, Jorge E.; Macke, Sebastian; Choi, Woo Seok; ...

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 LaCoO 3 film on NdGaO 3 reveals a pronounced valence-state reconstruction from Co 3+ in the bulk to Co 2+ at the surface, with an areal density close tomore » 0.5 Co 2+ ions per unit cell. An identical film capped with polar (001) LaAlO 3 maintains the Co 3+ 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 CoO 2 layer at its LaO-terminated polar surface.« less

Simultaneous First-Order Valence and Oxygen Vacancy Order/Disorder Transitions in (Pr 0.85 Y 0.15 ) 0.7 Ca 0.3 CoO 3-δ via Analytical Transmission Electron Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulec, Ahmet; Phelan, Daniel; Leighton, Chris

Perovskite cobaltites have been studied for years as some of the few solids to exhibit thermally driven spin-state crossovers. The unanticipated first-order spin and electronic transitions recently discovered in Pr-based cobaltites are notably different from these conventional crossovers, and are understood in terms of a unique valence transition. In essence, the Pr valence is thought to spontaneously shift from 3+ toward 4+ on cooling, driving subsequent transitions in Co valence and electronic/magnetic properties. Here, we apply temperature-dependent transmission electron microscopy and spectroscopy to study this phenomenon, for the first time with atomic spatial resolution, in the prototypical (Pr 0.85Y 0.15)(0.70)more » Ca 0.30CoO 3-δ. In addition to the direct spectroscopic observation of charge transfer between Pr and Co at the 165 K transition (on both the Pr and O edges), we also find a simultaneous order/disorder transition associated with O vacancies. Remarkably, the first-order valence change drives a transition between ordered and random O vacancies, at constant O vacancy density, demonstrating reversible crystallization of such vacancies even at cryogenic temperatures.« less

Chunking Strategy as a Tool for Teaching Electron Configuration

ERIC Educational Resources Information Center

Adhikary, Chandan; Sana, Sibananda; Chattopadhyay, K. N.

2015-01-01

Chunk-based strategy and mnemonics have been developed to write ground state electron configurations of elements, which is a routine exercise for the higher secondary (pre-university) level general chemistry students. To assimilate a better understanding of the nature of chemical reactions, an adequate knowledge of the periodic table of elements…

Chemical Bonding: The Orthogonal Valence-Bond View

PubMed Central

Sax, Alexander F.

2015-01-01

Chemical bonding is the stabilization of a molecular system by charge- and spin-reorganization processes in chemical reactions. These processes are said to be local, because the number of atoms involved is very small. With multi-configurational self-consistent field (MCSCF) wave functions, these processes can be calculated, but the local information is hidden by the delocalized molecular orbitals (MO) used to construct the wave functions. The transformation of such wave functions into valence bond (VB) wave functions, which are based on localized orbitals, reveals the hidden information; this transformation is called a VB reading of MCSCF wave functions. The two-electron VB wave functions describing the Lewis electron pair that connects two atoms are frequently called covalent or neutral, suggesting that these wave functions describe an electronic situation where two electrons are never located at the same atom; such electronic situations and the wave functions describing them are called ionic. When the distance between two atoms decreases, however, every covalent VB wave function composed of non-orthogonal atomic orbitals changes its character from neutral to ionic. However, this change in the character of conventional VB wave functions is hidden by its mathematical form. Orthogonal VB wave functions composed of orthonormalized orbitals never change their character. When localized fragment orbitals are used instead of atomic orbitals, one can decide which local information is revealed and which remains hidden. In this paper, we analyze four chemical reactions by transforming the MCSCF wave functions into orthogonal VB wave functions; we show how the reactions are influenced by changing the atoms involved or by changing their local symmetry. Using orthogonal instead of non-orthogonal orbitals is not just a technical issue; it also changes the interpretation, revealing the properties of wave functions that remain otherwise undetected. PMID:25906476

High-Energy Electron Confinement in a Magnetic Cusp Configuration

NASA Astrophysics Data System (ADS)

Park, Jaeyoung; Krall, Nicholas A.; Sieck, Paul E.; Offermann, Dustin T.; Skillicorn, Michael; Sanchez, Andrew; Davis, Kevin; Alderson, Eric; Lapenta, Giovanni

2015-04-01

We report experimental results validating the concept that plasma confinement is enhanced in a magnetic cusp configuration when β (plasma pressure/magnetic field pressure) is of order unity. This enhancement is required for a fusion power reactor based on cusp confinement to be feasible. The magnetic cusp configuration possesses a critical advantage: the plasma is stable to large scale perturbations. However, early work indicated that plasma loss rates in a reactor based on a cusp configuration were too large for net power production. Grad and others theorized that at high β a sharp boundary would form between the plasma and the magnetic field, leading to substantially smaller loss rates. While not able to confirm the details of Grad's work, the current experiment does validate, for the first time, the conjecture that confinement is substantially improved at high β . This represents critical progress toward an understanding of the plasma dynamics in a high-β cusp system. We hope that these results will stimulate a renewed interest in the cusp configuration as a fusion confinement candidate. In addition, the enhanced high-energy electron confinement resolves a key impediment to progress of the Polywell fusion concept, which combines a high-β cusp configuration with electrostatic fusion for a compact, power-producing nuclear fusion reactor.

Oscillator strengths of some Ba lines - A treatment including core-valence correlation and relativistic effects

NASA Technical Reports Server (NTRS)

Bauschlicher, C. W., Jr.; Jaffe, R. L.; Langhoff, S. R.; Partridge, H.; Mascarello, F. G.

1985-01-01

Theoretical calculations of selected excitation energies and oscillator strengths for Ba are presented that overcome the difficulties of previous theoretical treatments. A relativistic effective-core potential treatment is used to account for the relativistic core contraction, but the outermost ten electrons are treated explicitly. Core-valence correlation can be included in this procedure in a rigorous and systematic way through a configuration-interaction calculation. Insight is gained into the importance of relativistic effects by repeating many of the calculations using an all-electron nonrelativistic treatment employing an extended Slater basis set. It is found that the intensity of the intercombination line 3P1-1S0 is accurately determined by accounting for the deviation from LS coupling through spin-orbit mixing with the 1P1 state, and that deviations from the Lande interval rule provide an accurate measure of the degree of mixing.

Reactive Force Fields via Explicit Valency

NASA Astrophysics Data System (ADS)

Kale, Seyit

Computational simulations are invaluable in elucidating the dynamics of biological macromolecules. Unfortunately, reactions present a fundamental challenge. Calculations based on quantum mechanics can predict bond formation and rupture; however they suffer from severe length- and time-limitations. At the other extreme, classical approaches provide orders of magnitude faster simulations; however they regard chemical bonds as immutable entities. A few exceptions exist, but these are not always trivial to adopt for routine use. We bridge this gap by providing a novel, pseudo-classical approach, based on explicit valency. We unpack molecules into valence electron pairs and atomic cores. Particles bear ionic charges and interact via pairwise-only potentials. The potentials are informed of quantum effects in the short-range and obey dissociation limits in the long-range. They are trained against a small set of isolated species, including geometries and thermodynamics of small hydrides and of dimers formed by them. The resulting force field captures the essentials of reactivity, polarizability and flexibility in a simple, seamless setting. We call this model LEWIS, after the chemical theory that inspired the use of valence pairs. Following the introduction in Chapter 1, we initially focus on the properties of water. Chapter 2 considers gas phase clusters. To transition to the liquid phase, Chapter 3 describes a novel pairwise long-range compensation that performs comparably to infinite lattice summations. The approach is suited to ionic solutions in general. In Chapters 4 and 5, LEWIS is shown to correctly predict the dipolar and quadrupolar response in bulk liquid, and can accommodate proton transfers in both acid and base. Efficiency permits the study of proton defects at dilutions not accessible to experiment or quantum mechanics. Chapter 6 discusses explicit valency approaches in other hydrides, forming the basis of a reactive organic force field. Examples of simple

Valence evaluation with approaching or withdrawing cues: directly testing valence-arousal conflict theory.

PubMed

Wang, Yan Mei; Li, Ting; Li, Lin

2017-07-19

The valence-arousal conflict theory assumes that both valence and arousal will trigger approaching or withdrawing tendencies. It also predicts that the speed of processing emotional stimuli will depend on whether valence and arousal trigger conflicting or congruent motivational tendencies. However, most previous studies have provided evidence of the interaction between valence and arousal only, and have not provided direct proof of the interactive links between valence, arousal and motivational tendencies. The present study provides direct evidence for the relationship between approach-withdrawal tendencies and the valence-arousal conflict. In an empirical test, participants were instructed to judge the valence of emotional words after visual-spatial cues that appeared to be either approaching or withdrawing from participants. A three-way interaction (valence, arousal, and approach-withdrawal tendency) was observed such that the response time was shorter if participants responded to a negative high-arousal stimulus after a withdrawing cue, or to a positive low-arousal stimulus after an approaching cue. These findings suggest that the approach-withdrawal tendency indeed plays a crucial role in valence-arousal conflict, and that the effect depends on the congruency of valence, arousal and tendency at an early stage of processing.

Use of valence band Auger electron spectroscopy to study thin film growth: oxide and diamond-like carbon films

NASA Astrophysics Data System (ADS)

Steffen, H. J.

1994-12-01

It is demonstrated how Auger line shape analysis with factor analysis (FA), least-squares fitting and even simple peak height measurements may provide detailed information about the composition, different chemical states and also defect concentration or crystal order. Advantage is taken of the capability of Auger electron spectroscopy to give valence band structure information with high surface sensitivity and the special aspect of FA to identify and discriminate quantitatively unknown chemical species. Valence band spectra obtained from Ni, Fe, Cr and NiFe40Cr20 during oxygen exposure at room temperature reveal the oxidation process in the initial stage of the thin layer formation. Furthermore, the carbon chemical states that were formed during low energy C(+) and Ne(+) ion irradiation of graphite are delineated and the evolution of an amorphous network with sp3 bonds is disclosed. The analysis represents a unique method to quantify the fraction of sp3-hybridized carbon in diamond-like materials.

On Valence-Band Splitting in Layered MoS2.

PubMed

Zhang, Youwei; Li, Hui; Wang, Haomin; Liu, Ran; Zhang, Shi-Li; Qiu, Zhi-Jun

2015-08-25

As a representative two-dimensional semiconducting transition-metal dichalcogenide (TMD), the electronic structure in layered MoS2 is a collective result of quantum confinement, interlayer interaction, and crystal symmetry. A prominent energy splitting in the valence band gives rise to many intriguing electronic, optical, and magnetic phenomena. Despite numerous studies, an experimental determination of valence-band splitting in few-layer MoS2 is still lacking. Here, we show how the valence-band maximum (VBM) splits for one to five layers of MoS2. Interlayer coupling is found to contribute significantly to phonon energy but weakly to VBM splitting in bilayers, due to a small interlayer hopping energy for holes. Hence, spin-orbit coupling is still predominant in the splitting. A temperature-independent VBM splitting, known for single-layer MoS2, is, thus, observed for bilayers. However, a Bose-Einstein type of temperature dependence of VBM splitting prevails in three to five layers of MoS2. In such few-layer MoS2, interlayer coupling is enhanced with a reduced interlayer distance, but thermal expansion upon temperature increase tends to decouple adjacent layers and therefore decreases the splitting energy. Our findings that shed light on the distinctive behaviors about VBM splitting in layered MoS2 may apply to other hexagonal TMDs as well. They will also be helpful in extending our understanding of the TMD electronic structure for potential applications in electronics and optoelectronics.

Lie algebraic approach to valence bond theory of π-electron systems: a preliminary study of excited states

NASA Astrophysics Data System (ADS)

Paldus, J.; Li, X.

1992-10-01

Following a brief outline of various developments and exploitations of the unitary group approach (UGA), and its extension referred to as Clifford algebra UGA (CAUGA), in molecular electronic structure calculations, we present a summary of a recently introduced implementation of CAUGA for the valence bond (VB) method based on the Pariser-Parr-Pople (PPP)-type Hamiltonian. The existing applications of this PPP-VB approach have been limited to groundstates of various π-electron systems or, at any rate, to the lowest states of a given multiplicity. In this paper the method is applied to the low-lying excited states of several archetypal models, namely cyclobutadiene and benzene, representing antiaromatic and aromatic systems, hexatriene, representing linear polyenic systems and, finally, naphthalene, representing polyacenes.

A complete active space valence bond method with nonorthogonal orbitals

NASA Astrophysics Data System (ADS)

Hirao, Kimihiko; Nakano, Haruyuki; Nakayama, Kenichi

1997-12-01

A complete active space self-consistent field (SCF) wave function is transformed into a valence bond type representation built from nonorthogonal orbitals, each strongly localized on a single atom. Nonorthogonal complete active space SCF orbitals are constructed by Ruedenberg's projected localization procedure so that they have maximal overlaps with the corresponding minimum basis set of atomic orbitals of the free-atoms. The valence bond structures which are composed of such nonorthogonal quasiatomic orbitals constitute the wave function closest to the concept of the oldest and most simple valence bond method. The method is applied to benzene, butadiene, hydrogen, and methane molecules and compared to the previously proposed complete active space valence bond approach with orthogonal orbitals. The results demonstrate the validity of the method as a powerful tool for describing the electronic structure of various molecules.

Low-lying electronic states of Li 2+ and Li 2-

NASA Astrophysics Data System (ADS)

Konowalow, Daniel D.; Fish, James L.

1984-02-01

Potential curves for the eight lowest lying electronic states of Li2+ and the two lowest-lying states of Li2- are obtained by valence configuration calculations which-utilize an effective core potential. The calculated ionization potential of the ground state of Li2 is found to b. 5.16 eV and its electron affinity is 0.429 eV. Both values are in excellent agreement with recent experimental values and with value deduced from other high quality ab initio quantum mechanical treatments. When our potential curve for the Li2+(12Σg+ state, is corrected for the core-valence correlation error we obtain spectroscopic constants which agree nicely with the experimental values of Bernheim, Gold and Tipton (BGT). For example, we findDe = 10460 ± 140 cm-1 while BGT reportDe = 10469 ± 6 cm-1.

Pressure-induced valence change and moderate heavy fermion state in Eu-compounds

NASA Astrophysics Data System (ADS)

Honda, Fuminori; Okauchi, Keigo; Sato, Yoshiki; Nakamura, Ai; Akamine, Hiromu; Ashitomi, Yosuke; Hedo, Masato; Nakama, Takao; Takeuchi, Tetsuya; Valenta, Jaroslav; Prchal, Jiri; Sechovský, Vladimir; Aoki, Dai; Ōnuki, Yoshichika

2018-05-01

A pressure-induced valence transition has attracted much attention in Eu-compounds. Among them, EuRh2Si2, EuNi2Ge2, and EuCo2Ge2 reveal the valence transition around 1, 2, and 3 GPa, respectively. We have succeeded in growing single crystals of EuT2X2 (T: transition metal, X: Si, Ge) and studied electronic properties under pressure. EuRh2Si2 indicates a first-order valence transition between 1 and 2 GPa, with a large and prominent hysteresis in the electrical resistivity. At higher pressures, the first-order valence transition changes to a cross-over regime with an intermediate valence state. Tuning of the valence state with pressure is reflected in a drastic change of the temperature dependence of the electrical resistivity in EuRh2Si2 single crystals. Effect of pressure on the valence states on EuRh2Si2, EuIr2Si2, EuNi2Ge2, and EuCo2Ge2, as well as an isostructural related compound EuGa4, are reviewed.

Core-core and core-valence correlation energy atomic and molecular benchmarks for Li through Ar

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ranasinghe, Duminda S.; Frisch, Michael J.; Petersson, George A., E-mail: gpetersson@wesleyan.edu

2015-12-07

We have established benchmark core-core, core-valence, and valence-valence absolute coupled-cluster single double (triple) correlation energies (±0.1%) for 210 species covering the first- and second-rows of the periodic table. These species provide 194 energy differences (±0.03 mE{sub h}) including ionization potentials, electron affinities, and total atomization energies. These results can be used for calibration of less expensive methodologies for practical routine determination of core-core and core-valence correlation energies.

Configurational forces in electronic structure calculations using Kohn-Sham density functional theory

NASA Astrophysics Data System (ADS)

Motamarri, Phani; Gavini, Vikram

2018-04-01

We derive the expressions for configurational forces in Kohn-Sham density functional theory, which correspond to the generalized variational force computed as the derivative of the Kohn-Sham energy functional with respect to the position of a material point x . These configurational forces that result from the inner variations of the Kohn-Sham energy functional provide a unified framework to compute atomic forces as well as stress tensor for geometry optimization. Importantly, owing to the variational nature of the formulation, these configurational forces inherently account for the Pulay corrections. The formulation presented in this work treats both pseudopotential and all-electron calculations in a single framework, and employs a local variational real-space formulation of Kohn-Sham density functional theory (DFT) expressed in terms of the nonorthogonal wave functions that is amenable to reduced-order scaling techniques. We demonstrate the accuracy and performance of the proposed configurational force approach on benchmark all-electron and pseudopotential calculations conducted using higher-order finite-element discretization. To this end, we examine the rates of convergence of the finite-element discretization in the computed forces and stresses for various materials systems, and, further, verify the accuracy from finite differencing the energy. Wherever applicable, we also compare the forces and stresses with those obtained from Kohn-Sham DFT calculations employing plane-wave basis (pseudopotential calculations) and Gaussian basis (all-electron calculations). Finally, we verify the accuracy of the forces on large materials systems involving a metallic aluminum nanocluster containing 666 atoms and an alkane chain containing 902 atoms, where the Kohn-Sham electronic ground state is computed using a reduced-order scaling subspace projection technique [P. Motamarri and V. Gavini, Phys. Rev. B 90, 115127 (2014), 10.1103/PhysRevB.90.115127].

High-nuclearity mixed-valence clusters and mixed-valence chains: general approach to the calculation of the energy levels and bulk magnetic properties.

PubMed

Clemente-Juan, J M; Borrás-Almenar, J J; Coronado, E; Palii, A V; Tsukerblat, B S

2009-05-18

A general approach to the problem of electron delocalization in the high-nuclearity mixed-valence (MV) clusters containing an arbitrary number of localized spins and itinerant electrons is developed. Along with the double exchange, we consider the isotropic magnetic exchange between the localized electrons as well as the Coulomb intercenter repulsion. As distinguished from the previous approaches dealing with the MV systems in which itinerant electrons are delocalized over all constituent metal sites, here, we consider a more common case of systems exhibiting partial delocalization and containing several delocalized domains. Taking full advantage of the powerful angular momentum technique, we were able to derive closed form analytical expressions for the matrix elements of the full Hamiltonian. These expressions provide an efficient tool for treating complex mixed-valence systems, because they contain only products of 6j-symbols (that appear while treating the delocalized parts) and 9j-symbols (exchange interactions in localized parts) and do not contain high-order recoupling coefficients and 3j-symbols that essentially constrained all previous theories of mixed valency. The approach developed here is accompanied by an efficient computational procedure that allows us to calculate the bulk thermodynamic properties (magnetic susceptibility, magnetization, and magnetic specific heat) of high-nuclearity MV clusters. Finally, this approach has been used to discuss the magnetic properties of the octanuclear MV cluster [Fe(8)(mu(4)-O)(4)(4-Cl-pz)(12)Cl(4)](-) and the diphthalocyanine chains [YPc(2)].CH(2)Cl(2) and [ScPc(2)].CH(2)Cl(2) composed of MV dimers interacting through the magnetic exchange and Coulomb repulsion.

Electron doped layered nickelates: Spanning the phase diagram of the cuprates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Botana, Antia S.; Pardo, Victor; Norman, Michael R.

2017-07-01

Pr4Ni3O8 is an overdoped analog of hole-doped layered cuprates. Here we show via ab initio calculations that Ce-doped Pr4Ni3O8 (Pr3CeNi3O8) has the same electronic structure as the antiferromagnetic insulating phase of parent cuprates.We find that substantial Ce doping should be thermodynamically stable and that other 4+ cations would yield a similar antiferromagnetic insulating state, arguing this configuration is robust for layered nickelates of low-enough valence. The analogies with cuprates at different d fillings suggest that intermediate Ce-doping concentrations near 1/8 should be an appropriate place to search for superconductivity in these low-valence Ni oxides.

Theory of Valence Transition

NASA Astrophysics Data System (ADS)

Misawa, S.; Takano, F.

1981-01-01

The valence transition phenomena occurring in rare-earth compounds are studied by using the periodic Anderson model with the electron-phonon coupling. This electron-phonon interaction G is treated in the Hartree-Fock approximation. The Coulomb repulsion U between f-electrons on the same site is taken to be ∞, and the decoupling method of Roth is used for the higher order Green function considering the mixing interaction to be small. We put the condition that the total number of electrons is a constant, and calculate the numbers of f- and d-electrons as functions of the original energy of f-electron by using the Green functions. The first order transition is shown to occur if G ≳ (1/2)W, where W is the width of the original d-band. The energy of f-electron at which the insulator and the metallic phase have the same ground state energy is calculated asɛc ≃ (1/2)(G-(1/2)W) + (2V^2/W) log |(G-W/2)/(G+W/2)|- (V^2/8W) log | (G-W/2)(G-(3/2)W) |. The magnetic susceptibilities of both phases are also calculated, but the result is not good, showing the decoupling method used here is not appropriate for the calculation of magnetic properties.

The Consequences of Spin-Orbit Coupling on the 5d3 Electronic Configuration

NASA Astrophysics Data System (ADS)

Christianson, A. D.

The impact of spin-orbit coupling on collective properties of matter is of considerable interest. The most intensively investigated materials in this regard are Iridium-based transition metal oxides which exhibit a host of interesting ground states that originate from a 5d5 Jeff = 1/2 electronic configuration. Moving beyond the Jeff = 1/2 paradigm to other electronic configurations where spin-orbit coupling plays a prominent role is a key objective of ongoing research. Here we focus on several Osmium-based transition metal oxides such as NaOsO3, Cd2Os2O7, Ca3LiOsO6, Sr2ScOsO6, Ba2YOsO6, and Sr2FeOsO6, which are nominally in the 5d3 electronic configuration. Within the LS coupling picture and a strong octahedral crystal field, the 5d3 configuration is expected to be an orbital singlet and spin-orbit effects should be minimal. Nevertheless, our neutron and x-ray scattering investigations of these materials as well as investigations by other groups show dramatic effects of spin-orbit coupling including reduced moment magnetic order, enhanced spin-phonon coupling, and large spin gaps. In particular, the anisotropy induced by spin-orbit coupling tips the balance of the frustrated interactions and drives the selection of particular magnetic ground states. To understand the mechanism driving the spin-orbit effects, we have explored the ground state t2g manifold with resonant inelastic x-ray scattering and observe a spectrum inexplicable by an LS coupling picture. On the other hand, an intermediate coupling approach reveals that the ground state wave function is a J =3/2 configuration which answers the question of how strong spin-orbit coupling effects arise in 5d3 systems.

Density matrix-based time-dependent configuration interaction approach to ultrafast spin-flip dynamics

NASA Astrophysics Data System (ADS)

Wang, Huihui; Bokarev, Sergey I.; Aziz, Saadullah G.; Kühn, Oliver

2017-08-01

Recent developments in attosecond spectroscopy yield access to the correlated motion of electrons on their intrinsic timescales. Spin-flip dynamics is usually considered in the context of valence electronic states, where spin-orbit coupling is weak and processes related to the electron spin are usually driven by nuclear motion. However, for core-excited states, where the core-hole has a nonzero angular momentum, spin-orbit coupling is strong enough to drive spin-flips on a much shorter timescale. Using density matrix-based time-dependent restricted active space configuration interaction including spin-orbit coupling, we address an unprecedentedly short spin-crossover for the example of L-edge (2p→3d) excited states of a prototypical Fe(II) complex. This process occurs on a timescale, which is faster than that of Auger decay (∼4 fs) treated here explicitly. Modest variations of carrier frequency and pulse duration can lead to substantial changes in the spin-state yield, suggesting its control by soft X-ray light.

Direct Electron Impact Excitation of Rydberg-Valence States of Molecular Nitrogen

NASA Astrophysics Data System (ADS)

Malone, C. P.; Johnson, P. V.; Liu, X.; Ajdari, B.; Muleady, S.; Kanik, I.; Khakoo, M. A.

2012-12-01

Collisions between electrons and neutral N2 molecules result in emissions that provide an important diagnostic probe for understanding the ionospheric energy balance and the effects of space weather in upper atmospheres. Also, transitions to singlet ungerade states cause N2 to be a strong absorber of solar radiation in the EUV spectral range where many ro-vibrational levels of these Rydberg-valence (RV) states are predissociative. Thus, their respective excitation and emission cross sections are important parameters for understanding the [N]/[N2] ratio in the thermosphere of nitrogen dominated atmospheres. The following work provides improved constraints on absolute and relative excitation cross sections of numerous RV states of N2, enabling more physically accurate atmospheric modeling. Here, we present recent integral cross sections (ICSs) for electron impact excitation of RV states of N2 [6], which were based on the differential cross sections (DCSs) derived from electron energy-loss (EEL) spectra of [5]. This work resulted in electronic excitation cross sections over the following measured vibrational levels: b 1Πu (v‧=0-14), c3 1Πu (v‧=0-3), o3 1Πu (v‧=0-3), b‧ 1Σu+ (v‧=0-10), c‧4 1Σu+ (v‧=0-3), G 3Πu (v‧=0-3), and F 3Πu (v‧=0-3). We further adjusted the cross sections of the RV states by extending the vibronic contributions to unmeasured v‧-levels via the relative excitation probabilities (REPs) as discussed in [6]. This resulted in REP-scaled ICSs over the following vibrational levels for the singlet ungerade states: b(0-19), c3(0-4), o3(0-4), b‧(0-16), and c‧4(0-8). Comparison of the ICSs of [6] with available EEL based measurements, theoretical calculations, and emission based work generally shows good agreement within error estimations, except with the recent reevaluation provided by [1]. Further, we have extended these results, using the recent EEL data of [3], to include the unfolding of better resolved features above ~13

Core-valence stockholder AIM analysis and its connection to nonadiabatic effects in small molecules.

PubMed

Amaral, Paulo H R; Mohallem, José R

2017-05-21

A previous theory of separation of motions of core and valence fractions of electrons in a molecule [J. R. Mohallem et al., Chem. Phys. Lett. 501, 575 (2011)] is invoked as basis for the useful concept of Atoms-in-Molecules (AIM) in the stockholder scheme. The output is a new tool for the analysis of the chemical bond that identifies core and valence electron density fractions (core-valence stockholder AIM (CVSAIM)). One-electron effective potentials for each atom are developed, which allow the identification of the parts of the AIM which move along with the nuclei (cores). This procedure results in a general method for obtaining effective masses that yields accurate non-adiabatic corrections to vibrational energies, necessary to attain cm -1 accuracy in molecular spectroscopy. The clear-cut determination of the core masses is exemplified for either homonuclear (H 2 + , H 2 ) or heteronuclear (HeH + , LiH) molecules. The connection of CVSAIM with independent physically meaningful quantities can resume the question of whether they are observable or not.

Core-valence stockholder AIM analysis and its connection to nonadiabatic effects in small molecules

PubMed Central

Amaral, Paulo H. R.; Mohallem, José R.

2017-01-01

A previous theory of separation of motions of core and valence fractions of electrons in a molecule [J. R. Mohallem et al., Chem. Phys. Lett. 501, 575 (2011)] is invoked as basis for the useful concept of Atoms-in-Molecules (AIM) in the stockholder scheme. The output is a new tool for the analysis of the chemical bond that identifies core and valence electron density fractions (core-valence stockholder AIM (CVSAIM)). One-electron effective potentials for each atom are developed, which allow the identification of the parts of the AIM which move along with the nuclei (cores). This procedure results in a general method for obtaining effective masses that yields accurate non-adiabatic corrections to vibrational energies, necessary to attain cm−1 accuracy in molecular spectroscopy. The clear-cut determination of the core masses is exemplified for either homonuclear (H2+, H2) or heteronuclear (HeH+, LiH) molecules. The connection of CVSAIM with independent physically meaningful quantities can resume the question of whether they are observable or not. PMID:28527456

Resolution-of-identity stochastic time-dependent configuration interaction for dissipative electron dynamics in strong fields.

PubMed

Klinkusch, Stefan; Tremblay, Jean Christophe

2016-05-14

In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electron ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.

A configurable electronics system for the ESS-Bilbao beam position monitors

NASA Astrophysics Data System (ADS)

Muguira, L.; Belver, D.; Etxebarria, V.; Varnasseri, S.; Arredondo, I.; del Campo, M.; Echevarria, P.; Garmendia, N.; Feuchtwanger, J.; Jugo, J.; Portilla, J.

2013-09-01

A versatile and configurable system has been developed in order to monitorize the beam position and to meet all the requirements of the future ESS-Bilbao Linac. At the same time the design has been conceived to be open and configurable so that it could eventually be used in different kinds of accelerators, independent of the charged particle, with minimal change. The design of the Beam Position Monitors (BPMs) system includes a test bench both for button-type pick-ups (PU) and striplines (SL), the electronic units and the control system. The electronic units consist of two main parts. The first part is an Analog Front-End (AFE) unit where the RF signals are filtered, conditioned and converted to base-band. The second part is a Digital Front-End (DFE) unit which is based on an FPGA board where the base-band signals are sampled in order to calculate the beam position, the amplitude and the phase. To manage the system a Multipurpose Controller (MC) developed at ESSB has been used. It includes the FPGA management, the EPICS integration and Archiver Instances. A description of the system and a comparison between the performance of both PU and SL BPM designs measured with this electronics system are fully described and discussed.

Thermal and electron transport studies on the valence fluctuating compound YbNiAl4

NASA Astrophysics Data System (ADS)

Falkowski, M.; Kowalczyk, A.

2018-05-01

We report the thermoelectric power S and thermal conductivity κ measurements on the valence fluctuating compound YbNiAl4, furthermore taking into account the impact of the applied magnetic field. We discuss our new results with revisiting the magnetic [χ(T)], transport [ρ(T)], and thermodynamic [Cp(T)] properties in order to better understand the phenomenon of thermal and electron transport in this compound. The field dependence of the magnetoresistivity data is also given. The temperature dependence of thermoelectric power S(T) was found to exhibit a similar behaviour as expected for Yb-based compounds with divalent or nearly divalent Yb ions. In addition, the values of total thermal conductivity as a function of temperature κ(T) of YbNiAl4 are fairly low compared to those of pure metals which may be linked to the fact that the conduction band is perturbed by strong hybridization. A deeper analysis of the specific heat revealed the low-T anomaly of the ratio Cp(T)/T3, most likely associated with the localized low-frequency oscillators in this alloy. In addition, the Kadowaki-Woods ratio and the Wilson ratio are discussed with respect to the electronic correlations in YbNiAl4.

Module Configuration

DOEpatents

Oweis, Salah; D'Ussel, Louis; Chagnon, Guy; Zuhowski, Michael; Sack, Tim; Laucournet, Gaullume; Jackson, Edward J.

2002-06-04

A stand alone battery module including: (a) a mechanical configuration; (b) a thermal management configuration; (c) an electrical connection configuration; and (d) an electronics configuration. Such a module is fully interchangeable in a battery pack assembly, mechanically, from the thermal management point of view, and electrically. With the same hardware, the module can accommodate different cell sizes and, therefore, can easily have different capacities. The module structure is designed to accommodate the electronics monitoring, protection, and printed wiring assembly boards (PWAs), as well as to allow airflow through the module. A plurality of modules may easily be connected together to form a battery pack. The parts of the module are designed to facilitate their manufacture and assembly.

A theoretical study of the dissociative recombination of SH+ with electrons through the 2Π states of SH.

PubMed

Kashinski, D O; Talbi, D; Hickman, A P; Di Nallo, O E; Colboc, F; Chakrabarti, K; Schneider, I F; Mezei, J Zs

2017-05-28

A quantitative theoretical study of the dissociative recombination of SH + with electrons has been carried out. Multireference, configuration interaction calculations were used to determine accurate potential energy curves for SH + and SH. The block diagonalization method was used to disentangle strongly interacting SH valence and Rydberg states and to construct a diabatic Hamiltonian whose diagonal matrix elements provide the diabatic potential energy curves. The off-diagonal elements are related to the electronic valence-Rydberg couplings. Cross sections and rate coefficients for the dissociative recombination reaction were calculated with a stepwise version of the multichannel quantum defect theory, using the molecular data provided by the block diagonalization method. The calculated rates are compared with the most recent measurements performed on the ion Test Storage Ring (TSR) in Heidelberg, Germany.

Electronic, magnetic, transport, and thermal properties of single-crystalline UF e2A l10

NASA Astrophysics Data System (ADS)

Troć, R.; Samsel-Czekała, M.; Talik, E.; Wawryk, R.; Gajek, Z.; Pasturel, M.

2015-09-01

The valence and core-level x-ray photoemission spectra (XPS), performed on an UF e2A l10 single crystal, were measured using the Al Kα radiation. The results of valence XPS show practically two separate regions of spectral intensity, one just at the Fermi level (EF) and the other one being a wide content with its maximum at about 0.8 eV below EF. These give rise to two electronic configurations of the 5 f states in the studied aluminide, itinerant and localized ones, i.e., their dual character. In such a situation the corresponding valence spectra, calculated within the local density approximation (LDA), well explain the former configuration, being responsible for a metallic behavior of the studied compound. Moreover, this behavior is confirmed clearly also by our results of magnetotransport measurements. On the other hand, the obtained magnetic susceptibility, specific heat, electrical resistivity, and thermoelectric power data support very well the local character of the 5 f2 -electron configuration of the U4 + ion in UF e2A l10 having the orthorhombic and cage-type crystal structure. Based on that configuration, the magnetic and thermal characteristics of the compound were modeled by the effective crystal field (CF) potential in the intermediate coupling scheme using initial parameters obtained by the angular overlap model (AOM). The obtained final CF parameters yielded the CF level scheme, composed of only singlets, proper for orthorhombic symmetry. Such a set of singlets reproduces in a satisfactory way both the strongly anisotropic temperature variations of the magnetic susceptibility, measured along the three main crystallographic directions, as well as the Schottky anomaly, evaluated using specific heat results of isomorphic ThF e2A l10 as a phonon reference. Also, the strongly anisotropic behavior of the Seebeck coefficient and its low temperature maxima observed for the compound studied here have been explained roughly by the CF effect.

Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.

2013-05-30

Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexesmore » in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.« less

Density effects on electronic configurations in dense plasmas

NASA Astrophysics Data System (ADS)

Faussurier, Gérald; Blancard, Christophe

2018-02-01

We present a quantum mechanical model to describe the density effects on electronic configurations inside a plasma environment. Two different approaches are given by starting from a quantum average-atom model. Illustrations are shown for an aluminum plasma in local thermodynamic equilibrium at solid density and at a temperature of 100 eV and in the thermodynamic conditions of a recent experiment designed to characterize the effects of the ionization potential depression treatment. Our approach compares well with experiment and is consistent in that case with the approach of Stewart and Pyatt to describe the ionization potential depression rather than with the method of Ecker and Kröll.

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…

Correlation of intercalation potential with d-electron configurations for cathode compounds of lithium-ion batteries.

PubMed

Chen, Zhenlian; Zhang, Caixia; Zhang, Zhiyong; Li, Jun

2014-07-14

The d-electron localization is widely recognized as important to transport properties of transition metal compounds, but its role in the energy conversion of intercalation reactions of cathode compounds is still not fully explored. In this work, the correlation of intercalation potential with electron affinity, a key energy term controlling electron intercalation, then with d-electron configuration, is investigated. Firstly, we find that the change of the intercalation potential with respect to the transition metal cations within the same structure class is correlated in an approximately mirror relationship with the electron affinity, based on first-principles calculations on three typical categories of cathode compounds including layered oxides and polyoxyanions Then, by using a new model Hamiltonian based on the crystal-field theory, we reveal that the evolution is governed by the combination of the crystal-field splitting and the on-site d-d exchange interactions. Further, we show that the charge order in solid-solution composites and the compatibility of multi-electron redox steps could be inferred from the energy terms with the d-electron configuration alternations. These findings may be applied to rationally designing new chemistry for the lithium-ion batteries and other metal-ion batteries.

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

PubMed

Li, Tsung-Lung; Lu, Wen-Cai

2015-10-05

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. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Investigations of the valence-shell excitations of molecular ethane by high-energy electron scattering

NASA Astrophysics Data System (ADS)

Xu, Wei-Qing; Xu, Long-Quan; Qi, De-Guang; Chen, Tao; Liu, Ya-Wei; Zhu, Lin-Fan

2018-04-01

The differential cross sections and generalized oscillator strengths for the low-lying excitations of the valence-shell 1eg orbital electron in ethane have been measured for the first time at a high incident electron energy of 1500 eV and a scattering angular range of 1.5°-10°. A weak feature, termed X here, with a band center of about 7.5 eV has been observed, which was also announced by the previous experimental and theoretical studies. The dynamic behaviors of the generalized oscillator strengths for the 3s (8.7 eV), 3s+3p (9.31 eV, 9.41 eV), and X (˜7.5 eV) transitions on the momentum transfer squared have been obtained. The integral cross sections of these transitions from their thresholds to 5000 eV have been obtained with the aid of the BE-scaling (B is the binding energy and E is the excitation energy) method. The optical oscillator strengths of the above transitions determined by extrapolating their generalized oscillator strengths to the limit of the squared momentum transfer K2 → 0 are in good agreement with the ones from the photoabsorption spectrum [J. W. Au et al., Chem. Phys. 173, 209 (1993)], which indicates that the present differential cross sections, generalized oscillator strengths, and integral cross sections can serve as benchmark data.

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.

Eu 2+ –Eu 3+ valence transition in double, Eu-, and Na-doped PbSe from transport, magnetic, and electronic structure studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wiendlocha, Bartlomiej; Kim, SunPhil; Lee, Yeseul

The Eu atoms in Pb 1-xEu xSe have long been assumed to be divalent. We show that p-type doping of this magnetic semiconductor alloy with Na can modify the effective Eu valence: a mixed, Eu 2+–Eu 3+ state appears in Pb 1-x-yEu xNa ySe at particular values of y. Magnetization, carrier concentration, resistivity, and thermopower of Pb 1-x-yEu xNa ySe are reported for a number of samples with different x and y. A pronounced increase in thermopower at a given carrier concentration was identified and attributed to the presence of enhanced ionized impurity scattering. A strong decrease in the holemore » concentration is observed in Pb1-yNaySe when Eu is added to the system, which we attribute to a Eu 2+–Eu 3+ self-ionization process. This is evidenced by magnetization measurements, which reveal a significant reduction of the magnetic moment of Pb 1-xEu xSe upon alloying with Na. Further, a deviation of magnetization from a purely paramagnetic state, described by a Brillouin function, identifies antiferromagnetic interactions between the nearest-neighbor Eu atoms: a value of J ex/k B = -0.35 K was found for the exchange coupling parameter. The conclusion of a Eu 2+–Eu 3+ self-ionization process being in effect is supported further by the electronic structure calculations, which show that an instability of the 4f 7 configuration of the Eu 2+ ion appears with Na doping. In conclusion, schematically, it was found that the Eu 4f levels form states near enough to the Fermi energy that hole doping can lower the Fermi energy and trigger a reconfiguration of a 4f electronic shell.« less

Eu 2+ –Eu 3+ valence transition in double, Eu-, and Na-doped PbSe from transport, magnetic, and electronic structure studies

DOE PAGES

Wiendlocha, Bartlomiej; Kim, SunPhil; Lee, Yeseul; ...

2017-03-27

The Eu atoms in Pb 1-xEu xSe have long been assumed to be divalent. We show that p-type doping of this magnetic semiconductor alloy with Na can modify the effective Eu valence: a mixed, Eu 2+–Eu 3+ state appears in Pb 1-x-yEu xNa ySe at particular values of y. Magnetization, carrier concentration, resistivity, and thermopower of Pb 1-x-yEu xNa ySe are reported for a number of samples with different x and y. A pronounced increase in thermopower at a given carrier concentration was identified and attributed to the presence of enhanced ionized impurity scattering. A strong decrease in the holemore » concentration is observed in Pb1-yNaySe when Eu is added to the system, which we attribute to a Eu 2+–Eu 3+ self-ionization process. This is evidenced by magnetization measurements, which reveal a significant reduction of the magnetic moment of Pb 1-xEu xSe upon alloying with Na. Further, a deviation of magnetization from a purely paramagnetic state, described by a Brillouin function, identifies antiferromagnetic interactions between the nearest-neighbor Eu atoms: a value of J ex/k B = -0.35 K was found for the exchange coupling parameter. The conclusion of a Eu 2+–Eu 3+ self-ionization process being in effect is supported further by the electronic structure calculations, which show that an instability of the 4f 7 configuration of the Eu 2+ ion appears with Na doping. In conclusion, schematically, it was found that the Eu 4f levels form states near enough to the Fermi energy that hole doping can lower the Fermi energy and trigger a reconfiguration of a 4f electronic shell.« less

Valence State Driven Site Preference in the Quaternary Compound Ca5MgAgGe5: An Electron-Deficient Phase with Optimized Bonding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ponou, Simeon; Lidin, Sven; Zhang, Yuemei

The quaternary phase Ca5Mg0.95Ag1.05(1)Ge5 (3) was synthesized by high-temperature solid-state techniques, and its crystal structure was determined by single-crystal diffraction methods in the orthorhombic space group Pnma – Wyckoff sequence c12 with a = 23.1481(4) Å, b = 4.4736(1) Å, c = 11.0128(2) Å, V = 1140.43(4) Å3, Z = 4. The crystal structure can be described as linear intergrowths of slabs cut from the CaGe (CrB-type) and the CaMGe (TiNiSi-type; M = Mg, Ag) structures. Hence, 3 is a hettotype of the hitherto missing n = 3 member of the structure series with the general formula R2+nT2X2+n, previously describedmore » with n = 1, 2, and 4. The member with n = 3 was predicted in the space group Cmcm – Wyckoff sequence f5c2. The experimental space group Pnma (in the nonstandard setting Pmcn) corresponds to a klassengleiche symmetry reduction of index two of the predicted space group Cmcm. This transition originates from the switching of one Ge and one Ag position in the TiNiSi-related slab, a process that triggers an uncoupling of each of the five 8f sites in Cmcm into two 4c sites in Pnma. The Mg/Ag site preference was investigated using VASP calculations and revealed a remarkable example of an intermetallic compound for which the electrostatic valency principle is a critical structure-directing force. The compound is deficient by one valence electron according to the Zintl concept, but LMTO electronic structure calculations indicate electronic stabilization and overall bonding optimization in the polyanionic network. Other stability factors beyond the Zintl concept that may account for the electronic stabilization are discussed.« less

Resolution-of-identity stochastic time-dependent configuration interaction for dissipative electron dynamics in strong fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klinkusch, Stefan; Tremblay, Jean Christophe

In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electronmore » ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.« less

Direct Observation of Pressure-Driven Valence Electron Transfer in Ba 3 BiRu 2 O 9 , Ba 3 BiIr 2 O 9 , and Ba 4 BiIr 3 O 12

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blanchard, Peter E. R.; Chapman, Karena W.; Heald, Steve M.

The hexagonal perovskites Ba3BiIr2O9, Ba3BiRu2O9 and Ba4BiIr3O12 all undergo pressure-induced 1% volume collapses above 5 GPa. These first-order transitions have been ascribed to internal transfer of valence electrons between bismuth and iridium/ruthenium, which is driven by external applied pressure because the reduction in volume achieved by emptying the 6s shell of bismuth upon oxidation to Bi5+ is greater in magnitude than the increase in volume by reducing iridium or ruthenium. Here, we report direct observation of these valence transfers for the first time, using high-pressure X-ray absorption near-edge spectroscopy (XANES) measurements. Our data also support the highly unusual “4+” nominalmore » oxidation state of bismuth in these compounds, although the possibility of local disproportionation into Bi3+/Bi5+ cannot be definitively ruled out. Ab initio calculations reproduce the transition, support its interpretation as a valence electron transfer from Bi to Ir/Ru, and suggest that the high-pressure phase may show metallic behavior (in contrast to the insulating ambient-pressure phase).« less

Vibrational treatment of the formic acid double minimum case in valence coordinates

NASA Astrophysics Data System (ADS)

Richter, Falk; Carbonnière, P.

2018-02-01

One single full dimensional valence coordinate HCOOH ground state potential energy surface accurate for both cis and trans conformers for all levels up to 6000 cm-1 relative to trans zero point energy has been generated at CCSD(T)-F12a/aug-cc-pVTZ level. The fundamentals and a set of eigenfunctions complete up to about 3120 and 2660 cm-1 for trans- and cis-HCOOH, respectively, have been calculated and assigned using the improved relaxation method of the Heidelberg multi-configuration time-dependent Hartree package and an exact expression for the kinetic energy in valence coordinates generated by the TANA program. The calculated trans fundamental transition frequencies agree with experiment to within 5 cm-1. A few reassignments are suggested. Our results discard any cis trans delocalization effects for vibrational eigenfunctions up to 3640 cm-1 relative to trans zero point energy.

A Transition from Localized to Strongly Correlated Electron Behavior and Mixed Valence Driven by Physical or Chemical Pressure in ACo 2As 2 (A = Eu and Ca)

DOE PAGES

Tan, Xiaoyan; Fabbris, Gilberto; Haskel, Daniel; ...

2016-02-03

In this paper, we demonstrate that the action of physical pressure, chemical compression, or aliovalent substitution in ACo 2As 2 (A = Eu and Ca) has a general consequence of causing these antiferromagnetic materials to become ferromagnets. In all cases, the mixed valence triggered at the electropositive A site results in the increase of the Co 3d density of states at the Fermi level. Remarkably, the dramatic alteration of magnetic behavior results from the very minor (<0.15 electron) change in the population of the 3d orbitals. The mixed valence state of Eu observed in the high-pressure (HP) form of EuComore » 2As 2 exhibits a remarkable stability, achieving the average oxidation state of +2.25 at 12.6 GPa. In the case of CaCo 2As 2, substituting even 10% of Eu or La into the Ca site causes ferromagnetic ordering of Co moments. Similar to HP-EuCo 2As 2, the itinerant 3d ferromagnetism emerges from electronic doping into the Co layer because of chemical compression of Eu sites in Ca 0.9Eu 0.1Co 1.91As 2 or direct electron doping in Ca 0.85La 0.15Co 1.89As 2. Finally, the results reported herein demonstrate the general possibility of amplifying minor localized electronic effects to achieve major changes in material’s properties via involvement of strongly correlated electrons.« less

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Qisheng; Miller, Gordon J.

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e –/atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Furthermore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

DOE PAGES

Lin, Qisheng; Miller, Gordon J.

2017-12-18

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e –/atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Furthermore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate.

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

What is the valence of Mn in GaMnN?

NASA Astrophysics Data System (ADS)

Nelson, Ryky; Berlijn, Tom; Moreno, Juana; Jarrell, Mark; Ku, Wei

2014-03-01

Motivated by the potential high Curie temperature of GaMnN, we investigate the controversial Mn-valence in this diluted magnetic semiconductor. From a first-principles Wannier functions analysis of the high energy Hilbert space we find unambiguously the charge state of Mn to be close to 2 + (d5), but in a mixed spin configuration with average magnetic moments of 4 μB. Using more extended Wannier orbitals to capture the lower-energy physics, we further demonstrate the feasibility of both the effective d4 description (appropriate to deal with the local magnetic moment and Jahn-Teller distortion), and the effective d5 description (relevant to study long-range magnetic order). Our derivation highlights the general richness of low-energy sectors in interacting many-body systems and the generic need for multiple effective descriptions, and advocates for a diminished relevance of atomic valence measured by various experimental probes. This research is supported in part by LA-SiGMA, NSF Award Number #EPS-1003897. TB was supported by DOE CMCSN and as a Wigner Fellow at the Oak Ridge National Laboratory.

Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update

NASA Technical Reports Server (NTRS)

Karner, J. M.; Sutton, S. R.; Papike, J. J.; Shearer, C. K.; Jones, J. H.; Newville, M.

2004-01-01

We have been developing an oxygen barometer based on the valence state of V (V(2+), V(3+), V(4+), and V(5+)) in solar system basaltic glasses. The V valence is determined by synchrotron micro x-ray absorption near edge structure (XANES), which uses x-ray absorption associated with core-electronic transitions (absorption edges) to reveal a pre-edge peak whose intensity is directly proportional to the valence state of an element. XANES has advantages over other techniques that determine elemental valence because measurements can be made non-destructively in air and in situ on conventional thin sections at a micrometer spatial resolution with elemental sensitivities of approx. 100 ppm. Recent results show that fO2 values derived from the V valence technique are consistent with fO2 estimates determined by other techniques for materials that crystallized above the IW buffer. The fO2's determined by V valence (IW-3.8 to IW-2) for the lunar pyroclastic glasses, however, are on the order of 1 to 2.8 log units below previous estimates. Furthermore, the calculated fO2's decrease with increasing TiO2 contents from the A17 VLT to the A17 Orange glasses. In order to investigate these results further, we have synthesized lunar green and orange glasses and examined them by XANES.

Optical activity and electronic absorption spectra of some simple nucleosides related to cytidine and uridine: all-valence-shell molecular orbital calculations.

PubMed Central

Miles, D W; Redington, P K; Miles, D L; Eyring, H

1981-01-01

The circular dichroism and electronic absorption of three simple model systems for cytidine and uridine have been measured to 190 nm. The molecular spectral properties (excitation wavelengths, oscillator strengths, rotational strengths, and polarization directions) and electronic transitional patterns were investigated by using wave functions of the entire nucleoside with the goal of establishing the reliability of the theoretical method. The computed electronic absorption quantities were shown to be in satisfactory agreement with experimental data. It was found that the computed optical rotatory strengths of the B2u and E1u electronic transitions and lowest observed n-pi transition are in good agreement with experimental values. Electronic transitions were characterized by their electronic transitional patterns derived from population analysis of the transition density matrix. The theoretical rotational strengths associated with the B2u and E1u transitions stabilize after the use of just a few singly excited configurations in the configuration interaction basis and, hypothetically, are more reliable as indicators of conformation in pyrimidine nucleosides related to cytidine. PMID:6950393

A Restricted Open Configuration Interaction with Singles Method To Calculate Valence-to-Core Resonant X-ray Emission Spectra: A Case Study

PubMed Central

2017-01-01

In this work, a new protocol for the calculation of valence-to-core resonant X-ray emission (VtC RXES) spectra is introduced. The approach is based on the previously developed restricted open configuration interaction with singles (ROCIS) method and its parametrized version, based on a ground-state Kohn–Sham determinant (DFT/ROCIS) method. The ROCIS approach has the following features: (1) In the first step approximation, many-particle eigenstates are calculated in which the total spin is retained as a good quantum number. (2) The ground state with total spin S and excited states with spin S′ = S, S ± 1, are obtained. (3) These states have a qualitatively correct multiplet structure. (4) Quasi-degenerate perturbation theory is used to treat the spin–orbit coupling operator variationally at the many-particle level. (5) Transition moments are obtained between the relativistic many-particle states. The method has shown great potential in the field of X-ray spectroscopy, in particular in the field of transition-metal L-edge, which cannot be described correctly with particle–hole theories. In this work, the method is extended to the calculation of resonant VtC RXES [alternatively referred to as 1s-VtC resonant inelastic X-ray scattering (RIXS)] spectra. The complete Kramers–Dirac–Heisenerg equation is taken into account. Thus, state interference effects are treated naturally within this protocol. As a first application of this protocol, a computational study on the previously reported VtC RXES plane on a molecular managanese(V) complex is performed. Starting from conventional X-ray absorption spectra (XAS), we present a systematic study that involves calculations and electronic structure analysis of both the XAS and non-resonant and resonant VtC XES spectra. The very good agreement between theory and experiment, observed in all cases, allows us to unravel the complicated intensity mechanism of these spectroscopic techniques as a synergic function of state

A minimalistic approach to static and dynamic electron correlations: Amending generalized valence bond method with extended random phase approximation correlation correction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatterjee, Koushik; Jawulski, Konrad; Pastorczak, Ewa

A perfect-pairing generalized valence bond (GVB) approximation is known to be one of the simplest approximations, which allows one to capture the essence of static correlation in molecular systems. In spite of its attractive feature of being relatively computationally efficient, this approximation misses a large portion of dynamic correlation and does not offer sufficient accuracy to be generally useful for studying electronic structure of molecules. We propose to correct the GVB model and alleviate some of its deficiencies by amending it with the correlation energy correction derived from the recently formulated extended random phase approximation (ERPA). On the examples ofmore » systems of diverse electronic structures, we show that the resulting ERPA-GVB method greatly improves upon the GVB model. ERPA-GVB recovers most of the electron correlation and it yields energy barrier heights of excellent accuracy. Thanks to a balanced treatment of static and dynamic correlation, ERPA-GVB stays reliable when one moves from systems dominated by dynamic electron correlation to those for which the static correlation comes into play.« less

Valence structures of aromatic bioactive compounds: a combined theoretical and experimental study.

PubMed

Wickrama Arachchilage, Anoja Pushpamali; Feyer, Vitaliy; Plekan, Oksana; Iakhnenko, Marianna; Prince, Kevin C; Wang, Feng

2012-09-01

Valence electronic structures of three recently isolated aryl bioactive compounds, namely 2-phenylethanol (2PE), p-hydroxyphenylethanol (HPE) and 4-hydroxybenzaldehyde (HBA), are studied using a combined theoretical and experimental method. Density functional theory-based calculations indicate that the side chains cause electron charge redistribution and therefore influence the aromaticity of the benzene derivatives. The simulated IR spectra further reveal features induced by the side chains. Solvent effects on the IR spectra are simulated using the polarizable continuum model, which exhibits enhancement of the O-H stretch vibrations with significant red-shift of 464 cm(-1) in 2PE. A significant spectral peak splitting of 94 cm(-1) between O(4)-H and O(8)-H of HPE is revealed in an aqueous environment. Experimental measurements for valence binding energy spectra for 2PE, HPE and HBA are presented and analyzed using outer-valence Green function calculations. The experimental (predicted) first ionization energies are measured as 9.19 (8.79), 8.47 (8.27) and 8.97 (8.82) eV for 2PE, HPE and HBA, respectively. The frontier orbitals (highest occupied molecular orbitals, HOMOs, and lowest unoccupied molecular orbitals, LUMOs) have similar atomic orbital characters although the HOMO-LUMO energy gaps are quite different.

EELS Valence Mapping in Electron Beam Sensitive FeFx/C Nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cosandey, F.; Al-Sharab, J.F.; Amatucci, Glenn G.

A new type of positive electrodes for Li-Ion batteries has been synthesized based on FeF{sub 2}/C and FeF3/C nanocomposites with particle size in the 8-12 nm range [1]. The measured high capacities rely on a complete reduction of Fe to its metallic state according to the following reaction: xLi{sup +}+xe{sup -} +Fe{sup x+}Fx = xLiF + Fe{sup 0}, where x=3 and x=2 for FeF3/C and FeF2/C respectively. This electrochemical reaction involves a change in valence state of Fe from 3+ or 2+ to 0 that can be determined uniquely by EELS from the peak energy of the L{sub 3} linemore » and from the L{sub 3}/L{sub 2} line intensity ratio. In this paper, we report EELS mapping results on the electrochemical conversion processes and in particular the mapping of the Fe valence state before and after discharge. This work was performed with a Hitachi HF2000 equipped with a Gatan PEELS and with a FEI CM200 FEG TEM equipped with a Gatan GIF. Both instruments were operated in STEM mode at 200kV with an EELS collection half angle of {beta}=5 mrad and spectrum imaging software.« less

Pseudo Jahn-Teller coupling in trioxides XO3(0,1,-1) with 22 and 23 valence electrons

NASA Astrophysics Data System (ADS)

Grein, Friedrich

2013-05-01

D3h and C2v geometries and energies, vertical excitation energies, as well as minimal energy paths as function of the O1(z)-X-O2 angle α were obtained for XO3(0,1,-1) (X = B, Al, Ga; C, Si, Ge; N, P, As; S, Se) molecules and ions with 22 and 23 valence electrons (VE), using density functional theory (DFT), coupled cluster with single and double substitutions with noniterative triple excitations (CCSD(T)), equation of motion (EOM)-CCSD, time-dependent DFT, and multi-reference configuration interaction methods. It is shown that pseudo Jahn-Teller (PJT) coupling increases as the central atom X becomes heavier, due to decreases in excitation energies. As is well known for CO3, the excited 1E' states of the 22 VE systems SiO3, GeO3; NO_3 ^ +, PO3+, AsO3+; BO3-, AlO3-, GaO3- have strong vibronic coupling with the 1A1' ground state via the e' vibrational modes, leading to a C2v minimum around α = 145°. For first and second row X atoms, there is an additional D3h minimum (α = 120°). Interacting excited states have minima around 135°. In the 23 VE systems CO3-, SiO3-; NO3, PO3; SO3+, coupling of the excited 2E' with the 2A2' ground state via the e' mode does not generate a C2v state. Minima of interacting excited states are close to 120°. However, due to very strong PJT coupling, a double-well potential is predicted for GeO3-, AsO3, and SeO3+, with a saddle point at D3h symmetry. Interaction of the b2 highest occupied molecular orbital with the b2 lowest unoccupied molecular orbital, both oxygen lone pair molecular orbitals, is seen as the reason for the C2v stabilization of 22 VE molecules.

B-site cation order/disorder and their valence states in Ba3MnNb2O9 perovskite oxide

NASA Astrophysics Data System (ADS)

Xin, Yan; Huang, Qing; Shafieizadeh, Zahra; Zhou, Haidong

2018-06-01

Polycrystalline samples Ba3MnNb2O9 synthesized by solid state reaction and single crystal samples grown by optical floating zone have been characterized using scanning transmission electron microscopy and electron energy loss spectroscopy. Three types of B-site Mn and Nb ordering phase are observed: fully ordered 1Mn:2Nb; fully disordered; nano-sized 1Mn:1Nb ordered. No electronic structure change for crystals with different ordering/disordering. The Mn valence is determined to be 2+, and Nb valence is 5+. Oxygen 2p orbitals hybridize with Mn 3d and Nb 4d orbitals. Factors that affect the electron energy loss near edge structures of transition metal white-lines in electron energy loss spectroscopy are explicitly illustrated and discussed.

Composition dependence of electronic, magnetic, transport and morphological properties of mixed valence manganite thin films

DOE PAGES

Singh, Surendra; Freeland, J. W.; Fitzsimmons, Michael R.; ...

2016-07-27

Mixed-valence manganese oxides present striking properties like the colossal magnetoresistance, metal-insulator transition (MIT) that may result from coexistence of ferromagnetic, metallic and insulating phases. Percolation of such phase coexistence in the vicinity of MIT leads to first-order transition in these manganites. However the length scales over which the electronic and magnetic phases are separated across MIT which appears compelling for bulk systems has been elusive in (La 1-yPr y) 1-xCaxMnO 3 films. Here we show the in-plane length scale over which charge and magnetism are correlated in (La 0.4Pr 0.6) 1-xCaxMnO3 films with x = 0.33 and 0.375, across themore » MIT temperature. We combine electrical transport (resistance) measurements, x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism (XMCD), and specular/off-specular x-ray resonant magnetic scattering (XRMS) measurements as a function of temperature to elucidate relationships between electronic, magnetic and morphological structure of the thin films. Using off-specular XRMS we obtained the charge-charge and charge-magnetic correlation length of these LPCMO films across the MIT. We observed different charge-magnetic correlation length for two films which increases below the MIT. The different correlation length shown by two films may be responsible for different macroscopic (transport and magnetic) properties.« less

A novel electron gun for inline MRI-linac configurations.

PubMed

Constantin, Dragoş E; Holloway, Lois; Keall, Paul J; Fahrig, Rebecca

2014-02-01

This work introduces a new electron gun geometry capable of robust functioning in the presence of a high strength external magnetic field for axisymmetric magnetic resonance imaging (MRI)-linac configurations. This allows an inline MRI-linac to operate without the need to isolate the linear accelerator (linac) using a magnetic shield. This MRI-linac integration approach not only leaves the magnet homogeneity unchanged but also provides the linac flexibility to move along the magnet axis of symmetry if the source to target distance needs to be adjusted. Simple electron gun geometry modifications of a Varian 600 C electron gun are considered and solved in the presence of an external magnetic field in order to determine a set of design principles for the new geometry. Based on these results, a new gun geometry is proposed and optimized in the fringe field of a 0.5 T open bore MRI magnet (GE Signa SP). A computer model for the 6 MeV Varian 600 C linac is used to determine the capture efficiency of the new electron gun-linac system in the presence of the fringe field of the same MRI scanner. The behavior of the new electron gun plus the linac system is also studied in the fringe fields of two other magnets, a 1.0 T prototype open bore magnet and a 1.5 T GE Conquest scanner. Simple geometrical modifications of the original electron gun geometry do not provide feasible solutions. However, these tests show that a smaller transverse cathode diameter with a flat surface and a slightly larger anode diameter could alleviate the current loss due to beam interactions with the anode in the presence of magnetic fields. Based on these findings, an initial geometry resembling a parallel plate capacitor with a hole in the anode is proposed. The optimization procedure finds a cathode-anode distance of 5 mm, a focusing electrode angle of 5°, and an anode drift tube length of 17.1 mm. Also, the linac can be displaced with ± 15 cm along the axis of the 0.5 T magnet without capture

A novel electron gun for inline MRI-linac configurations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Constantin, Dragoş E., E-mail: dragos.constantin@varian.com; Fahrig, Rebecca; Holloway, Lois

2014-02-15

Purpose: This work introduces a new electron gun geometry capable of robust functioning in the presence of a high strength external magnetic field for axisymmetric magnetic resonance imaging (MRI)-linac configurations. This allows an inline MRI-linac to operate without the need to isolate the linear accelerator (linac) using a magnetic shield. This MRI-linac integration approach not only leaves the magnet homogeneity unchanged but also provides the linac flexibility to move along the magnet axis of symmetry if the source to target distance needs to be adjusted. Methods: Simple electron gun geometry modifications of a Varian 600C electron gun are considered andmore » solved in the presence of an external magnetic field in order to determine a set of design principles for the new geometry. Based on these results, a new gun geometry is proposed and optimized in the fringe field of a 0.5 T open bore MRI magnet (GE Signa SP). A computer model for the 6 MeV Varian 600C linac is used to determine the capture efficiency of the new electron gun-linac system in the presence of the fringe field of the same MRI scanner. The behavior of the new electron gun plus the linac system is also studied in the fringe fields of two other magnets, a 1.0 T prototype open bore magnet and a 1.5 T GE Conquest scanner. Results: Simple geometrical modifications of the original electron gun geometry do not provide feasible solutions. However, these tests show that a smaller transverse cathode diameter with a flat surface and a slightly larger anode diameter could alleviate the current loss due to beam interactions with the anode in the presence of magnetic fields. Based on these findings, an initial geometry resembling a parallel plate capacitor with a hole in the anode is proposed. The optimization procedure finds a cathode-anode distance of 5 mm, a focusing electrode angle of 5°, and an anode drift tube length of 17.1 mm. Also, the linac can be displaced with ±15 cm along the axis of the 0

A novel electron gun for inline MRI-linac configurations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Constantin, Dragoş E., E-mail: dragos.constantin@varian.com; Fahrig, Rebecca; Holloway, Lois

Purpose: This work introduces a new electron gun geometry capable of robust functioning in the presence of a high strength external magnetic field for axisymmetric magnetic resonance imaging (MRI)-linac configurations. This allows an inline MRI-linac to operate without the need to isolate the linear accelerator (linac) using a magnetic shield. This MRI-linac integration approach not only leaves the magnet homogeneity unchanged but also provides the linac flexibility to move along the magnet axis of symmetry if the source to target distance needs to be adjusted. Methods: Simple electron gun geometry modifications of a Varian 600C electron gun are considered andmore » solved in the presence of an external magnetic field in order to determine a set of design principles for the new geometry. Based on these results, a new gun geometry is proposed and optimized in the fringe field of a 0.5 T open bore MRI magnet (GE Signa SP). A computer model for the 6 MeV Varian 600C linac is used to determine the capture efficiency of the new electron gun-linac system in the presence of the fringe field of the same MRI scanner. The behavior of the new electron gun plus the linac system is also studied in the fringe fields of two other magnets, a 1.0 T prototype open bore magnet and a 1.5 T GE Conquest scanner. Results: Simple geometrical modifications of the original electron gun geometry do not provide feasible solutions. However, these tests show that a smaller transverse cathode diameter with a flat surface and a slightly larger anode diameter could alleviate the current loss due to beam interactions with the anode in the presence of magnetic fields. Based on these findings, an initial geometry resembling a parallel plate capacitor with a hole in the anode is proposed. The optimization procedure finds a cathode-anode distance of 5 mm, a focusing electrode angle of 5°, and an anode drift tube length of 17.1 mm. Also, the linac can be displaced with ±15 cm along the axis of the 0

Determination of a natural valence-band offset - The case of HgTe and CdTe

NASA Technical Reports Server (NTRS)

Shih, C. K.; Spicer, W. E.

1987-01-01

A method to determine a natural valence-band offset (NVBO), i.e., the change in the valence-band maximum energy which is intrinsic to the bulk band structures of semiconductors is proposed. The HgTe-CdTe system is used as an example in which it is found that the valence-band maximum of HgTe lies 0.35 + or - 0.06 eV above that of CdTe. The NVBO of 0.35 eV is in good agreement with the X-ray photoemission spectroscopy measurement of the heterojunction offset. The procedure to determine the NVBO between semiconductors, and its implication on the heterojunction band lineup and the electronic structures of semiconductor alloys, are discussed.

A pilot training manual for the terminal configured vehicle electronic horizontal situation indicator

NASA Technical Reports Server (NTRS)

Houck, J. A.

1981-01-01

The initial phase of a training program for the Terminal Configured Vehicle Electronic Situation indicator (EHSI) is presented. The EHSI and its symbology is introduced and interpretation of the symbols is explained. Basic symbols shown on the display at all times are first presented. Additional optional symbols to be used as appropriate during different portions of a flight are then introduced and various display configurations interpreted. The upper half of each page is a reproduction of the EHSI display or other pertinent instructional material and the bottom half contains explanatory text, simplifying production of an audiovisual package for use with large training classes. Two quizzes on the course material are included.

Simultaneous conditioning of valence and arousal.

PubMed

Gawronski, Bertram; Mitchell, Derek G V

2014-01-01

Evaluative conditioning (EC) refers to the change in the valence of a conditioned stimulus (CS) due to its pairing with a positive or negative unconditioned stimulus (US). To the extent that core affect can be characterised by the two dimensions of valence and arousal, EC has important implications for the origin of affective responses. However, the distinction between valence and arousal is rarely considered in research on EC or conditioned responses more generally. Measuring the subjective feelings elicited by a CS, the results from two experiments showed that (1) repeated pairings of a CS with a positive or negative US of either high or low arousal led to corresponding changes in both CS valence and CS arousal, (2) changes in CS arousal, but not changes in CS valence, were significantly related to recollective memory for CS-US pairings, (3) subsequent presentations of the CS without the US reduced the conditioned valence of the CS, with conditioned arousal being less susceptible to extinction and (4) EC effects were stronger for high arousal than low arousal USs. The results indicate that the conditioning of affective responses can occur simultaneously along two independent dimensions, supporting evidence in related areas that calls for a consideration of both valence and arousal. Implications for research on EC and the acquisition of emotional dispositions are discussed.

Barrier-free proton transfer in the valence anion of 2'-deoxyadenosine-5'-monophosphate. II. A computational study.

PubMed

Kobyłecka, Monika; Gu, Jiande; Rak, Janusz; Leszczynski, Jerzy

2008-01-28

The propensity of four representative conformations of 2(')-deoxyadenosine-5(')-monophosphate (5(')-dAMPH) to bind an excess electron has been studied at the B3LYP6-31++G(d,p) level. While isolated canonical adenine does not support stable valence anions in the gas phase, all considered neutral conformations of 5(')-dAMPH form adiabatically stable anions. The type of an anionic 5(')-dAMPH state, i.e., the valence, dipole bound, or mixed (valence/dipole bound), depends on the internal hydrogen bond(s) pattern exhibited by a particular tautomer. The most stable anion results from an electron attachment to the neutral syn-south conformer. The formation of this anion is associated with a barrier-free proton transfer triggered by electron attachment and the internal rotation around the C4(')-C5(') bond. The adiabatic electron affinity of the a_south-syn anion is 1.19 eV, while its vertical detachment energy is 1.89 eV. Our results are compared with the photoelectron spectrum (PES) of 5(')-dAMPH(-) measured recently by Stokes et al., [J. Chem. Phys. 128, 044314 (2008)]. The computational VDE obtained for the most stable anionic structure matches well with the experimental electron binding energy region of maximum intensity. A further understanding of DNA damage might require experimental and computational studies on the systems in which purine nucleotides are engaged in hydrogen bonding.

Feasibility of Valence-to-Core X-ray Emission Spectroscopy for Tracking Transient Species

DOE PAGES

March, Anne Marie; Assefa, Tadesse A.; Bressler, Christian; ...

2015-02-09

X-ray spectroscopies, when combined in laser-pump, X-ray-probe measurement schemes, can be powerful tools for tracking the electronic and geometric structural changes that occur during the course of a photoinitiated chemical reaction. X-ray absorption spectroscopy (XAS) is considered an established technique for such measurements, and X-ray emission spectroscopy (XES) of the strongest core-to-core emission lines (Kα and Kβ) is now being utilized. Flux demanding valence-to-core XES promises to be an important addition to the time-resolved spectroscopic toolkit. Here In this paper we present measurements and density functional theory calculations on laser-excited, solution-phase ferrocyanide that demonstrate the feasibility of valence-to-core XES formore » time-resolved experiments. Lastly, we discuss technical improvements that will make valence-to-core XES a practical pump–probe technique.« less

SparseMaps—A systematic infrastructure for reduced-scaling electronic structure methods. III. Linear-scaling multireference domain-based pair natural orbital N-electron valence perturbation theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Yang; Sivalingam, Kantharuban; Neese, Frank, E-mail: Frank.Neese@cec.mpg.de

2016-03-07

Multi-reference (MR) electronic structure methods, such as MR configuration interaction or MR perturbation theory, can provide reliable energies and properties for many molecular phenomena like bond breaking, excited states, transition states or magnetic properties of transition metal complexes and clusters. However, owing to their inherent complexity, most MR methods are still too computationally expensive for large systems. Therefore the development of more computationally attractive MR approaches is necessary to enable routine application for large-scale chemical systems. Among the state-of-the-art MR methods, second-order N-electron valence state perturbation theory (NEVPT2) is an efficient, size-consistent, and intruder-state-free method. However, there are still twomore » important bottlenecks in practical applications of NEVPT2 to large systems: (a) the high computational cost of NEVPT2 for large molecules, even with moderate active spaces and (b) the prohibitive cost for treating large active spaces. In this work, we address problem (a) by developing a linear scaling “partially contracted” NEVPT2 method. This development uses the idea of domain-based local pair natural orbitals (DLPNOs) to form a highly efficient algorithm. As shown previously in the framework of single-reference methods, the DLPNO concept leads to an enormous reduction in computational effort while at the same time providing high accuracy (approaching 99.9% of the correlation energy), robustness, and black-box character. In the DLPNO approach, the virtual space is spanned by pair natural orbitals that are expanded in terms of projected atomic orbitals in large orbital domains, while the inactive space is spanned by localized orbitals. The active orbitals are left untouched. Our implementation features a highly efficient “electron pair prescreening” that skips the negligible inactive pairs. The surviving pairs are treated using the partially contracted NEVPT2 formalism. A detailed

SparseMaps—A systematic infrastructure for reduced-scaling electronic structure methods. III. Linear-scaling multireference domain-based pair natural orbital N-electron valence perturbation theory

NASA Astrophysics Data System (ADS)

Guo, Yang; Sivalingam, Kantharuban; Valeev, Edward F.; Neese, Frank

2016-03-01

Multi-reference (MR) electronic structure methods, such as MR configuration interaction or MR perturbation theory, can provide reliable energies and properties for many molecular phenomena like bond breaking, excited states, transition states or magnetic properties of transition metal complexes and clusters. However, owing to their inherent complexity, most MR methods are still too computationally expensive for large systems. Therefore the development of more computationally attractive MR approaches is necessary to enable routine application for large-scale chemical systems. Among the state-of-the-art MR methods, second-order N-electron valence state perturbation theory (NEVPT2) is an efficient, size-consistent, and intruder-state-free method. However, there are still two important bottlenecks in practical applications of NEVPT2 to large systems: (a) the high computational cost of NEVPT2 for large molecules, even with moderate active spaces and (b) the prohibitive cost for treating large active spaces. In this work, we address problem (a) by developing a linear scaling "partially contracted" NEVPT2 method. This development uses the idea of domain-based local pair natural orbitals (DLPNOs) to form a highly efficient algorithm. As shown previously in the framework of single-reference methods, the DLPNO concept leads to an enormous reduction in computational effort while at the same time providing high accuracy (approaching 99.9% of the correlation energy), robustness, and black-box character. In the DLPNO approach, the virtual space is spanned by pair natural orbitals that are expanded in terms of projected atomic orbitals in large orbital domains, while the inactive space is spanned by localized orbitals. The active orbitals are left untouched. Our implementation features a highly efficient "electron pair prescreening" that skips the negligible inactive pairs. The surviving pairs are treated using the partially contracted NEVPT2 formalism. A detailed comparison

Social Annotation Valence: The Impact on Online Informed Consent Beliefs and Behavior.

PubMed

Balestra, Martina; Shaer, Orit; Okerlund, Johanna; Westendorf, Lauren; Ball, Madeleine; Nov, Oded

2016-07-20

Social media, mobile and wearable technology, and connected devices have significantly expanded the opportunities for conducting biomedical research online. Electronic consent to collecting such data, however, poses new challenges when contrasted to traditional consent processes. It reduces the participant-researcher dialogue but provides an opportunity for the consent deliberation process to move from solitary to social settings. In this research, we propose that social annotations, embedded in the consent form, can help prospective participants deliberate on the research and the organization behind it in ways that traditional consent forms cannot. Furthermore, we examine the role of the comments' valence on prospective participants' beliefs and behavior. This study focuses specifically on the influence of annotations' valence on participants' perceptions and behaviors surrounding online consent for biomedical research. We hope to shed light on how social annotation can be incorporated into digitally mediated consent forms responsibly and effectively. In this controlled between-subjects experiment, participants were presented with an online consent form for a personal genomics study that contained social annotations embedded in its margins. Individuals were randomly assigned to view the consent form with positive-, negative-, or mixed-valence comments beside the text of the consent form. We compared participants' perceptions of being informed and having understood the material, their trust in the organization seeking the consent, and their actual consent across conditions. We find that comment valence has a marginally significant main effect on participants' perception of being informed (F2=2.40, P=.07); specifically, participants in the positive condition (mean 4.17, SD 0.94) felt less informed than those in the mixed condition (mean 4.50, SD 0.69, P=.09). Comment valence also had a marginal main effect on the extent to which participants reported trusting the

Interpretation of monoclinic hafnia valence electron energy-loss spectra by time-dependent density functional theory

NASA Astrophysics Data System (ADS)

Hung, L.; Guedj, C.; Bernier, N.; Blaise, P.; Olevano, V.; Sottile, F.

2016-04-01

We present the valence electron energy-loss spectrum and the dielectric function of monoclinic hafnia (m -HfO2) obtained from time-dependent density-functional theory (TDDFT) predictions and compared to energy-filtered spectroscopic imaging measurements in a high-resolution transmission-electron microscope. Fermi's golden rule density-functional theory (DFT) calculations can capture the qualitative features of the energy-loss spectrum, but we find that TDDFT, which accounts for local-field effects, provides nearly quantitative agreement with experiment. Using the DFT density of states and TDDFT dielectric functions, we characterize the excitations that result in the m -HfO2 energy-loss spectrum. The sole plasmon occurs between 13 and 16 eV, although the peaks ˜28 and above 40 eV are also due to collective excitations. We furthermore elaborate on the first-principles techniques used, their accuracy, and remaining discrepancies among spectra. More specifically, we assess the influence of Hf semicore electrons (5 p and 4 f ) on the energy-loss spectrum, and find that the inclusion of transitions from the 4 f band damps the energy-loss intensity in the region above 13 eV. We study the impact of many-body effects in a DFT framework using the adiabatic local-density approximation (ALDA) exchange-correlation kernel, as well as from a many-body perspective using "scissors operators" matched to an ab initio G W calculation to account for self-energy corrections. These results demonstrate some cancellation of errors between self-energy and excitonic effects, even for excitations from the Hf 4 f shell. We also simulate the dispersion with increasing momentum transfer for plasmon and collective excitation peaks.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bickmore, Barry R.; Rosso, Kevin M.; Tadanier, Christopher J.

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 predictingmore » 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.« less

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

PubMed

Lin, Qisheng; Miller, Gordon J

2018-01-16

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e - /atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Therefore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate. During our efforts to find quasicrystals and crystalline approximants by valence electron tuning near 2.0 e - /atom, we observed that compositions close to those of quasicrystals are exceptional sources for unprecedented valence electron-poor polar intermetallics, e.g., Ca 4 Au 10 In 3 containing (Au 10 In 3 ) wavy layers, Li 14.7 Mg 36.8 Cu 21.5 Ga 66 adopting a type IV clathrate framework, and Sc 4 Mg x Cu 15-x Ga 7.5 that is incommensurately modulated. In particular, exploratory syntheses of AAu 3 T (A = Ca, Sr, Ba and T = Ge, Sn) phases led to interesting bonding features for Au, such as columns, layers, and lonsdaleite-type tetrahedral frameworks. Overall, the breadth of Au-rich polar intermetallics originates, in part, from significant relativistics effect on the valence electrons of Au, effects which result in greater 6s/5d orbital mixing, a small effective metallic radius, and an enhanced Mulliken electronegativity, all leading to ultimate enhanced binding with nearly all metals including itself. Two other successful strategies to mine electron-poor polar intermetallics include lithiation and "cation-rich" phases. Along these lines, we have studied lithiated Zn-rich compounds in which structural

Imaging ultrafast excited state pathways in transition metal complexes by X-ray transient absorption and scattering using X-ray free electron laser source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Lin X.; Shelby, Megan L.; Lestrange, Patrick J.

2016-01-01

This report will describe our recent studies of transition metal complex structural dynamics on the fs and ps time scales using an X-ray free electron laser source, Linac Coherent Light Source (LCLS). Ultrafast XANES spectra at the Ni K-edge of nickel(II) tetramesitylporphyrin (NiTMP) were successfully measured for optically excited state at a timescale from 100 fs to 50 ps, providing insight into its sub-ps electronic and structural relaxation processes. Importantly, a transient reduced state Ni(I) (π, 3dx2-y2) electronic state is captured through the interpretation of a short-lived excited state absorption on the low-energy shoulder of the edge, which is aidedmore » by the computation of X-ray transitions for postulated excited electronic states. The observed and computed inner shell to valence orbital transition energies demonstrate and quantify the influence of electronic configuration on specific metal orbital energies. A strong influence of the valence orbital occupation on the inner shell orbital energies indicates that one should not use the transition energy from 1s to other orbitals to draw conclusions about the d-orbital energies. For photocatalysis, a transient electronic configuration could influence d-orbital energies up to a few eV and any attempt to steer the reaction pathway should account for this to ensure that external energies can be used optimally in driving desirable processes. NiTMP structural evolution and the influence of the porphyrin macrocycle conformation on relaxation kinetics can be likewise inferred from this study.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jing; Liang, Le; Zhang, Lanting, E-mail: lantingzh@sjtu.edu.cn, E-mail: lmsun@sjtu.edu.cn

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 clearlymore » 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.« less

What is the valence of Mn in Ga 1-xMn xN?

DOE PAGES

Berlijn, Tom; Jarrell, Mark; Nelson, Ryky; ...

2015-11-04

Motivated by the potential high Curie temperature of Ga 1-xMn xN, we investigate the controversial Mn valence in this diluted magnetic semiconductor. From a first-principles Wannier-function analysis of the high energy Hilbert space, we find unambiguously the Mn valence to be close to 2+(d 5), but in a mixed spin configuration with average magnetic moments of 4µ B. By integrating out high-energy degrees of freedom differently, we further demonstrate the feasibility of both effective d 4 and d 5 descriptions. These two descriptions offer simple pictures for local and extended properties of the system, and highlight the dual nature ofmore » its doped hole. Specifically, in the effective d 5 description, we demonstrate novel physical effects absent in previous studies. Thus, our derivation highlights the richness of low-energy sectors in interacting many-body systems and the generic need for multiple effective descriptions.« less

Tunable electronic properties of graphene through controlling bonding configurations of doped nitrogen atoms.

PubMed

Zhang, Jia; Zhao, Chao; Liu, Na; Zhang, Huanxi; Liu, Jingjing; Fu, Yong Qing; Guo, Bin; Wang, Zhenlong; Lei, Shengbin; Hu, PingAn

2016-06-21

Single-layer and mono-component doped graphene is a crucial platform for a better understanding of the relationship between its intrinsic electronic properties and atomic bonding configurations. Large-scale doped graphene films dominated with graphitic nitrogen (GG) or pyrrolic nitrogen (PG) were synthesized on Cu foils via a free radical reaction at growth temperatures of 230-300 °C and 400-600 °C, respectively. The bonding configurations of N atoms in the graphene lattices were controlled through reaction temperature, and characterized using Raman spectroscopy, X-ray photoelectron spectroscopy and scanning tunneling microscope. The GG exhibited a strong n-type doping behavior, whereas the PG showed a weak n-type doping behavior. Electron mobilities of the GG and PG were in the range of 80.1-340 cm(2) V(-1)·s(-1) and 59.3-160.6 cm(2) V(-1)·s(-1), respectively. The enhanced doping effect caused by graphitic nitrogen in the GG produced an asymmetry electron-hole transport characteristic, indicating that the long-range scattering (ionized impurities) plays an important role in determining the carrier transport behavior. Analysis of temperature dependent conductance showed that the carrier transport mechanism in the GG was thermal excitation, whereas that in the PG, was a combination of thermal excitation and variable range hopping.

Strategies to Engage Students' Production of Electron Configurations in a Prototypical Chemistry Classroom Community

ERIC Educational Resources Information Center

Grueber, David J.

2012-01-01

This study investigated associations between teacher-student interaction and students' persistence to complete written electron configurations in a high school chemistry classroom. Analyses of the interactions were guided with an Expectancy-Value framework to identify the discourse strategies used by the teacher to build engagement in a classroom…

Excited state electron affinity calculations for aluminum

NASA Astrophysics Data System (ADS)

Hussein, Adnan Yousif

2017-08-01

Excited states of negative aluminum ion are reviewed, and calculations of electron affinities of the states (3s^23p^2)^1D and (3s3p^3){^5}{S}° relative to the (3s^23p)^2P° and (3s3p^2)^4P respectively of the neutral aluminum atom are reported in the framework of nonrelativistic configuration interaction (CI) method. A priori selected CI (SCI) with truncation energy error (Bunge in J Chem Phys 125:014107, 2006) and CI by parts (Bunge and Carbó-Dorca in J Chem Phys 125:014108, 2006) are used to approximate the valence nonrelativistic energy. Systematic studies of convergence of electron affinity with respect to the CI excitation level are reported. The calculated value of the electron affinity for ^1D state is 78.675(3) meV. Detailed Calculations on the ^5S°c state reveals that is 1216.8166(3) meV below the ^4P state.

Barrier-free proton transfer in the valence anion of 2'-deoxyadenosine-5'-monophosphate. II. A computational study

NASA Astrophysics Data System (ADS)

Kobyłecka, Monika; Gu, Jiande; Rak, Janusz; Leszczynski, Jerzy

2008-01-01

The propensity of four representative conformations of 2'-deoxyadenosine-5'-monophosphate (5'-dAMPH) to bind an excess electron has been studied at the B3LYP /6-31++G(d,p) level. While isolated canonical adenine does not support stable valence anions in the gas phase, all considered neutral conformations of 5'-dAMPH form adiabatically stable anions. The type of an anionic 5'-dAMPH state, i.e., the valence, dipole bound, or mixed (valence/dipole bound), depends on the internal hydrogen bond(s) pattern exhibited by a particular tautomer. The most stable anion results from an electron attachment to the neutral syn-south conformer. The formation of this anion is associated with a barrier-free proton transfer triggered by electron attachment and the internal rotation around the C4'-C5' bond. The adiabatic electron affinity of the a&barbelow;south-syn anion is 1.19eV, while its vertical detachment energy is 1.89eV. Our results are compared with the photoelectron spectrum (PES) of 5'-dAMPH- measured recently by Stokes et al., [J. Chem. Phys. 128, 044314 (2008)]. The computational VDE obtained for the most stable anionic structure matches well with the experimental electron binding energy region of maximum intensity. A further understanding of DNA damage might require experimental and computational studies on the systems in which purine nucleotides are engaged in hydrogen bonding.

Social Annotation Valence: The Impact on Online Informed Consent Beliefs and Behavior

PubMed Central

Shaer, Orit; Okerlund, Johanna; Westendorf, Lauren; Ball, Madeleine; Nov, Oded

2016-01-01

Background Social media, mobile and wearable technology, and connected devices have significantly expanded the opportunities for conducting biomedical research online. Electronic consent to collecting such data, however, poses new challenges when contrasted to traditional consent processes. It reduces the participant-researcher dialogue but provides an opportunity for the consent deliberation process to move from solitary to social settings. In this research, we propose that social annotations, embedded in the consent form, can help prospective participants deliberate on the research and the organization behind it in ways that traditional consent forms cannot. Furthermore, we examine the role of the comments’ valence on prospective participants’ beliefs and behavior. Objective This study focuses specifically on the influence of annotations’ valence on participants’ perceptions and behaviors surrounding online consent for biomedical research. We hope to shed light on how social annotation can be incorporated into digitally mediated consent forms responsibly and effectively. Methods In this controlled between-subjects experiment, participants were presented with an online consent form for a personal genomics study that contained social annotations embedded in its margins. Individuals were randomly assigned to view the consent form with positive-, negative-, or mixed-valence comments beside the text of the consent form. We compared participants’ perceptions of being informed and having understood the material, their trust in the organization seeking the consent, and their actual consent across conditions. Results We find that comment valence has a marginally significant main effect on participants’ perception of being informed (F2=2.40, P=.07); specifically, participants in the positive condition (mean 4.17, SD 0.94) felt less informed than those in the mixed condition (mean 4.50, SD 0.69, P=.09). Comment valence also had a marginal main effect on the

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group's Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl3SCN and CCl2FSCN.

PubMed

Rodríguez Pirani, Lucas S; Della Védova, Carlos O; Geronés, Mariana; Romano, Rosana M; Cavasso-Filho, Reinaldo; Ge, Maofa; Ma, Chunping; Erben, Mauricio F

2017-12-07

Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2p regions. Two simple and closely related molecules, namely, CCl 3 SCN and CCl 2 FSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green's function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CCl 3 SCN and CCl 2 FSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CX 3 SCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX 3 group is observed. Irradiation of CCl 3 SCN and CCl 2 FSCN with photons in the valence energy regions leads to the formation of CCl 2 X + and CClXSCN + ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra.

The convergence of complete active space self-consistent-field configuration interaction including all single and double excitation energies to the complete basis set limit

NASA Astrophysics Data System (ADS)

Petersson, George A.; Malick, David K.; Frisch, Michael J.; Braunstein, Matthew

2006-07-01

Examination of the convergence of full valence complete active space self-consistent-field configuration interaction including all single and double excitation (CASSCF-CISD) energies with expansion of the one-electron basis set reveals a pattern very similar to the convergence of single determinant energies. Calculations on the lowest four singlet states and the lowest four triplet states of N2 with the sequence of n-tuple-ζ augmented polarized (nZaP) basis sets (n =2, 3, 4, 5, and 6) are used to establish the complete basis set limits. Full configuration-interaction (CI) and core electron contributions must be included for very accurate potential energy surfaces. However, a simple extrapolation scheme that has no adjustable parameters and requires nothing more demanding than CAS(10e -,8orb)-CISD/3ZaP calculations gives the Re, ωe, ωeXe, Te, and De for these eight states with rms errors of 0.0006Å, 4.43cm-1, 0.35cm-1, 0.063eV, and 0.018eV, respectively.

Highly correlated configuration interaction calculations on water with large orbital bases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Almora-Díaz, César X., E-mail: xalmora@fisica.unam.mx

2014-05-14

A priori selected configuration interaction (SCI) with truncation energy error [C. F. Bunge, J. Chem. Phys. 125, 014107 (2006)] and CI by parts [C. F. Bunge and R. Carbó-Dorca, J. Chem. Phys. 125, 014108 (2006)] are used to approximate the total nonrelativistic electronic ground state energy of water at fixed experimental geometry with CI up to sextuple excitations. Correlation-consistent polarized core-valence basis sets (cc-pCVnZ) up to sextuple zeta and augmented correlation-consistent polarized core-valence basis sets (aug-cc-pCVnZ) up to quintuple zeta quality are employed. Truncation energy errors range between less than 1 μhartree, and 100 μhartree for the largest orbital set. Coupledmore » cluster CCSD and CCSD(T) calculations are also obtained for comparison. Our best upper bound, −76.4343 hartree, obtained by SCI with up to sextuple excitations with a cc-pCV6Z basis recovers more than 98.8% of the correlation energy of the system, and it is only about 3 kcal/mol above the “experimental” value. Despite that the present energy upper bounds are far below all previous ones, comparatively large dispersion errors in the determination of the extrapolated energies to the complete basis set do not allow to determine a reliable estimation of the full CI energy with an accuracy better than 0.6 mhartree (0.4 kcal/mol)« less

Electronic structure of stoichiometric and oxygen-deficient ferroelectric Hf0.5Zr0.5O2.

PubMed

Perevalov, T V; Islamov, D R; Gritsenko, V A; Prosvirin, I P

2018-05-11

The electronic structure of oxygen-deficient Hf 0.5 Zr 0.5 O 2 in the non-centrosymmetric orthorhombic (ferroelectric) phase was investigated by means of x-ray photoelectron spectroscopy and first-principle density functional theory calculations. It was established that a peak in the photoelectron spectra observed at an energy above the valence band top of ferroelectric Hf 0.5 Zr 0.5 O 2 in ion-etched samples was due to oxygen vacancies. A method for evaluating the oxygen vacancies concentration in the material from the comparison of experimental and theoretical photoelectron spectra of the valence band is proposed. It is found that oxygen polyvacancies are not formed in ferroelectric Hf 0.5 Zr 0.5 O 2 : an energy-favorable spatial arrangement of several oxygen vacancies in the crystal corresponds to the configuration formed by noninteracting vacancies distant from each other. The oxygen vacancies in five charged states were simulated. The electron levels in the bandgap caused by charged oxygen vacancies indicate that any type of oxygen vacancies in ferroelectric Hf 0.5 Zr 0.5 O 2 can capture both electrons and holes, i.e. can act as an amphoteric localization center for charge carriers.

Electronic structure of stoichiometric and oxygen-deficient ferroelectric Hf0.5Zr0.5O2

NASA Astrophysics Data System (ADS)

Perevalov, T. V.; Islamov, D. R.; Gritsenko, V. A.; Prosvirin, I. P.

2018-05-01

The electronic structure of oxygen-deficient Hf0.5Zr0.5O2 in the non-centrosymmetric orthorhombic (ferroelectric) phase was investigated by means of x-ray photoelectron spectroscopy and first-principle density functional theory calculations. It was established that a peak in the photoelectron spectra observed at an energy above the valence band top of ferroelectric Hf0.5Zr0.5O2 in ion-etched samples was due to oxygen vacancies. A method for evaluating the oxygen vacancies concentration in the material from the comparison of experimental and theoretical photoelectron spectra of the valence band is proposed. It is found that oxygen polyvacancies are not formed in ferroelectric Hf0.5Zr0.5O2: an energy-favorable spatial arrangement of several oxygen vacancies in the crystal corresponds to the configuration formed by noninteracting vacancies distant from each other. The oxygen vacancies in five charged states were simulated. The electron levels in the bandgap caused by charged oxygen vacancies indicate that any type of oxygen vacancies in ferroelectric Hf0.5Zr0.5O2 can capture both electrons and holes, i.e. can act as an amphoteric localization center for charge carriers.

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

Performance evaluation and comparison of three-terminal energy selective electron devices with different connective ways and filter configurations

NASA Astrophysics Data System (ADS)

Peng, Wanli; Zhang, Yanchao; Yang, Zhimin; Chen, Jincan

2018-02-01

Three-terminal energy selective electron (ESE) devices consisting of three electronic reservoirs connected by two energy filters and an electronic conductor with negligible resistance may work as ESE refrigerators and amplifiers. They have three possible connective ways for the electronic conductor and six electronic transmission forms. The configuration of energy filters may be described by the different transmission functions such as the rectangular and Lorentz transmission functions. The ESE devices with three connective ways can be, respectively, regarded as three equivalent hybrid systems composed of an ESE heat engine and an ESE refrigerator/heat pump. With the help of the theory of the ESE devices operated between two electronic reservoirs, the coefficients of performance and cooling rates (heat-pumping rates) of hybrid systems are directly derived. The general performance characteristics of hybrid systems are revealed. The optimal regions of these devices are determined. The performances of the devices with three connective ways of the electronic conductor and two configurations of energy filters are compared in detail. The advantages and disadvantages of each of three-terminal ESE devices are expounded. The results obtained here may provide some guidance for the optimal design and operation of three-terminal ESE devices.

Photoabsorption in sodium clusters: first principles configuration interaction calculations

NASA Astrophysics Data System (ADS)

Priya, Pradip Kumar; Rai, Deepak Kumar; Shukla, Alok

2017-05-01

We present systematic and comprehensive correlated-electron calculations of the linear photoabsorption spectra of small neutral closed- and open-shell sodium clusters (Nan, n = 2 - 6), as well as closed-shell cation clusters (Nan+, n = 3, 5). We have employed the configuration interaction (CI) methodology at the full CI (FCI) and quadruple CI (QCI) levels to compute the ground, and the low-lying excited states of the clusters. For most clusters, besides the minimum energy structures, we also consider their energetically close isomers. The photoabsorption spectra were computed under the electric-dipole approximation, employing the dipole-matrix elements connecting the ground state with the excited states of each isomer. Our calculations were tested rigorously for convergence with respect to the basis set, as well as with respect to the size of the active orbital space employed in the CI calculations. These calculations reveal that as far as electron-correlation effects are concerned, core excitations play an important role in determining the optimized ground state geometries of various clusters, thereby requiring all-electron correlated calculations. But, when it comes to low-lying optical excitations, only valence electron correlation effects play an important role, and excellent agreement with the experimental results is obtained within the frozen-core approximation. For the case of Na6, the largest cluster studied in this work, we also discuss the possibility of occurrence of plasmonic resonance in the optical absorption spectrum. Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjd/e2017-70728-3

Valence and magnitude ambiguity in feedback processing.

PubMed

Gu, Ruolei; Feng, Xue; Broster, Lucas S; Yuan, Lu; Xu, Pengfei; Luo, Yue-Jia

2017-05-01

Outcome feedback which indicates behavioral consequences are crucial for reinforcement learning and environmental adaptation. Nevertheless, outcome information in daily life is often totally or partially ambiguous. Studying how people interpret this kind of information would provide important knowledge about the human evaluative system. This study concentrates on the neural processing of partially ambiguous feedback, that is, either its valence or magnitude is unknown to participants. To address this topic, we sequentially presented valence and magnitude information; electroencephalography (EEG) response to each kind of presentation was recorded and analyzed. The event-related potential components feedback-related negativity (FRN) and P3 were used as indices of neural activity. Consistent with previous literature, the FRN elicited by ambiguous valence was not significantly different from that elicited by negative valence. On the other hand, the FRN elicited by ambiguous magnitude was larger than both the large and small magnitude, indicating the motivation to seek unambiguous magnitude information. The P3 elicited by ambiguous valence and ambiguous magnitude was not significantly different from that elicited by negative valence and small magnitude, respectively, indicating the emotional significance of feedback ambiguity. Finally, the aforementioned effects also manifested in the stage of information integration. These findings indicate both similarities and discrepancies between the processing of valence ambiguity and that of magnitude ambiguity, which may help understand the mechanisms of ambiguous information processing.

An Introduction to the Periodic Law for General Chemistry Students.

ERIC Educational Resources Information Center

Schlenker, Richard M.

A brief introduction to the periodic table of the elements is presented. The periodic relationships are demonstrated through the use of seven tables which include a breakdown of the periodic table by groups or families, valence ring electron populations by period, electronic configurations of the elements, electron configurations of the elements…

Emotional valence and physical space: limits of interaction.

PubMed

de la Vega, Irmgard; de Filippis, Mónica; Lachmair, Martin; Dudschig, Carolin; Kaup, Barbara

2012-04-01

According to the body-specificity hypothesis, people associate positive things with the side of space that corresponds to their dominant hand and negative things with the side corresponding to their nondominant hand. Our aim was to find out whether this association holds also true for a response time study using linguistic stimuli, and whether such an association is activated automatically. Four experiments explored this association using positive and negative words. In Exp. 1, right-handers made a lexical judgment by pressing a left or right key. Attention was not explicitly drawn to the valence of the stimuli. No valence-by-side interaction emerged. In Exp. 2 and 3, right-handers and left-handers made a valence judgment by pressing a left or a right key. A valence-by-side interaction emerged: For positive words, responses were faster when participants responded with their dominant hand, whereas for negative words, responses were faster for the nondominant hand. Exp. 4 required a valence judgment without stating an explicit mapping of valence and side. No valence-by-side interaction emerged. The experiments provide evidence for an association between response side and valence, which, however, does not seem to be activated automatically but rather requires a task with an explicit response mapping to occur.

Complex multireference configuration interaction calculations for the K-vacancy Auger states of N{sup q+} (q = 2-5) ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Yi-Geng; Data Center for High Energy Density Physics, Institute of Applied Physics and Computational Mathematics, P.O. Box 8009, Beijing 100088; Wu, Yong, E-mail: wu-yong@iapcm.ac.cn

2016-02-07

K-vacancy Auger states of N{sup q+} (q = 2-5) ions are studied by using the complex multireference single- and double-excitation configuration interaction (CMRD-CI) method. The calculated resonance parameters are in good agreement with the available experimental and theoretical data. It shows that the resonance positions and widths converge quickly with the increase of the atomic basis sets in the CMRD-CI calculations; the standard atomic basis set can be employed to describe the atomic K-vacancy Auger states well. The strong correlations between the valence and core electrons play important roles in accurately determining those resonance parameters, Rydberg electrons contribute negligibly inmore » the calculations. Note that it is the first time that the complex scaling method has been successfully applied for the B-like nitrogen. CMRD-CI is readily extended to treat the resonance states of molecules in the near future.« less

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

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.

Role of random magnetic anisotropy on the valence, magnetocaloric and resistivity properties in a hexagonal Sm2Ni0.87Si2.87 compound

NASA Astrophysics Data System (ADS)

Pakhira, Santanu; Kundu, Asish K.; Mazumdar, Chandan; Ranganathan, R.

2018-05-01

In this work, we report the effect of random magnetic anisotropy (RMA) on the valence, magnetocaloric and resistivity properties in a glassy intermetallic material Sm2Ni0.87Si2.87. On the basis of detailed studies on the valence band and core level electronic structure, we have established that both the Sm3+ and Sm2+ ions are present in the system, suggesting the compound to be of mixed valence in nature. The significant observation of positive magnetic entropy change in zero-field cooled measurement has been argued due to the presence of RMA that develops due to local electronic environmental variations between the rare-earth ions in the system. The quantum interference effect caused by the elastic electron–electron interaction is responsible for the resistivity upturn at low-temperature for this disordered metallic conductor.

Pair natural orbital and canonical coupled cluster reaction enthalpies involving light to heavy alkali and alkaline earth metals: the importance of sub-valence correlation.

PubMed

Minenkov, Yury; Bistoni, Giovanni; Riplinger, Christoph; Auer, Alexander A; Neese, Frank; Cavallo, Luigi

2017-04-05

In this work, we tested canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) for a set of 32 ligand exchange and association/dissociation reaction enthalpies involving ionic complexes of Li, Be, Na, Mg, Ca, Sr, Ba and Pb(ii). Two strategies were investigated: in the former, only valence electrons were included in the correlation treatment, giving rise to the computationally very efficient FC (frozen core) approach; in the latter, all non-ECP electrons were included in the correlation treatment, giving rise to the AE (all electron) approach. Apart from reactions involving Li and Be, the FC approach resulted in non-homogeneous performance. The FC approach leads to very small errors (<2 kcal mol -1 ) for some reactions of Na, Mg, Ca, Sr, Ba and Pb, while for a few reactions of Ca and Ba deviations up to 40 kcal mol -1 have been obtained. Large errors are both due to artificial mixing of the core (sub-valence) orbitals of metals and the valence orbitals of oxygen and halogens in the molecular orbitals treated as core, and due to neglecting core-core and core-valence correlation effects. These large errors are reduced to a few kcal mol -1 if the AE approach is used or the sub-valence orbitals of metals are included in the correlation treatment. On the technical side, the CCSD(T) and DLPNO-CCSD(T) results differ by a fraction of kcal mol -1 , indicating the latter method as the perfect choice when the CPU efficiency is essential. For completely black-box applications, as requested in catalysis or thermochemical calculations, we recommend the DLPNO-CCSD(T) method with all electrons that are not covered by effective core potentials included in the correlation treatment and correlation-consistent polarized core valence basis sets of cc-pwCVQZ(-PP) quality.

Parametrization of Stillinger-Weber potential based on valence force field model: application to single-layer MoS2 and black phosphorus

NASA Astrophysics Data System (ADS)

Jiang, Jin-Wu

2015-08-01

We propose parametrizing the Stillinger-Weber potential for covalent materials starting from the valence force-field model. All geometrical parameters in the Stillinger-Weber potential are determined analytically according to the equilibrium condition for each individual potential term, while the energy parameters are derived from the valence force-field model. This parametrization approach transfers the accuracy of the valence force field model to the Stillinger-Weber potential. Furthermore, the resulting Stilliinger-Weber potential supports stable molecular dynamics simulations, as each potential term is at an energy-minimum state separately at the equilibrium configuration. We employ this procedure to parametrize Stillinger-Weber potentials for single-layer MoS2 and black phosphorous. The obtained Stillinger-Weber potentials predict an accurate phonon spectrum and mechanical behaviors. We also provide input scripts of these Stillinger-Weber potentials used by publicly available simulation packages including GULP and LAMMPS.

Parametrization of Stillinger-Weber potential based on valence force field model: application to single-layer MoS2 and black phosphorus.

PubMed

Jiang, Jin-Wu

2015-08-07

We propose parametrizing the Stillinger-Weber potential for covalent materials starting from the valence force-field model. All geometrical parameters in the Stillinger-Weber potential are determined analytically according to the equilibrium condition for each individual potential term, while the energy parameters are derived from the valence force-field model. This parametrization approach transfers the accuracy of the valence force field model to the Stillinger-Weber potential. Furthermore, the resulting Stilliinger-Weber potential supports stable molecular dynamics simulations, as each potential term is at an energy-minimum state separately at the equilibrium configuration. We employ this procedure to parametrize Stillinger-Weber potentials for single-layer MoS2 and black phosphorous. The obtained Stillinger-Weber potentials predict an accurate phonon spectrum and mechanical behaviors. We also provide input scripts of these Stillinger-Weber potentials used by publicly available simulation packages including GULP and LAMMPS.

Spin and valence dependence of iron partitioning in Earth’s deep mantle

PubMed Central

Piet, Hélène; Badro, James; Nabiei, Farhang; Dennenwaldt, Teresa; Shim, Sang-Heon; Cantoni, Marco; Hébert, Cécile; Gillet, Philippe

2016-01-01

We performed laser-heated diamond anvil cell experiments combined with state-of-the-art electron microanalysis (focused ion beam and aberration-corrected transmission electron microscopy) to study the distribution and valence of iron in Earth’s lower mantle as a function of depth and composition. Our data reconcile the apparently discrepant existing dataset, by clarifying the effects of spin (high/low) and valence (ferrous/ferric) states on iron partitioning in the deep mantle. In aluminum-bearing compositions relevant to Earth’s mantle, iron concentration in silicates drops above 70 GPa before increasing up to 110 GPa with a minimum at 85 GPa; it then dramatically drops in the postperovskite stability field above 116 GPa. This compositional variation should strengthen the lowermost mantle between 1,800 km depth and 2,000 km depth, and weaken it between 2,000 km depth and the D” layer. The succession of layers could dynamically decouple the mantle above 2,000 km from the lowermost mantle, and provide a rheological basis for the stabilization and nonentrainment of large low-shear-velocity provinces below that depth. PMID:27647917

[Emotional valence of words in schizophrenia].

PubMed

Jalenques, I; Enjolras, J; Izaute, M

2013-06-01

Emotion recognition is a domain in which deficits have been reported in schizophrenia. A number of emotion classification studies have indicated that emotion processing deficits in schizophrenia are more pronounced for negative affects. Given the difficulty of developing material suitable for the study of these emotional deficits, it would be interesting to examine whether patients suffering from schizophrenia are responsive to positively and negatively charged emotion-related words that could be used within the context of remediation strategies. The emotional perception of words was examined in a clinical experiment involving schizophrenia patients. This emotional perception was expressed by the patients in terms of the valence associated with the words. In the present study, we investigated whether schizophrenia patients would assign the same negative and positive valences to words as healthy individuals. Twenty volunteer, clinically stable, outpatients from the Psychiatric Service of the University Hospital of Clermont-Ferrand were recruited. Diagnoses were based on DSM-IV criteria. Global psychiatric symptoms were assessed using the Positive and Negative Symptoms Scale (PANSS). The patients had to evaluate the emotional valence of a set of 300 words on a 5-point scale ranging from "very unpleasant" to "very pleasant". . The collected results were compared with those obtained by Bonin et al. (2003) [13] from 97 University students. Correlational analyses of the two studies revealed that the emotional valences were highly correlated, i.e. the schizophrenia patients estimated very similar emotional valences. More precisely, it was possible to examine three separate sets of 100 words each (positive words, neutral words and negative words). The positive words that were evaluated were the more positive words from the norms collected by Bonin et al. (2003) [13], and the negative words were the more negative examples taken from these norms. The neutral words

Intermediate-valence state of the Sm and Eu in SmB6 and EuCu2Si2: neutron spectroscopy data and analysis

NASA Astrophysics Data System (ADS)

Savchenkov, P. S.; Alekseev, P. A.; Podlesnyak, A.; Kolesnikov, A. I.; Nemkovski, K. S.

2018-02-01

Magnetic neutron scattering data for Sm (SmB6, Sm(Y)S) and Eu (EuCu2Si2-x Ge x ) intermediate-valence compounds have been analysed in terms of a generalized model of the intermediate-radius exciton. Special attention is paid to the correlation between the average ion’s valence and parameters of the low-energy excitation in the neutron spectra, such as the resonance mode, including its magnetic form factor. Along with specific features of the formation of the intermediate-valence state for Sm and Eu ions, common physical mechanisms have been revealed for systems based on these elements from the middle of the rare-earth series. A consistent description of the existing experimental data has been obtained by using the concept of a loosely bound hole for the Eu f-electron shell in the intermediate-valence state, in analogy with the previously established loosely bound electron model for the Sm ion.

Intermediate-valence state of the Sm and Eu in SmB 6 and EuCu 2 Si 2 : neutron spectroscopy data and analysis

DOE PAGES

Savchenkov, P. S.; Alekseev, P. A.; Podlesnyak, A.; ...

2018-01-11

For this study, magnetic neutron scattering data for Sm (SmB 6, Sm(Y)S) and Eu (EuCu 2Si 2- x Ge x ) intermediate-valence compounds have been analysed in terms of a generalized model of the intermediate-radius exciton. Special attention is paid to the correlation between the average ion's valence and parameters of the low-energy excitation in the neutron spectra, such as the resonance mode, including its magnetic form factor. Along with specific features of the formation of the intermediate-valence state for Sm and Eu ions, common physical mechanisms have been revealed for systems based on these elements from the middle ofmore » the rare-earth series. A consistent description of the existing experimental data has been obtained by using the concept of a loosely bound hole for the Eu f-electron shell in the intermediate-valence state, in analogy with the previously established loosely bound electron model for the Sm ion.« less

Intermediate-valence state of the Sm and Eu in SmB 6 and EuCu 2 Si 2 : neutron spectroscopy data and analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savchenkov, P. S.; Alekseev, P. A.; Podlesnyak, A.

For this study, magnetic neutron scattering data for Sm (SmB 6, Sm(Y)S) and Eu (EuCu 2Si 2- x Ge x ) intermediate-valence compounds have been analysed in terms of a generalized model of the intermediate-radius exciton. Special attention is paid to the correlation between the average ion's valence and parameters of the low-energy excitation in the neutron spectra, such as the resonance mode, including its magnetic form factor. Along with specific features of the formation of the intermediate-valence state for Sm and Eu ions, common physical mechanisms have been revealed for systems based on these elements from the middle ofmore » the rare-earth series. A consistent description of the existing experimental data has been obtained by using the concept of a loosely bound hole for the Eu f-electron shell in the intermediate-valence state, in analogy with the previously established loosely bound electron model for the Sm ion.« less

Exploring the Nature of the H[subscript 2] Bond. 1. Using Spreadsheet Calculations to Examine the Valence Bond and Molecular Orbital Methods

ERIC Educational Resources Information Center

Halpern, Arthur M.; Glendening, Eric D.

2013-01-01

A three-part project for students in physical chemistry, computational chemistry, or independent study is described in which they explore applications of valence bond (VB) and molecular orbital-configuration interaction (MO-CI) treatments of H[subscript 2]. Using a scientific spreadsheet, students construct potential-energy (PE) curves for several…

On the correlations between the polyhedron eccentricity parameters and the bond-valence sums for the cations with one lone electron pair. Addendum.

PubMed

Sidey, Vasyl

2009-06-01

Systematic variations of the bond-valence sums calculated from the poorly determined bond-valence parameters [Sidey (2008), Acta Cryst. B64, 515-518] have been illustrated using a simple graphical scheme.

Analysis of Ti valence states in resistive switching regions of a rutile TiO2‑ x four-terminal memristive device

NASA Astrophysics Data System (ADS)

Yamaguchi, Kengo; Takeuchi, Shotaro; Tohei, Tetsuya; Ikarashi, Nobuyuki; Sakai, Akira

2018-06-01

We have performed Ti valence state analysis of our four-terminal rutile TiO2‑ x single-crystal memristors using scanning transmission electron microscopy–electron energy loss spectroscopy (STEM–EELS). Analysis of Ti-L2,3 edge EELS spectra revealed that the electrocolored region formed by the application of voltage includes a valence state reflecting highly reduced TiO2‑ x due to the accumulation of oxygen vacancies. Such a valence state mainly exists within ∼50 nm from the crystal surface and extends along specific crystal directions. These electrically reduced surface layers are considered to directly contribute to the resistive switching (RS) in the four-terminal device. The present results add new insights into the microscopic mechanisms of the RS phenomena and should contribute to further development and improvements of TiO2‑ x based memristive devices.

First-principle simulations of electronic structure in semicrystalline polyethylene

NASA Astrophysics Data System (ADS)

Moyassari, A.; Unge, M.; Hedenqvist, M. S.; Gedde, U. W.; Nilsson, F.

2017-05-01

In order to increase our fundamental knowledge about high-voltage cable insulation materials, realistic polyethylene (PE) structures, generated with a novel molecular modeling strategy, have been analyzed using first principle electronic structure simulations. The PE structures were constructed by first generating atomistic PE configurations with an off-lattice Monte Carlo method and then equilibrating the structures at the desired temperature and pressure using molecular dynamics simulations. Semicrystalline, fully crystalline and fully amorphous PE, in some cases including crosslinks and short-chain branches, were analyzed. The modeled PE had a structure in agreement with established experimental data. Linear-scaling density functional theory (LS-DFT) was used to examine the electronic structure (e.g., spatial distribution of molecular orbitals, bandgaps and mobility edges) on all the materials, whereas conventional DFT was used to validate the LS-DFT results on small systems. When hybrid functionals were used, the simulated bandgaps were close to the experimental values. The localization of valence and conduction band states was demonstrated. The localized states in the conduction band were primarily found in the free volume (result of gauche conformations) present in the amorphous regions. For branched and crosslinked structures, the localized electronic states closest to the valence band edge were positioned at branches and crosslinks, respectively. At 0 K, the activation energy for transport was lower for holes than for electrons. However, at room temperature, the effective activation energy was very low (˜0.1 eV) for both holes and electrons, which indicates that the mobility will be relatively high even below the mobility edges and suggests that charge carriers can be hot carriers above the mobility edges in the presence of a high electrical field.

What is the Valence of Mn in Ga(1-x)Mn(x)N?

PubMed

Nelson, Ryky; Berlijn, Tom; Moreno, Juana; Jarrell, Mark; Ku, Wei

2015-11-06

We investigate the current debate on the Mn valence in Ga(1-x)Mn(x)N, a diluted magnetic semiconductor (DMS) with a potentially high Curie temperature. From a first-principles Wannier-function analysis, we unambiguously find the Mn valence to be close to 2+ (d(5)), but in a mixed spin configuration with average magnetic moments of 4μ(B). By integrating out high-energy degrees of freedom differently, we further derive for the first time from first-principles two low-energy pictures that reflect the intrinsic dual nature of the doped holes in the DMS: (1) an effective d(4) picture ideal for local physics, and (2) an effective d(5) picture suitable for extended properties. In the latter, our results further reveal a few novel physical effects, and pave the way for future realistic studies of magnetism. Our study not only resolves one of the outstanding key controversies of the field, but also exemplifies the general need for multiple effective descriptions to account for the rich low-energy physics in many-body systems in general.

When One Configuration Is Not Enough

ERIC Educational Resources Information Center

McMillin, David R.

2008-01-01

For most molecules molecular orbital theory predicts a ground-state electronic configuration that is useful for rationalizing relative bond lengths, magnetic properties, and so forth. However, when electron correlation is a dominant consideration, the ground-state configuration may provide a poor representation of the system. In such cases,…

Non-orthogonal internally contracted multi-configurational perturbation theory (NICPT): Dynamic electron correlation for large, compact active spaces

NASA Astrophysics Data System (ADS)

Kähler, Sven; Olsen, Jeppe

2017-11-01

A computational method is presented for systems that require high-level treatments of static and dynamic electron correlation but cannot be treated using conventional complete active space self-consistent field-based methods due to the required size of the active space. Our method introduces an efficient algorithm for perturbative dynamic correlation corrections for compact non-orthogonal MCSCF calculations. In the algorithm, biorthonormal expansions of orbitals and CI-wave functions are used to reduce the scaling of the performance determining step from quadratic to linear in the number of configurations. We describe a hierarchy of configuration spaces that can be chosen for the active space. Potential curves for the nitrogen molecule and the chromium dimer are compared for different configuration spaces. Already the most compact spaces yield qualitatively correct potentials that with increasing size of configuration spaces systematically approach complete active space results.

Valence Band Control of Metal Silicide Films via Stoichiometry.

PubMed

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

2016-07-07

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.

Electronic and spectroscopic characterizations of SNP isomers

NASA Astrophysics Data System (ADS)

Trabelsi, Tarek; Al Mogren, Muneerah Mogren; Hochlaf, Majdi; Francisco, Joseph S.

2018-02-01

High-level ab initio electronic structure calculations were performed to characterize SNP isomers. In addition to the known linear SNP, cyc-PSN, and linear SPN isomers, we identified a fourth isomer, linear PSN, which is located ˜2.4 eV above the linear SNP isomer. The low-lying singlet and triplet electronic states of the linear SNP and SPN isomers were investigated using a multi-reference configuration interaction method and large basis set. Several bound electronic states were identified. However, their upper rovibrational levels were predicted to pre-dissociate, leading to S + PN, P + NS products, and multi-step pathways were discovered. For the ground states, a set of spectroscopic parameters were derived using standard and explicitly correlated coupled-cluster methods in conjunction with augmented correlation-consistent basis sets extrapolated to the complete basis set limit. We also considered scalar and core-valence effects. For linear isomers, the rovibrational spectra were deduced after generation of their 3D-potential energy surfaces along the stretching and bending coordinates and variational treatments of the nuclear motions.

Positive valence music restores executive control over sustained attention

PubMed Central

Lewis, Bridget A.

2017-01-01

Music sometimes improves performance in sustained attention tasks. But the type of music employed in previous investigations has varied considerably, which can account for equivocal results. Progress has been hampered by lack of a systematic database of music varying in key characteristics like tempo and valence. The aims of this study were to establish a database of popular music varying along the dimensions of tempo and valence and to examine the impact of music varying along these dimensions on restoring attentional resources following performance of a sustained attention to response task (SART) vigil. Sixty-nine participants rated popular musical selections that varied in valence and tempo to establish a database of four musical types: fast tempo positive valence, fast tempo negative valence, slow tempo positive valence, and slow tempo negative valence. A second group of 89 participants performed two blocks of the SART task interspersed with either no break or a rest break consisting of 1 of the 4 types of music or silence. Presenting positive valence music (particularly of slow tempo) during an intermission between two successive blocks of the SART significantly decreased miss rates relative to negative valence music or silence. Results support an attentional restoration theory of the impact of music on sustained attention, rather than arousal theory and demonstrate a means of restoring sustained attention. Further, the results establish the validity of a music database that will facilitate further investigations of the impact of music on performance. PMID:29145395

Positive valence music restores executive control over sustained attention.

PubMed

Baldwin, Carryl L; Lewis, Bridget A

2017-01-01

Music sometimes improves performance in sustained attention tasks. But the type of music employed in previous investigations has varied considerably, which can account for equivocal results. Progress has been hampered by lack of a systematic database of music varying in key characteristics like tempo and valence. The aims of this study were to establish a database of popular music varying along the dimensions of tempo and valence and to examine the impact of music varying along these dimensions on restoring attentional resources following performance of a sustained attention to response task (SART) vigil. Sixty-nine participants rated popular musical selections that varied in valence and tempo to establish a database of four musical types: fast tempo positive valence, fast tempo negative valence, slow tempo positive valence, and slow tempo negative valence. A second group of 89 participants performed two blocks of the SART task interspersed with either no break or a rest break consisting of 1 of the 4 types of music or silence. Presenting positive valence music (particularly of slow tempo) during an intermission between two successive blocks of the SART significantly decreased miss rates relative to negative valence music or silence. Results support an attentional restoration theory of the impact of music on sustained attention, rather than arousal theory and demonstrate a means of restoring sustained attention. Further, the results establish the validity of a music database that will facilitate further investigations of the impact of music on performance.

Location of the valence band maximum in the band structure of anisotropic 1 T'-ReSe2

NASA Astrophysics Data System (ADS)

Eickholt, P.; Noky, J.; Schwier, E. F.; Shimada, K.; Miyamoto, K.; Okuda, T.; Datzer, C.; Drüppel, M.; Krüger, P.; Rohlfing, M.; Donath, M.

2018-04-01

Transition-metal dichalcogenides (TMDCs) are a focus of current research due to their fascinating optical and electronic properties with possible technical applications. ReSe2 is an interesting material of the TMDC family, with unique anisotropic properties originating from its distorted 1 T structure (1 T '). To develop a fundamental understanding of the optical and electric properties, we studied the underlying electronic structure with angle-resolved photoemission (ARPES) as well as band-structure calculations within the density functional theory (DFT)-local density approximation (LDA) and GdW approximations. We identified the Γ ¯M¯1 direction, which is perpendicular to the a axis, as a distinct direction in k space with the smallest bandwidth of the highest valence band. Using photon-energy-dependent ARPES, two valence band maxima are identified within experimental limits of about 50 meV: one at the high-symmetry point Z , and a second one at a non-high-symmetry point in the Brillouin zone. Thus, the position in k space of the global valence band maximum is undecided experimentally. Theoretically, an indirect band gap is predicted on a DFT-LDA level, while quasiparticle corrections lead to a direct band gap at the Z point.

Ultrafast Molecular Three-Electron Auger Decay.

PubMed

Feifel, Raimund; Eland, John H D; Squibb, Richard J; Mucke, Melanie; Zagorodskikh, Sergey; Linusson, Per; Tarantelli, Francesco; Kolorenč, Přemysl; Averbukh, Vitali

2016-02-19

Three-electron Auger decay is an exotic and elusive process, in which two outer-shell electrons simultaneously refill an inner-shell double vacancy with emission of a single Auger electron. Such transitions are forbidden by the many-electron selection rules, normally making their decay lifetimes orders of magnitude longer than the few-femtosecond lifetimes of normal (two-electron) Auger decay. Here we present theoretical predictions and direct experimental evidence for a few-femtosecond three-electron Auger decay of a double inner-valence-hole state in CH_{3}F. Our analysis shows that in contrast to double core holes, double inner-valence vacancies in molecules can decay exclusively by this ultrafast three-electron Auger process, and we predict that this phenomenon occurs widely.

Identification of Cr valence states in Cr and Nd co-doped Lu3Al5O12 laser ceramics

NASA Astrophysics Data System (ADS)

Zhang, Pande; Jiang, Benxue; Fan, Jintai; Mao, Xiaojian; Zhang, Long

2017-09-01

Cr and Nd co-doped laser ceramics, as the potential gain materials in inertial confinement fusion (ICF), have been widely investigated. And the study on valence states of chromium ions is important. The effects of sintering additives and annealing atmosphere on the valence state of chromium were studied in detail, and the results shown that the Cr valence states were demonstrated to be Cr2+ and Cr3+ ions in HIP-sintered Cr(0.2 at.%), Nd(0.8 at.%): LuAG laser ceramics. And the intensity of the near-infrared absorption band caused by Cr2+ ions was attenuated with the decreasing SiO2 concentration and increasing MgO amount. The near-infrared absorption could be eliminated by annealing in air. And the transformation of valence states of Cr ions in the Cr,Nd:LuAG ceramics were also confirmed by electron paramagnetic resonance and X-ray photoelectron spectroscopy.

Block correlated second order perturbation theory with a generalized valence bond reference function.

PubMed

Xu, Enhua; Li, Shuhua

2013-11-07

The block correlated second-order perturbation theory with a generalized valence bond (GVB) reference (GVB-BCPT2) is proposed. In this approach, each geminal in the GVB reference is considered as a "multi-orbital" block (a subset of spin orbitals), and each occupied or virtual spin orbital is also taken as a single block. The zeroth-order Hamiltonian is set to be the summation of the individual Hamiltonians of all blocks (with explicit two-electron operators within each geminal) so that the GVB reference function and all excited configuration functions are its eigenfunctions. The GVB-BCPT2 energy can be directly obtained without iteration, just like the second order Mo̸ller-Plesset perturbation method (MP2), both of which are size consistent. We have applied this GVB-BCPT2 method to investigate the equilibrium distances and spectroscopic constants of 7 diatomic molecules, conformational energy differences of 8 small molecules, and bond-breaking potential energy profiles in 3 systems. GVB-BCPT2 is demonstrated to have noticeably better performance than MP2 for systems with significant multi-reference character, and provide reasonably accurate results for some systems with large active spaces, which are beyond the capability of all CASSCF-based methods.

Architectural Representation of Valence in the Limbic System

PubMed Central

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

2016-01-01

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

Tunable electronic properties of graphene through controlling bonding configurations of doped nitrogen atoms

PubMed Central

Zhang, Jia; Zhao, Chao; Liu, Na; Zhang, Huanxi; Liu, Jingjing; Fu, Yong Qing; Guo, Bin; Wang, Zhenlong; Lei, Shengbin; Hu, PingAn

2016-01-01

Single–layer and mono–component doped graphene is a crucial platform for a better understanding of the relationship between its intrinsic electronic properties and atomic bonding configurations. Large–scale doped graphene films dominated with graphitic nitrogen (GG) or pyrrolic nitrogen (PG) were synthesized on Cu foils via a free radical reaction at growth temperatures of 230–300 °C and 400–600 °C, respectively. The bonding configurations of N atoms in the graphene lattices were controlled through reaction temperature, and characterized using Raman spectroscopy, X–ray photoelectron spectroscopy and scanning tunneling microscope. The GG exhibited a strong n–type doping behavior, whereas the PG showed a weak n–type doping behavior. Electron mobilities of the GG and PG were in the range of 80.1–340 cm2 V−1·s−1 and 59.3–160.6 cm2 V−1·s−1, respectively. The enhanced doping effect caused by graphitic nitrogen in the GG produced an asymmetry electron–hole transport characteristic, indicating that the long–range scattering (ionized impurities) plays an important role in determining the carrier transport behavior. Analysis of temperature dependent conductance showed that the carrier transport mechanism in the GG was thermal excitation, whereas that in the PG, was a combination of thermal excitation and variable range hopping. PMID:27325386

Pressure dependence of Ce valence in CeRhIn 5

DOE PAGES

Brubaker, Z. E.; Stillwell, R. L.; Chow, P.; ...

2017-12-14

We have studied the Ce valence as a function of pressure in CeRhIn5 at 300 K and at 22 K using x-ray absorption spectroscopy in partial fluorescent yield mode. At room temperature, we found no detectable change in Ce valence greater than 0.01 up to a pressure of 5.5 GPa. At 22 K, the valence remains robust against pressure below 6 GPa, in contrast to the predicted valence crossover at P = 2.35 GPa. In conclusion, this work yields an upper limit for the change in Ce-valence and suggests that the critical valence fluctuation scenario, in its current form, ismore » unlikely.« less

The Effect of Cerium Oxide Nanoparticle Valence State on Reactive Oxygen Species and Toxicity.

PubMed

Dunnick, Katherine M; Pillai, Rajalekshmi; Pisane, Kelly L; Stefaniak, Aleksandr B; Sabolsky, Edward M; Leonard, Stephen S

2015-07-01

Cerium oxide (CeO2) nanoparticles, which are used in a variety of products including solar cells, gas sensors, and catalysts, are expected to increase in industrial use. This will subsequently lead to additional occupational exposures, making toxicology screenings crucial. Previous toxicology studies have presented conflicting results as to the extent of CeO2 toxicity, which is hypothesized to be due to the ability of Ce to exist in both a +3 and +4 valence state. Thus, to study whether valence state and oxygen vacancy concentration are important in CeO2 toxicity, CeO2 nanoparticles were doped with gadolinium to adjust the cation (Ce, Gd) and anion (O) defect states. The hypothesis that doping would increase toxicity and decrease antioxidant abilities as a result of increased oxygen vacancies and inhibition of +3 to +4 transition was tested. Differences in toxicity and reactivity based on valence state were determined in RLE-6TN rat alveolar epithelial and NR8383 rat alveolar macrophage cells using enhanced dark field microscopy, electron paramagnetic resonance (EPR), and annexin V/propidium iodide cell viability stain. Results from EPR indicated that as doping increased, antioxidant potential decreased. Alternatively, doping had no effect on toxicity at 24 h. The present results imply that as doping increases, thus subsequently increasing the Ce(3+)/Ce(4+) ratio, antioxidant potential decreases, suggesting that differences in reactivity of CeO2 are due to the ability of Ce to transition between the two valence states and the presence of increased oxygen vacancies, rather than dependent on a specific valence state.

Magnetic-field induced quantum critical points of valence transition in Ce- and Yb-based heavy fermions

NASA Astrophysics Data System (ADS)

Watanabe, Shinji; Tsuruta, Atsushi; Miyake, Kazumasa; Flouquet, Jacques

2009-03-01

Valence instability and its critical fluctuations have attracted much attention recently in the heavy-electron systems. Valence fluctuations are essentially charge fluctuations, and it is highly non-trivial how the quantum critical point (QCP) as well as the critical end point is controlled by the magnetic field. To clarify this fundamental issue, we have studied the mechanism of how the critical points of the first-order valence transitions are controlled by the magnetic field [1]. We show that the critical temperature is suppressed to be the QCP by the magnetic field and unexpectedly the QCP exhibits nonmonotonic field dependence in the ground-state phase diagram, giving rise to emergence of metamagnetism even in the intermediate valence-crossover regime. The driving force of the field-induced QCP is clarified to be a cooperative phenomenon of Zeeman effect and Kondo effect, which creates a distinct energy scale from the Kondo temperature. This mechanism explains a peculiar magnetic response in CeIrIn5 and metamagnetic transition in YbXCu4 for X=In as well as a sharp contrast between X=Ag and Cd. We present the novel phenomena under the magnetic field to discuss significance of the proximity of the critical points of the first-order valence transition. [1] S. Watanabe et al. PRL100, (2008) 236401.

Characterization of the HSiN HNSi system in its electronic ground state

NASA Astrophysics Data System (ADS)

Lind, Maria C.; Pickard, Frank C.; Ingels, Justin B.; Paul, Ankan; Yamaguchi, Yukio; Schaefer, Henry F.

2009-03-01

The electronic ground states (X˜Σ+1) of HSiN, HNSi, and the transition state connecting the two isomers were systematically studied using configuration interaction with single and double (CISD) excitations, coupled cluster with single and double (CCSD) excitations, CCSD with perturbative triple corrections [CCSD(T)], multireference complete active space self-consistent field (CASSCF), and internally contracted multireference configuration interaction (ICMRCI) methods. The correlation-consistent polarized valence (cc-pVXZ), augmented correlation-consistent polarized valence (aug-cc-pVXZ) (X=T,Q,5), correlation-consistent polarized core-valence (cc-pCVYZ), and augmented correlation-consistent polarized core-valence (aug-cc-pCVYZ) (Y=T,Q) basis sets were used. Via focal point analyses, we confirmed the HNSi isomer as the global minimum on the ground state HSiN HNSi zero-point vibrational energy corrected surface and is predicted to lie 64.7kcalmol-1 (22640cm-1, 2.81eV) below the HSiN isomer. The barrier height for the forward isomerization reaction (HSiN→HNSi) is predicted to be 9.7kcalmol-1, while the barrier height for the reverse process (HNSi→HSiN) is determined to be 74.4kcalmol-1. The dipole moments of the HSiN and HNSi isomers are predicted to be 4.36 and 0.26D, respectively. The theoretical vibrational isotopic shifts for the HSiN/DSiN and HNSi/DNSi isotopomers are in strong agreement with the available experimental values. The dissociation energy for HSiN [HSiN(X˜Σ+1)→H(S2)+SiN(XΣ+2)] is predicted to be D0=59.6kcalmol-1, whereas the dissociation energy for HNSi [HNSi(X˜Σ+1)→H(S2)+NSi(XΣ+2)] is predicted to be D0=125.0kcalmol-1 at the CCSD(T)/aug-cc-pCVQZ level of theory. Anharmonic vibrational frequencies computed using second order vibrational perturbation theory are in good agreement with available matrix isolation experimental data for both HSiN and HNSi isomers root mean squared derivation (RMSD=9cm-1).

Difference between resistance degradation of fixed valence acceptor (Mg) and variable valence acceptor (Mn)-doped BaTiO3 ceramics

NASA Astrophysics Data System (ADS)

Yoon, Seok-Hyun; Randall, Clive A.; Hur, Kang-Heon

2010-09-01

The difference in the resistance degradation behavior was investigated between fixed valence acceptor (Mg) and the variable valence acceptor (Mn)-doped BaTiO3 ceramics with an increase of each acceptor concentration. Coarse-grained specimens with uniform grain sizes and different acceptor concentrations were prepared. In the case of Mg-doped BaTiO3, the time to degradation systematically decreased with the increase in Mg concentration. In contrast, there is a systematically increased time to degradation with the increase in Mn concentration in Mn-doped BaTiO3. The fast degradation by the increase in Mg concentration directly corresponded to an increase in the Warburg impedance and ionic transference number (tion) associated with an increase in oxygen vacancy concentration ([VO••]). On the other hand, no distinct Warburg impedance or ionic conduction contribution could be observed with the increase in Mn concentration. It is supposed that the increase in [VO••] is negligible in spite of the increase in acceptor Mn concentration, when it is compared to Mg-doped BaTiO3. The much lower [VO••] and more dominant electron/hole trapping effect due to multivalence nature of Mn are supposed to cause such a contrary degradation behavior between Mg and Mn-doped BaTiO3. Reoxidation in a slightly reducing atmosphere (N2) showed better resistance to degradation behavior than in a oxidizing air atmosphere in both Mg and Mn-doped BaTiO3, which is anticipated to be an increase in the electron/hole trapping sites. All these behaviors could be explained by the low temperature defect chemical model that shows difference in the defect structure between Mg and Mn-doped BaTiO3, and its dependence on the oxygen partial pressure (pO2) during reoxidation and cooling. Not only the [VO••], but also the density of electron/hole trap sites, are believed to be crucial in controlling resistance degradation.

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.

Affective valence signals agency within and between individuals.

PubMed

Chang, Yen-Ping; Algoe, Sara B; Chen, Lung Hung

2017-03-01

Affective valence is a core component of all emotional experiences. Building on recent evidence and theory, we reason that valence informs individuals about their agency-the mental capability of doing and intending. Expressed affect may also lead to perceptions of agency by others. Supporting the hypothesis that valence influences self- and other-perception of agency, across 5 studies, we showed that participants perceived more agency in themselves in positive versus neutral and negative personal (Study 1) and interpersonal (Study 2) events. Participants also perceived more agency in fictional characters showing positive versus negative affect, regardless of how acceptable the characters' behavior was (Studies 3 and 4). Finally, we had participants personify 24 specific emotions across the valence dimension, and found that the more positive and less negative an emotion was, the more agency participants ascribed to the "person" (Study 5). We discuss the results in terms of how valence may help with human self- and social regulation. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

The Valence- and Conduction-Band Structure of the Sapphire (1102) Surface.

DTIC Science & Technology

1984-12-01

surface. The pbotomission spectrum of the valece-baud region has boon adjusted to rmove croas-section effect s and comparod to the recent theoretical ...transitions in Al203. Several theoretical deteminations of the electron structure of various A1203 analoaues have bes performed. These calculations were...picture of the valence sad core density of states in sapphire. The rew, 31 velesee-bend data of Fit. I& and the theoretical 003 shows is Fig. 1.. which

Synthesis, characterization, and photophysical properties of a series of supramolecular mixed-valence compounds.

PubMed

Pfennig, B W; Fritchman, V A; Hayman, K A

2001-01-15

The synthesis and characterization of 10 cyano-bridged trinuclear mixed-valence compounds of the form [(NH3)5M-NC-FeII(CN)4-CN-M'(NH3)5]n+ (M = RuIII, OsIII, CrIII, or PtIV; n = 2, 3, or 4) is reported. The electronic spectra of these supramolecular compounds exhibit a single intervalent (IT) absorption band for each nondegenerate Fe-->M/M' transition. The redox potential of the Fe(II) center is shifted more positive with the addition of each coordinated metal complex, while the redox potentials of the pendant metals vary only slightly from their dinuclear counterparts. As a result, the Fe-->M IT bands are blue-shifted from those in the corresponding dinuclear mixed-valence compounds. The energies of these IT bands show a linear correlation with the ground-state thermodynamic driving force, as predicted by classical electron transfer theory. Estimates of the degree of electronic coupling (Hab) between the metal centers using a theoretical analysis of the IT band shapes indicate that most of these values are similar to those for the corresponding dinuclear species. Notable exceptions occur for the Fe-->M IT transitions in Os-Fe-M (M = Cr or Pt). The enhanced electronic coupling in these two species can be explained as a result of excited state mixing between electron transfer and/or ligand-based charge transfer states and an intensity-borrowing mechanism. Additionally, the possibility of electronic coupling between the remote metal centers in the Ru-Fe-Ru species is discussed in order to explain the observation of two closely spaced redox waves for the degenerate Ru(III) acceptors.

On the unusual stability of valence anions of thymine based on very rare tautomers. A computational study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mazurkiewicz, Kamil; Bachorz, Rafal; Gutowski, Maciej S.

2006-12-07

We characterized valence-type and dipole-bound anionic states of thymine using various electronic structure methods, with the most accurate results obtained at the CCSD(T)/aug-cc-pVDZ level of theory followed by extrapolations to complete basis set limits. We found that the most stable anion in the gas phase is related to neither the canonical 2,4-dioxo nor a rare imino-hydroxy tautomer. Instead, it is related to an imino-oxo tautomer, in which the N1H proton is transferred to the C5 atom. This valence anion is characterized by an electron vertical detachment energy (VDE) of 1251 meV and it is adiabatically stable with respect to themore » canonical neutral by 2.4 kcal/mol. It is also more stable than the dipole-bound and valence anion of the canonical tautomer. The latter is adiabatically unbound with respect to by 0.1 kcal/mol and this instability is smaller than the uncertainty of the computational model used. The VDE values for and are 55 and 457 meV, respectively. Another, anionic, low-lying imino-oxo tautomer with a VDE of 2458 meV has a proton transferred from N3H to C5. It is less stable than by 3.2 kcal/mol. The mechanism of formation of anionic tautomers with the carbons C5 or C6 protonated may involve intermolecular proton transfer or dissociative electron attachment to the canonical neutral tautomer followed by a barrier-free attachment of a hydrogen atom to C5. The six-member ring structure of anionic tautomers with carbon atoms protonated might be unstable upon an excess electron detachment. Indeed, the neutral systems resulting from electron detachment from and evolve, along barrier-free decomposition pathways, to a linear or a bicyclo structure, respectively, which might be viewed as lesions to DNA.« less

Laser-induced electron dynamics including photoionization: A heuristic model within time-dependent configuration interaction theory.

PubMed

Klinkusch, Stefan; Saalfrank, Peter; Klamroth, Tillmann

2009-09-21

We report simulations of laser-pulse driven many-electron dynamics by means of a simple, heuristic extension of the time-dependent configuration interaction singles (TD-CIS) approach. The extension allows for the treatment of ionizing states as nonstationary states with a finite, energy-dependent lifetime to account for above-threshold ionization losses in laser-driven many-electron dynamics. The extended TD-CIS method is applied to the following specific examples: (i) state-to-state transitions in the LiCN molecule which correspond to intramolecular charge transfer, (ii) creation of electronic wave packets in LiCN including wave packet analysis by pump-probe spectroscopy, and, finally, (iii) the effect of ionization on the dynamic polarizability of H(2) when calculated nonperturbatively by TD-CIS.

Actively controlling coolant-cooled cold plate configuration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chainer, Timothy J.; Parida, Pritish R.

Cooling apparatuses are provided to facilitate active control of thermal and fluid dynamic performance of a coolant-cooled cold plate. The cooling apparatus includes the cold plate and a controller. The cold plate couples to one or more electronic components to be cooled, and includes an adjustable physical configuration. The controller dynamically varies the adjustable physical configuration of the cold plate based on a monitored variable associated with the cold plate or the electronic component(s) being cooled by the cold plate. By dynamically varying the physical configuration, the thermal and fluid dynamic performance of the cold plate are adjusted to, formore » example, optimally cool the electronic component(s), and at the same time, reduce cooling power consumption used in cooling the electronic component(s). The physical configuration can be adjusted by providing one or more adjustable plates within the cold plate, the positioning of which may be adjusted based on the monitored variable.« less

Taboo, emotionally valenced, and emotionally neutral word norms.

PubMed

Janschewitz, Kristin

2008-11-01

Although taboo words are used to study emotional memory and attention, no easily accessible normative data are available that compare taboo, emotionally valenced, and emotionally neutral words on the same scales. Frequency, inappropriateness, valence, arousal, and imageability ratings for taboo, emotionally valenced, and emotionally neutral words were made by 78 native-English-speaking college students from a large metropolitan university. The valenced set comprised both positive and negative words, and the emotionally neutral set comprised category-related and category-unrelated words. To account for influences of demand characteristics and personality factors on the ratings, frequency and inappropriateness measures were decomposed into raters' personal reactions to the words versus raters' perceptions of societal reactions to the words (personal use vs. familiarity and offensiveness vs. tabooness, respectively). Although all word sets were rated higher in familiarity and tabooness than in personal use and offensiveness, these differences were most pronounced for the taboo set. In terms of valence, the taboo set was most similar to the negative set, although it yielded higher arousal ratings than did either valenced set. Imageability for the taboo set was comparable to that of both valenced sets. The ratings of each word are presented for all participants as well as for single-sex groups. The inadequacies of the application of normative data to research that uses emotional words and the conceptualization of taboo words as a coherent category are discussed. Materials associated with this article may be accessed at the Psychonomic Society's Archive of Norms, Stimuli, and Data, www.psychonomic.org/archive.

Electronic interaction in an outer-sphere mixed-valence double salt: a polarized neutron diffraction study of K(3)(MnO(4))(2).

PubMed

Cannon, Roderick D; Jayasooriya, Upali A; Tilford, Claire; Anson, Christopher E; Sowrey, Frank E; Rosseinsky, David R; Stride, John A; Tasset, Francis; Ressouche, Eric; White, Ross P; Ballou, Rafik

2004-11-01

The mixed-valence double salt K(3)(MnO(4))(2) crystallizes in space group P2(1)/m with Z = 2. The manganese centers Mn1 and Mn2 constitute discrete "permanganate", [Mn(VII)O(4)](-), and "manganate", [Mn(VI)O(4)](2-), ions, respectively. There is a spin-ordering transition to an antiferromagnetic state at ca. T = 5 K. The spin-density distribution in the paramagnetic phase at T = 10 K has been determined by polarized neutron diffraction, confirming that unpaired spin is largely confined to the nominal manganate ion Mn2. Through use of both Fourier refinement and maximum entropy methods, the spin on Mn1 is estimated as 1.75 +/- 1% of one unpaired electron with an upper limit of 2.5%.

Electronic absorption and MCD spectra of M sub 2 (TMB) sub 4 sup 2+ , M = Rh and Ir. A valence-bond description of the upper electronic excited states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, D.C.; Miskowski, V.M.; Gray, H.B.

1990-05-09

Electronic absorption and magnetic circular dichroism (MCD) spectra of Rh{sub 2}(TMB){sub 4}{sup 2+} and Ir{sub 2}(TMB){sub 4}{sup 2+} are reported along with polarized single-crystal absorption spectra of (Ir{sub 2}(TMB){sub 4})(B(C{sub 6}H{sub 5}){sub 4}){sub 2} {times} CH{sub 3}C{sub 6}H{sub 5} (TMB = 2,5-diisocyano-2,5-dimethylhexane). Interpretation of the spectra is based on a valence-bond model that accommodates highly perturbed dimer transitions as well as monomer-like dimer excitations. In this model, half of the dimer electronic excited states possess ionic character; these states involve metal-to-metal charge transfer (MMCT). The most prominent of the weak features ({approximately} 430 nm) is assigned to the transition tomore » {sup 1}A{sub 1g} (a single-center d{sub z{sup 2}} {yields} p{sub z} excitation). High-energy features ({lambda} < 300 nm) in the spectra of Rh{sub 2}(TMB){sub 4}{sup 2+} and Ir{sub 2}(TMB){sub 4}{sup 2+} are assigned to MMCT arising from d{sub xzyz} {yields} p{sub z} excitations.« less

Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Addition of Hydrogen Atoms.

PubMed

Lindquist, Beth A; Takeshita, Tyler Y; Dunning, Thom H

2016-05-05

Ozone (O3) and sulfur dioxide (SO2) are valence isoelectronic species, yet their properties and reactivities differ dramatically. In particular, O3 is highly reactive, whereas SO2 is chemically relatively stable. In this paper, we investigate serial addition of hydrogen atoms to both the terminal atoms of O3 and SO2 and to the central atom of these species. It is well-known that the terminal atoms of O3 are much more amenable to bond formation than those of SO2. We show that the differences in the electronic structure of the π systems in the parent triatomic species account for the differences in the addition of hydrogen atoms to the terminal atoms of O3 and SO2. Further, we find that the π system in SO2, which is a recoupled pair bond dyad, facilitates the addition of hydrogen atoms to the sulfur atom, resulting in stable HSO2 and H2SO2 species.

Configuration interaction studies on the spectroscopic properties of PbO including spin-orbit coupling

NASA Astrophysics Data System (ADS)

Wang, Luo; Rui, Li; Zhiqiang, Gai; RuiBo, Ai; Hongmin, Zhang; Xiaomei, Zhang; Bing, Yan

2016-07-01

Lead oxide (PbO), which plays the key roles in a range of research fields, has received a great deal of attention. Owing to the large density of electronic states and heavy atom Pb including in PbO, the excited states of the molecule have not been well studied. In this work, high level multireference configuration interaction calculations on the low-lying states of PbO have been carried out by utilizing the relativistic effective core potential. The effects of the core-valence correlation correction, the Davidson modification, and the spin-orbital coupling on the electronic structure of the PbO molecule are estimated. The potential energy curves of 18 Λ-S states correlated to the lowest dissociation limit (Pb (3Pg) + O(3Pg)) are reported. The calculated spectroscopic parameters of the electronic states below 30000 cm-1, for instance, X1Σ+, 13Σ+, and 13Σ-, and their spin-orbit coupling interaction, are compared with the experimental results, and good agreements are derived. The dipole moments of the 18 Λ-S states are computed with the configuration interaction method, and the calculated dipole moments of X1Σ+ and 13Σ+ are consistent with the previous experimental results. The transition dipole moments from 11Π, 21Π, and 21Σ+ to X1Σ+ and other singlet excited states are estimated. The radiative lifetime of several low-lying vibrational levels of 11Π, 21Π, and 21Σ+ states are evaluated. Project supported by the National Natural Science Foundation of China (Grant Nos. 11404180 and 11574114), the Natural Science Foundation of Heilongjiang Province, China (Grant No. A2015010), the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province, China (Grant No. UNPYSCT-2015095), and the Natural Science Foundation of Jilin Province, China (Grant No. 20150101003JC).

Electronic structure of germanium selenide investigated using ultra-violet photo-electron spectroscopy

NASA Astrophysics Data System (ADS)

Mishra, P.; Lohani, H.; Kundu, A. K.; Patel, R.; Solanki, G. K.; Menon, Krishnakumar S. R.; Sekhar, B. R.

2015-07-01

The valence band electronic structure of GeSe single crystals has been investigated using angle resolved photoemission spectroscopy (ARPES) and x-ray photoelectron spectroscopy. The experimentally observed bands from ARPES, match qualitatively with our LDA-based band structure calculations along the Γ-Z, Γ-Y and Γ-T symmetry directions. The valence band maximum occurs nearly midway along the Γ-Z direction, at a binding energy of -0.5 eV, substantiating the indirect band gap of GeSe. Non-dispersive features associated with surface states and indirect transitions have been observed. The difference in hybridization of Se and Ge 4p orbitals leads to the variation of dispersion along the three symmetry directions. The predominance of the Se 4pz orbitals, evidenced from theoretical calculations, may be the cause for highly dispersive bands along the Γ-T direction. Detailed electronic structure analysis reveals the significance of the cation-anion 4p orbitals hybridization in the valence band dispersion of IV-VI semiconductors. This is the first comprehensive report of the electronic structure of a GeSe single crystal using ARPES in conjugation with theoretical band structure analysis.

Nonresonant valence-to-core x-ray emission spectroscopy of niobium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ravel, Bruce; Kropf, A. Jeremy; Yang, Dali

The valence-to-core (V2C) portion of x-ray emission spectroscopy (XES) measures the electron states close to the Fermi level. These states are involved in bonding, thus providing a measure of the chemistry of the material. For this paper, we show the V2C XES spectra for several niobium compounds. The Kβ" peak in the V2C XES results from the transition of a ligand 2s electron into the 1s core-hole of the niobium, a transition allowed by hybridization with the niobium 4p . This location in energy of this weak peak shows a strong ligand dependence, thus providing a sensitive probe of themore » ligand environment about the niobium.« less

Nonresonant valence-to-core x-ray emission spectroscopy of niobium

DOE PAGES

Ravel, Bruce; Kropf, A. Jeremy; Yang, Dali; ...

2018-03-23

The valence-to-core (V2C) portion of x-ray emission spectroscopy (XES) measures the electron states close to the Fermi level. These states are involved in bonding, thus providing a measure of the chemistry of the material. For this paper, we show the V2C XES spectra for several niobium compounds. The Kβ" peak in the V2C XES results from the transition of a ligand 2s electron into the 1s core-hole of the niobium, a transition allowed by hybridization with the niobium 4p . This location in energy of this weak peak shows a strong ligand dependence, thus providing a sensitive probe of themore » ligand environment about the niobium.« less

Effects of Emotional Valence and Arousal on Time Perception

PubMed Central

Van Volkinburg, Heather; Balsam, Peter

2016-01-01

We examined the influence of emotional arousal and valence on estimating time intervals. A reproduction task was used in which images from the International Affective Picture System served as the stimuli to be timed. Experiment 1 assessed the effects of positive and negative valence at a moderate arousal level and Experiment 2 replicated Experiment 1 with the addition of a high arousal condition. Overestimation increased as a function of arousal during encoding of times regardless of valence. For images presented during reproduction, overestimation occurred at the moderate arousal level for positive and negative valence but underestimation occurred in the negative valence high arousal condition. The overestimation of time intervals produced by emotional arousal during encoding and during reproduction suggests that emotional stimuli affect temporal information processing in a qualitatively different way during different phases of temporal information processing. PMID:27110491

Measurement of the low energy spectral contribution in coincidence with valence band (VB) energy levels of Ag(100) using VB-VB coincidence spectroscopy

NASA Astrophysics Data System (ADS)

Gladen, R. W.; Joglekar, P. V.; Lim, Z. H.; Shastry, K.; Hulbert, S. L.; Weiss, A. H.

A set of coincidence measurements were obtained for the study and measurement of the electron contribution arising from the inter-valence band (VB) transitions along with the inelastically scattered VB electron contribution. These Auger-unrelated contributions arise in the Auger spectrum (Ag 4p NVV) obtained using Auger Photoelectron Coincidence Spectroscopy (APECS). The measured Auger-unrelated contribution can be eliminated from Auger spectrum to obtain the spectrum related to Auger. In our VB-VB coincidence measurement, a photon beam of energy 180eV was used to probe the Ag(100) sample. The coincidence spectrum was obtained using two Cylindrical Mirror Analyzers (CMA's). The scan CMA measured the low energy electron contribution in the energy range 0-70eV in coincidence with VB electrons measured by the fixed CMA. In this talk, we present the data obtained for VB-VB coincidence at the valence band energy of 171eV along with the coincidence measurements in the energy range of 4p core and valence band. NSF DMR 0907679, NSF Award Number: 1213727. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, under Contract No. DEAC02-98CH10886.

Measurement of the low energy spectral contribution in coincidence with valence band (VB) energy levels of Ag(100) using VB-VB coincidence spectroscopy

NASA Astrophysics Data System (ADS)

Joglekar, P. V.; Gladen, R.; Lim, Z. H.; Shastry, K.; Hulbert, S. L.; Weiss, A. H.

2015-03-01

A set of coincidence measurements were obtained for the study and measurement of the electron contribution arising from the inter-valence band (VB) transitions along with the inelastically scattered VB electron contribution. These Auger-unrelated contributions arise in the Auger spectrum (Ag 4p NVV) obtained using Auger Photoelectron Coincidence Spectroscopy (APECS). The measured Auger-unrelated contribution can be eliminated from Auger spectrum to obtain the spectrum related to Auger. In our VB-VB coincidence measurement, a photon beam of energy 180eV was used to probe the Ag(100) sample. The coincidence spectrum was obtained using two Cylindrical Mirror Analyzers (CMA's). The scan CMA measured the low energy electron contribution in the energy range 0-70eV in coincidence with VB electrons measured by the fixed CMA. In this talk, we present the data obtained for VB-VB coincidence at the valence band energy of 171eV along with the coincidence measurements in the energy range of 4p core and valence band. NSF DMR 0907679, NSF Award Number: 1213727. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

Spectroscopic evidence for temperature dependent relative movement of light and heavy hole valence bands of PbQ (Q=Te,Se,S)

NASA Astrophysics Data System (ADS)

Chatterjee, Utpal; Zhao, Junjing; Kanatzidis, Mercouri; Malliakas, Christos

We have conducted temperature dependent Angle Resolved Photoemission Spectroscopy (ARPES) studies of the electronic structures of PbTe, PbSe and PbS. Our ARPES measurements provide direct evidences for the light hole upper valence bands (UVBs) and the so-called heavy hole lower valence bands (LVBs), and an unusual temperature dependent relative movement between their band maxima leading to a monotonic decrease in the energy separation between LVBs and UVBs with increase in temperature. This enables convergence of these valence bands and consequently an effective increase in the valley degeneracy in PbQ at higher temperatures, which has long been believed to be the driving factor behind their extraordinary thermoelectric performance.

Electronic structure of lanthanide scandates

NASA Astrophysics Data System (ADS)

Mizzi, Christopher A.; Koirala, Pratik; Marks, Laurence D.

2018-02-01

X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and density functional theory calculations were used to study the electronic structure of three lanthanide scandates: GdSc O3,TbSc O3 , and DySc O3 . X-ray photoelectron spectra simulated from first-principles calculations using a combination of on-site hybrid and GGA +U methods were found to be in good agreement with experimental x-ray photoelectron spectra. The hybrid method was used to model the ground state electronic structure and the GGA +U method accounted for the shift of valence state energies due to photoelectron emission via a Slater-Janak transition state approach. From these results, the lanthanide scandate valence bands were determined to be composed of Ln 4 f ,O 2 p , and Sc 3 d states, in agreement with previous work. However, contrary to previous work the minority Ln 4 f states were found to be located closer to, and in some cases at, the valence band maximum. This suggests that minority Ln 4 f electrons may play a larger role in lanthanide scandate properties than previously thought.

First determination of the valence band dispersion of CH3NH3PbI3 hybrid organic-inorganic perovskite

NASA Astrophysics Data System (ADS)

Lee, Min-I.; Barragán, Ana; Nair, Maya N.; Jacques, Vincent L. R.; Le Bolloc'h, David; Fertey, Pierre; Jemli, Khaoula; Lédée, Ferdinand; Trippé-Allard, Gaëlle; Deleporte, Emmanuelle; Taleb-Ibrahimi, Amina; Tejeda, Antonio

2017-07-01

The family of hybrid organic-inorganic halide perovskites is in the limelight because of their recently discovered high photovoltaic efficiency. These materials combine photovoltaic energy conversion efficiencies exceeding 22% and low-temperature and low-cost processing in solution; a breakthrough in the panorama of renewable energy. Solar cell operation relies on the excitation of the valence band electrons to the conduction band by solar photons. One factor strongly impacting the absorption efficiency is the band dispersion. The band dispersion has been extensively studied theoretically, but no experimental information was available. Herein, we present the first experimental determination of the valence band dispersion of methylammonium lead halide in the tetragonal phase. Our results pave the way for contrasting the electronic hopping or the electron effective masses in different theories by comparing to our experimental bands. We also show a significant broadening of the electronic states, promoting relaxed conditions for photon absorption, and demonstrate that the tetragonal structure associated to the octahedra network distortion below 50 °C induces only a minor modification of the electronic bands, with respect to the cubic phase at high temperature, thus minimizing the impact of the cubic-tetragonal transition on solar cell efficiencies.

Electronic structure and shearing in nanolaminated ternary carbides

NASA Astrophysics Data System (ADS)

Music, Denis; Sun, Zhimei; Voevodin, Andrey A.; Schneider, Jochen M.

2006-07-01

We have studied shearing in M 2AlC phases (M=Sc,Y,La,Ti,Zr,Hf,V,Nb,Ta,Cr,Mo,W) using ab initio calculations. We propose that these phases can be classified into two groups based on the valence electron concentration induced changes in C 44. One group comprises M=V B and VIB, where the C 44 values are approximately 170 GPa and independent of the corresponding MC. The other group includes M=IIIB and IVB, where the C 44 shows a linear dependency with the corresponding MC. This may be understood based on the electronic structure: shear resistant bands are filled in M 2AlC phases with M=V B and VIB, while they are not completely filled when M=IIIB and IVB. This notion is also consistent with our stress-strain analysis. These valence electron concentration induced changes in shear behaviour were compared to previously published valence electron concentration induced changes in compression behaviour [Z. Sun, D. Music, R. Ahuja, S. Li, J.M. Schneider, Phys. Rev. B 70 (2004) 092102]. These classification proposals exhibit identical critical valence electron concentration values for the group boundary. However, the physical mechanisms are not identical: the classification proposal for the bulk modulus is based on MC-A coupling, while shearing is based on MC-MC coupling.

Energy shift and conduction-to-valence band transition mediated by a time-dependent potential barrier in graphene

NASA Astrophysics Data System (ADS)

Chaves, Andrey; da Costa, D. R.; de Sousa, G. O.; Pereira, J. M.; Farias, G. A.

2015-09-01

We investigate the scattering of a wave packet describing low-energy electrons in graphene by a time-dependent finite-step potential barrier. Our results demonstrate that, after Klein tunneling through the barrier, the electron acquires an extra energy which depends on the rate of change of the barrier height with time. If this rate is negative, the electron loses energy and ends up as a valence band state after leaving the barrier, which effectively behaves as a positively charged quasiparticle.

The allocation of valenced concepts onto 3D space.

PubMed

Marmolejo-Ramos, Fernando; Tirado, Carlos; Arshamian, Edward; Vélez, Jorge Iván; Arshamian, Artin

2018-06-01

The valence-space metaphor research area investigates the metaphorical mapping of valenced concepts onto space. Research findings from this area indicate that positive, neutral, and negative concepts are associated with upward, midward, and downward locations, respectively, in the vertical plane. The same research area has also indicated that such concepts seem to have no preferential location on the horizontal plane. The approach-avoidance effect consists in decreasing the distance between positive stimuli and the body (i.e. approach) and increasing the distance between negative stimuli and the body (i.e. avoid). Thus, the valence-space metaphor accounts for the mapping of valenced concepts onto the vertical and horizontal planes, and the approach-avoidance effect accounts for the mapping of valenced concepts onto the "depth" plane. By using a cube conceived for the study of allocation of valenced concepts onto 3D space, we show in three studies that positive concepts are placed in upward locations and near the participants' body, negative concepts are placed in downward locations and far from the participants' body, and neutral concepts are placed in between these concepts in both planes.

Organic Electronic Devices Using Crosslinked Polyelectrolyte Multilayers as an Ultra-Thin Dielectric Material

DTIC Science & Technology

2006-09-01

energy band diagram illustrating the allowed energies for valence and conducting electrons. The dashes within the band gap (Eg) represent localized ...allowed energies for valence and conducting electrons. The dashes within the band gap (Eg) represent localized electron energy states, or traps, that...been observed with the formation of alternating bond lengths along the backbone.43 The localization of the π-electrons while forming the shorter double

Electronic structure and nature of the ground state of the mixed-valence binuclear tetra(mu-1,8-naphthyridine-N,N')-bis(halogenonickel) tetraphenylborate complexes: experimental and DFT characterization.

PubMed

Bencini, Alessandro; Berti, Elisabetta; Caneschi, Andrea; Gatteschi, Dante; Giannasi, Elisa; Invernizzi, Ivana

2002-08-16

The ground state electronic structure of the mixed-valence systems [Ni(2)(napy)(4)X(2)](BPh(4)) (napy=1,8-naphthyridine; X=Cl, Br, I) was studied with combined experimental (X-ray diffraction, temperature dependence of the magnetic susceptibility, and high-field EPR spectroscopy) and theoretical (DFT) methods. The zero-field splitting (zfs) ground S=3/2 spin state is axial with /D/ approximately 3 cm(-1). The iodide derivative was found to be isostructural with the previously reported bromide complex, but not isomorphous. The compound crystallizes in the monoclinic system, space group P2(1)/n, with a=17.240(5), b=26.200(5), c=11.340(5) A, beta=101.320(5) degrees. DFT calculations were performed on the S=3/2 state to characterize the ground state potential energy surface as a function of the nuclear displacements. The molecules can thus be classified as Class III mixed-valence compounds with a computed delocalization parameter, B=3716, 3583, and 3261 cm(-1) for the Cl, Br, and I derivatives, respectively.

Electron core ionization in compressed alkali metal cesium

NASA Astrophysics Data System (ADS)

Degtyareva, V. F.

2018-01-01

Elements of groups I and II in the periodic table have valence electrons of s-type and are usually considered as simple metals. Crystal structures of these elements at ambient pressure are close-packed and high-symmetry of bcc and fcc-types, defined by electrostatic (Madelung) energy. Diverse structures were found under high pressure with decrease of the coordination number, packing fraction and symmetry. Formation of complex structures can be understood within the model of Fermi sphere-Brillouin zone interactions and supported by Hume-Rothery arguments. With the volume decrease there is a gain of band structure energy accompanied by a formation of many-faced Brillouin zone polyhedra. Under compression to less than a half of the initial volume the interatomic distances become close to or smaller than the ionic radius which should lead to the electron core ionization. At strong compression it is necessary to assume that for alkali metals the valence electron band overlaps with the upper core electrons, which increases the valence electron count under compression.

Valence-Dependent Belief Updating: Computational Validation.

PubMed

Kuzmanovic, Bojana; Rigoux, Lionel

2017-01-01

People tend to update beliefs about their future outcomes in a valence-dependent way: they are likely to incorporate good news and to neglect bad news. However, belief formation is a complex process which depends not only on motivational factors such as the desire for favorable conclusions, but also on multiple cognitive variables such as prior beliefs, knowledge about personal vulnerabilities and resources, and the size of the probabilities and estimation errors. Thus, we applied computational modeling in order to test for valence-induced biases in updating while formally controlling for relevant cognitive factors. We compared biased and unbiased Bayesian models of belief updating, and specified alternative models based on reinforcement learning. The experiment consisted of 80 trials with 80 different adverse future life events. In each trial, participants estimated the base rate of one of these events and estimated their own risk of experiencing the event before and after being confronted with the actual base rate. Belief updates corresponded to the difference between the two self-risk estimates. Valence-dependent updating was assessed by comparing trials with good news (better-than-expected base rates) with trials with bad news (worse-than-expected base rates). After receiving bad relative to good news, participants' updates were smaller and deviated more strongly from rational Bayesian predictions, indicating a valence-induced bias. Model comparison revealed that the biased (i.e., optimistic) Bayesian model of belief updating better accounted for data than the unbiased (i.e., rational) Bayesian model, confirming that the valence of the new information influenced the amount of updating. Moreover, alternative computational modeling based on reinforcement learning demonstrated higher learning rates for good than for bad news, as well as a moderating role of personal knowledge. Finally, in this specific experimental context, the approach based on reinforcement

Valence-Dependent Belief Updating: Computational Validation

PubMed Central

Kuzmanovic, Bojana; Rigoux, Lionel

2017-01-01

People tend to update beliefs about their future outcomes in a valence-dependent way: they are likely to incorporate good news and to neglect bad news. However, belief formation is a complex process which depends not only on motivational factors such as the desire for favorable conclusions, but also on multiple cognitive variables such as prior beliefs, knowledge about personal vulnerabilities and resources, and the size of the probabilities and estimation errors. Thus, we applied computational modeling in order to test for valence-induced biases in updating while formally controlling for relevant cognitive factors. We compared biased and unbiased Bayesian models of belief updating, and specified alternative models based on reinforcement learning. The experiment consisted of 80 trials with 80 different adverse future life events. In each trial, participants estimated the base rate of one of these events and estimated their own risk of experiencing the event before and after being confronted with the actual base rate. Belief updates corresponded to the difference between the two self-risk estimates. Valence-dependent updating was assessed by comparing trials with good news (better-than-expected base rates) with trials with bad news (worse-than-expected base rates). After receiving bad relative to good news, participants' updates were smaller and deviated more strongly from rational Bayesian predictions, indicating a valence-induced bias. Model comparison revealed that the biased (i.e., optimistic) Bayesian model of belief updating better accounted for data than the unbiased (i.e., rational) Bayesian model, confirming that the valence of the new information influenced the amount of updating. Moreover, alternative computational modeling based on reinforcement learning demonstrated higher learning rates for good than for bad news, as well as a moderating role of personal knowledge. Finally, in this specific experimental context, the approach based on reinforcement

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

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.

Comparative electronic structure of a lanthanide and actinide diatomic oxide: Nd versus U

NASA Astrophysics Data System (ADS)

Krauss, M.; Stevens, W. J.

2003-01-01

Using a modified version of the Alchemy electronic structure code and relativistic pseudopotentials, the electronic structure of the ground and low lying excited states of UO, NdO, and NdO + have been calculated at the Hartree-Fock (HF) and multiconfiguration self-consistent field (MCSCF) levels of theory. Including results from an earlier study of UO + this provides the information for a comparative analysis of a lanthanide and an actinide diatomic oxide. UO and NdO are both described formally as M +2 O -2 and the cations as M +3 O -2 , but the HF and MCSCF calculations show that these systems are considerably less ionic due to large charge back-transfer in the πorbitals. The electronic states putatively arise from the ligand field (oxygen anion) perturbed f 4 , sf 3 , df 3 , sdf 2 , or s 2 f 2 states of M +2 and f 3 , sf 2 or df 2 states of M +3 . Molecular orbital results show a substantial stabilization of the sf 3 or s 2 f 2 configurations relative to the f 4 or df 3 configurations that are the even or odd parity ground states in the M +2 free ion. The compact f and d orbitals are more destabilized by the anion field than the diffuse s orbital. The ground states of the neutral species are dominated by orbitals arising from the M +2 sf 3 term, and all the potential energy curves arising from this configuration are similar, which allows an estimate of the vibrational frequencies for UO and NdO of 862 cm -1 and 836 cm -1 , respectively. For NdO + and UO + the excitation energies for the Ωstates were calculated with a valence configuration interaction method using ab initio effective spin-orbit operators to couple the molecular orbital configurations. The results for NdO + are very comparable with the results for UO + , and show the vibrational and electronic states to be interleaved.

First principles electron-correlated calculations of optical absorption in magnesium clusters★

NASA Astrophysics Data System (ADS)

Shinde, Ravindra; Shukla, Alok

2017-11-01

In this paper, we report large-scale configuration interaction (CI) calculations of linear optical absorption spectra of various isomers of magnesium clusters Mgn (n = 2-5), corresponding to valence transitions. Geometry optimization of several low-lying isomers of each cluster was carried out using coupled-cluster singles doubles (CCSD) approach, and these geometries were subsequently employed to perform ground and excited state calculations using either the full-CI (FCI) or the multi-reference singles-doubles configuration interaction (MRSDCI) approach, within the frozen-core approximation. Our calculated photoabsorption spectrum of magnesium dimer (Mg2) is in excellent agreement with the experiments both for peak positions, and intensities. Owing to the sufficiently inclusive electron-correlation effects, these results can serve as benchmarks against which future experiments, as well as calculations performed using other theoretical approaches, can be tested. Supplementary material in the form of one pdf fille available from the Journal web page at http://https://doi.org/10.1140/epjd/e2017-80356-6.

Valenced cues and contexts have different effects on event-based prospective memory.

PubMed

Graf, Peter; Yu, Martin

2015-01-01

This study examined the separate influence and joint influences on event-based prospective memory task performance due to the valence of cues and the valence of contexts. We manipulated the valence of cues and contexts with pictures from the International Affective Picture System. The participants, undergraduate students, showed higher performance when neutral compared to valenced pictures were used for cueing prospective memory. In addition, neutral pictures were more effective as cues when they occurred in a valenced context than in the context of neutral pictures, but the effectiveness of valenced cues did not vary across contexts that differed in valence. The finding of an interaction between cue and context valence indicates that their respective influence on event-based prospective memory task performance cannot be understood in isolation from each other. Our findings are not consistent with by the prevailing view which holds that the scope of attention is broadened and narrowed, respectively, by positively and negatively valenced stimuli. Instead, our findings are more supportive of the recent proposal that the scope of attention is determined by the motivational intensity associated with valenced stimuli. Consistent with this proposal, we speculate that the motivational intensity associated with different retrieval cues determines the scope of attention, that contexts with different valence values determine participants' task engagement, and that prospective memory task performance is determined jointly by attention scope and task engagement.

Valenced Cues and Contexts Have Different Effects on Event-Based Prospective Memory

PubMed Central

Graf, Peter; Yu, Martin

2015-01-01

This study examined the separate influence and joint influences on event-based prospective memory task performance due to the valence of cues and the valence of contexts. We manipulated the valence of cues and contexts with pictures from the International Affective Picture System. The participants, undergraduate students, showed higher performance when neutral compared to valenced pictures were used for cueing prospective memory. In addition, neutral pictures were more effective as cues when they occurred in a valenced context than in the context of neutral pictures, but the effectiveness of valenced cues did not vary across contexts that differed in valence. The finding of an interaction between cue and context valence indicates that their respective influence on event-based prospective memory task performance cannot be understood in isolation from each other. Our findings are not consistent with by the prevailing view which holds that the scope of attention is broadened and narrowed, respectively, by positively and negatively valenced stimuli. Instead, our findings are more supportive of the recent proposal that the scope of attention is determined by the motivational intensity associated with valenced stimuli. Consistent with this proposal, we speculate that the motivational intensity associated with different retrieval cues determines the scope of attention, that contexts with different valence values determine participants’ task engagement, and that prospective memory task performance is determined jointly by attention scope and task engagement. PMID:25647484

Pairing and (9/2)n configuration in nuclei in the 208Pb region

NASA Astrophysics Data System (ADS)

Stepanov, M.; Imasheva, L.; Ishkhanov, B.; Tretyakova, T.

2018-04-01

Excited states in low-energy spectra in nuclei near 208Pb are considered. The pure (j = 9/2)n configuration approximation with delta-force is used for ground state multiplet calculations. The multiplet splitting is determined by the pairing energy, which can be defined from the even-odd straggering of the nuclear masses. For the configurations with more than two valence nucleons, the seniority scheme is used. The results of the calculations agree with the experimental data for both stable and exotic nuclei within 0.06-6.16%. Due to simplicity and absence of the fitted parameters, the model can be easily applied for studies of nature of the excited states in a wide range of nuclei.

Coulomb scattering rates of excited states in monolayer electron-doped germanene

NASA Astrophysics Data System (ADS)

Shih, Po-Hsin; Chiu, Chih-Wei; Wu, Jhao-Ying; Do, Thi-Nga; Lin, Ming-Fa

2018-05-01

Excited conduction electrons, conduction holes, and valence holes in monolayer electron-doped germanene exhibit unusual Coulomb decay rates. The deexcitation processes are studied using the screened exchange energy. They might utilize the intraband single-particle excitations (SPEs), the interband SPEs, and the plasmon modes, depending on the quasiparticle states and the Fermi energies. The low-lying valence holes can decay through the undamped acoustic plasmon, so that they present very fast Coulomb deexcitations, nonmonotonous energy dependence, and anisotropic behavior. However, the low-energy conduction electrons and holes are similar to those in a two-dimensional electron gas. The higher-energy conduction states and the deeper-energy valence ones behave similarly in the available deexcitation channels and have a similar dependence of decay rate on the wave vector k .

Correlation of molecular valence- and K-shell photoionization resonances with bond lengths

NASA Technical Reports Server (NTRS)

Sheehy, J. A.; Gil, T. J.; Winstead, C. L.; Farren, R. E.; Langhoff, P. W.

1989-01-01

The relationship between the interatomic distance and the positions of valence-shell and K-shell sigma(asterisk) photoionization resonances is investigated theoretically for the molecules C2, F2, N2, O2, CO, NO, C2H2, C2H4, C2H6, HCN, H2CO, N20, CO2, and C2N2. The results of molecular-orbital computations are presented in three-dimensional diagrams, which are shown to be similar to the wave functions of a particle in a cylindrical well, confirming the validity of free-electron molecular-orbital (FEMO) approximations for modeling the potential along the symmetry axis. FEMO orbital energies and resonance positions are found to be in good agreement with previous theoretical and experimental results. Also included is a Feshbach-Fano analysis of the relevance of virtual-valence orbitals to the appearance of single-channel resonances in molecular photoionization cross sections.

Experimental Constraints on the Partitioning and Valence of V and Cr in Garnet and Coexisting Glass

NASA Technical Reports Server (NTRS)

Righter, K.; Sutton, S.; Berthet, S.; Newville, M.

2008-01-01

A series of experiments with garnet and coexisting melt have been carried out across a range of oxygen fugacities (near hematite-magnetite (HM) to below the iron-wustite (IW) buffers) at 1.7 GPa to study the partitioning and valence of Cr and V in both phases. Experiments were carried out in a non end loaded piston cylinder apparatus, and the run products were analyzed with electron microprobe and xray absorption near edge structure (XANES) analysis at beamline 13-ID at the Advanced Photon Source of Argonne National Lab. The valence of vanadium and chromium were determined using the position and intensity of the Ka pre-edge peaks, calibrated on a series of Cr and Vbearing standard glasses. This technique has been applied to V and Cr in glasses and V in spinels previously, and in these isotropic phases there are no orientational effects on the XANES spectra (Righter et al., 2006, Amer. Mineral. 91, 1643-1656). We also now demonstrate this to be true for V and Cr in garnet. Also, previous work has shown that V has a higher valence in the glass (or melt) than in the coexisting spinel. This is also true for V in garnet-glass pairs in this study. Vanadium valence in garnets varies from 2.7 below the IW buffer to 3.7 near HM, and for coexisting glass it varies from 3.2 to 4.3. Vanadium valence measured in some natural garnets from mantle localities indicates V in the more reduced range at 2.5. Comparisons will be made between fO2 estimated from V valence and other methods for garnet-bearing mantle samples. In contrast, Cr valence measured in garnet and coexisting glass for all experimental and natural samples is 2.9- 3.0, suggesting that the valence of Cr does not vary within either phase across a large fO2 range. These results demonstrate that while V varies from 2+ to 3+ to 4+ in garnet-melt systems, Cr does not, and this will ultimately affect the partitioning behavior of these two elements in natural systems. Garnet/melt D(Cr) are between 12 and 17 across this range

Decoding emotional valence from electroencephalographic rhythmic activity.

PubMed

Celikkanat, Hande; Moriya, Hiroki; Ogawa, Takeshi; Kauppi, Jukka-Pekka; Kawanabe, Motoaki; Hyvarinen, Aapo

2017-07-01

We attempt to decode emotional valence from electroencephalographic rhythmic activity in a naturalistic setting. We employ a data-driven method developed in a previous study, Spectral Linear Discriminant Analysis, to discover the relationships between the classification task and independent neuronal sources, optimally utilizing multiple frequency bands. A detailed investigation of the classifier provides insight into the neuronal sources related with emotional valence, and the individual differences of the subjects in processing emotions. Our findings show: (1) sources whose locations are similar across subjects are consistently involved in emotional responses, with the involvement of parietal sources being especially significant, and (2) even though the locations of the involved neuronal sources are consistent, subjects can display highly varying degrees of valence-related EEG activity in the sources.

Integrated front-end electronics in a detector compatible process: source-follower and charge-sensitive preamplifier configurations

NASA Astrophysics Data System (ADS)

Ratti, Lodovico; Manghisoni, Massimo; Re, Valerio; Speziali, Valeria

2001-12-01

This study is concerned with the simulation and design of low-noise front-end electronics monolithically integrated on the same high-resistivity substrate as multielectrode silicon detectors, in a process made available by the Istituto per la Ricerca Scientifica e Tecnologica (ITC-IRST) of Trento, Italy. The integrated front-end solutions described in this paper use N-channel JFETs as basic elements. The first one is based upon an all-NJFET charge preamplifier designed to match detector capacitances of a few picofarads and available in both a resistive and a non resistive feedback configuration. In the second solution, a single NJFET in the source-follower configuration is connected to the detector, while its source is wired to an external readout channel through an integrated capacitor.

Space-valence priming with subliminal and supraliminal words.

PubMed

Ansorge, Ulrich; Khalid, Shah; König, Peter

2013-01-01

To date it is unclear whether (1) awareness-independent non-evaluative semantic processes influence affective semantics and whether (2) awareness-independent affective semantics influence non-evaluative semantic processing. In the current study, we investigated these questions with the help of subliminal (masked) primes and visible targets in a space-valence across-category congruence effect. In line with (1), we found that subliminal space prime words influenced valence classification of supraliminal target words (Experiment 1): classifications were faster with a congruent prime (e.g., the prime "up" before the target "happy") than with an incongruent prime (e.g., the prime "up" before the target "sad"). In contrast to (2), no influence of subliminal valence primes on the classification of supraliminal space targets into up- and down-words was found (Experiment 2). Control conditions showed that standard masked response priming effects were found with both subliminal prime types, and that an across-category congruence effect was also found with supraliminal valence primes and spatial target words. The final Experiment 3 confirmed that the across-category congruence effect indeed reflected priming of target categorization of a relevant meaning category. Together, the data jointly confirmed prediction (1) that awareness-independent non-evaluative semantic priming influences valence judgments.

Space-Valence Priming with Subliminal and Supraliminal Words

PubMed Central

Ansorge, Ulrich; Khalid, Shah; König, Peter

2013-01-01

To date it is unclear whether (1) awareness-independent non-evaluative semantic processes influence affective semantics and whether (2) awareness-independent affective semantics influence non-evaluative semantic processing. In the current study, we investigated these questions with the help of subliminal (masked) primes and visible targets in a space-valence across-category congruence effect. In line with (1), we found that subliminal space prime words influenced valence classification of supraliminal target words (Experiment 1): classifications were faster with a congruent prime (e.g., the prime “up” before the target “happy”) than with an incongruent prime (e.g., the prime “up” before the target “sad”). In contrast to (2), no influence of subliminal valence primes on the classification of supraliminal space targets into up- and down-words was found (Experiment 2). Control conditions showed that standard masked response priming effects were found with both subliminal prime types, and that an across-category congruence effect was also found with supraliminal valence primes and spatial target words. The final Experiment 3 confirmed that the across-category congruence effect indeed reflected priming of target categorization of a relevant meaning category. Together, the data jointly confirmed prediction (1) that awareness-independent non-evaluative semantic priming influences valence judgments. PMID:23439863

Valence and L-shell photoionization of Cl-like argon using R-matrix techniques

NASA Astrophysics Data System (ADS)

Tyndall, N. B.; Ramsbottom, C. A.; Ballance, C. P.; Hibbert, A.

2016-02-01

Photoionization cross-sections are obtained using the relativistic Dirac Atomic R-matrix Codes (DARC) for all valence and L-shell energy ranges between 27 and 270 eV. A total of 557 levels arising from the dominant configurations 3s23p4, 3s3p5, 3p6, 3s23p3[3d, 4s, 4p], 3p53d, 3s23p23d2, 3s3p43d, 3s3p33d2 and 2s22p53s23p5 have been included in the target wavefunction representation of the Ar III ion, including up to 4p in the orbital basis. We also performed a smaller Breit-Pauli (BP) calculation containing the lowest 124 levels. Direct comparisons are made with previous theoretical and experimental work for both valence shell and L-shell photoionization. Excellent agreement was found for transitions involving the 2Po initial state to all allowed final states for both calculations across a range of photon energies. A number of resonant states have been identified to help analyse and explain the nature of the spectra at photon energies between 250 and 270 eV.

Valence-band and core-level photoemission study of single-crystal Bi2CaSr2Cu2O8 superconductors

NASA Astrophysics Data System (ADS)

Shen, Z.-X.; Lindberg, P. A. P.; Wells, B. O.; Mitzi, D. B.; Lindau, I.; Spicer, W. E.; Kapitulnik, A.

1988-12-01

High-quality single crystals of Bi2CaSr2Cu2O8 superconductors have been prepared and cleaved in ultrahigh vacuum. Low-energy electron diffraction measurements show that the surface structure is consistent with the bulk crystal structure. Ultraviolet photoemission and x-ray photoemission experiments were performed on these well-characterized sample surfaces. The valence-band and the core-level spectra obtained from the single-crystal surfaces are in agreement with spectra recorded from polycrystalline samples, justifying earlier results from polycrystalline samples. Cu satellites are observed both in the valence band and Cu 2p core level, signaling the strong correlation among the Cu 3d electrons. The O 1s core-level data exhibit a sharp, single peak at 529-eV binding energy without any clear satellite structures.

Ligand-hole localization in oxides with unusual valence Fe

PubMed Central

Chen, Wei-Tin; Saito, Takashi; Hayashi, Naoaki; Takano, Mikio; Shimakawa, Yuichi

2012-01-01

Unusual high-valence states of iron are stabilized in a few oxides. A-site-ordered perovskite-structure oxides contain such iron cations and exhibit distinct electronic behaviors at low temperatures, e.g. charge disproportionation (4Fe4+ → 2Fe3+ + 2Fe5+) in CaCu3Fe4O12 and intersite charge transfer (3Cu2+ + 4Fe3.75+ → 3Cu3+ + 4Fe3+) in LaCu3Fe4O12. Here we report the synthesis of solid solutions of CaCu3Fe4O12 and LaCu3Fe4O12 and explain how the instabilities of their unusual valence states of iron are relieved. Although these behaviors look completely different from each other in simple ionic models, they can both be explained by the localization of ligand holes, which are produced by the strong hybridization of iron d and oxygen p orbitals in oxides. The localization behavior in the charge disproportionation of CaCu3Fe4O12 is regarded as charge ordering of the ligand holes, and that in the intersite charge transfer of LaCu3Fe4O12 is regarded as a Mott transition of the ligand holes. PMID:22690318

Developmental reversals in false memory: Effects of emotional valence and arousal.

PubMed

Brainerd, C J; Holliday, R E; Reyna, V F; Yang, Y; Toglia, M P

2010-10-01

Do the emotional valence and arousal of events distort children's memories? Do valence and arousal modulate counterintuitive age increases in false memory? We investigated those questions in children, adolescents, and adults using the Cornell/Cortland Emotion Lists, a word list pool that induces false memories and in which valence and arousal can be manipulated factorially. False memories increased with age for unpresented semantic associates of word lists, and net accuracy (the ratio of true memory to total memory) decreased with age. These surprising developmental trends were more pronounced for negatively valenced materials than for positively valenced materials, they were more pronounced for high-arousal materials than for low-arousal materials, and developmental increases in the effects of arousal were small in comparison with developmental increases in the effects of valence. These findings have ramifications for legal applications of false memory research; materials that share the emotional hallmark of crimes (events that are negatively valenced and arousing) produced the largest age increases in false memory and the largest age declines in net accuracy. Copyright 2010 Elsevier Inc. All rights reserved.

Neon in ultrashort and intense x-rays from free electron lasers

NASA Astrophysics Data System (ADS)

Buth, Christian; Beerwerth, Randolf; Obaid, Razib; Berrah, Nora; Cederbaum, Lorenz S.; Fritzsche, Stephan

2018-03-01

We theoretically examine neon atoms in ultrashort and intense x-rays from free electron lasers and compare our results with data from experiments conducted at the Linac Coherent Light Source. For this purpose, we treat in detail the electronic structure in all possible nonrelativistic cationic configurations using a relativistic multiconfiguration approach. The interaction with the x-rays is described in rate-equation approximation. To understand the mechanisms of the interaction, a path analysis is devised which allows us to investigate what sequences of photoionization and decay processes lead to a specific configuration and with what probability. Thereby, we uncover a connection to the mathematics of graph theory and formal languages. In detail, we study the ion yields and find that plain rate equations do not provide a satisfactory description. We need to extend the rate equations for neon to incorporate double Auger decay of a K-shell vacancy and photoionization shake off for neutral neon. Shake off is included for valence and core ionization; the former has hitherto been overlooked but has important consequences for the ion yields from an x-ray energy below the core ionization threshold. Furthermore, we predict the photon yields from XUV and x-ray fluorescence these allow one insights into the configurations populated by the interaction with the x-rays. Finally, we discover that inaccuracies in those Auger decay widths employed in previous studies have only a minor influence on ion and photon yields.

Inhibition of unintentional extra carriers by Mn valence change for high insulating devices

PubMed Central

Guo, Daoyou; Li, Peigang; Wu, Zhenping; Cui, Wei; Zhao, Xiaolong; Lei, Ming; Li, Linghong; Tang, Weihua

2016-01-01

For intrinsic oxide semiconductors, oxygen vacancies served as the electron donors have long been, and inevitably still are, attributed as the primary cause of conductivity, making oxide semiconductors seem hard to act as high insulating materials. Meanwhile, the presence of oxygen vacancies often leads to a persistent photoconductivity phenomenon which is not conducive to the practical use in the fast photoelectric response devices. Herein, we propose a possible way to reduce the influence of oxygen vacancies by introducing a valence change doping in the monoclinic β-Ga2O3 epitaxial thin film. The unintentional extra electrons induced by oxygen vacancies can be strongly suppressed by the change valence of the doped Mn ions from +3 to +2. The resistance for the Mn-doped Ga2O3 increases two orders of magnitude in compared with the pure Ga2O3. As a result, photodetector based on Mn-doped Ga2O3 thin films takes on a lower dark current, a higher sensitivity, and a faster photoresponse time, exhibiting a promising candidate using in high performance solar-blind photodetector. The study presents that the intentional doping of Mn may provide a convenient and reliable method of obtaining high insulating thin film in oxide semiconductor for the application of specific device. PMID:27068227

Core Levels, Band Alignments, and Valence-Band States in CuSbS 2 for Solar Cell Applications

DOE PAGES

Whittles, Thomas J.; Veal, Tim D.; Savory, Christopher N.; ...

2017-11-10

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuInxGa (1-x)Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from themore » antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.« less

Core Levels, Band Alignments, and Valence-Band States in CuSbS2 for Solar Cell Applications.

PubMed

Whittles, Thomas J; Veal, Tim D; Savory, Christopher N; Welch, Adam W; de Souza Lucas, Francisco Willian; Gibbon, James T; Birkett, Max; Potter, Richard J; Scanlon, David O; Zakutayev, Andriy; Dhanak, Vinod R

2017-12-06

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuIn x Ga (1-x) Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from the antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.

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. Copyright © 2014 The Voice Foundation. Published by Mosby, Inc. All rights reserved.

High Power Factor and Enhanced Thermoelectric Performance of SnTe-AgInTe2: Synergistic Effect of Resonance Level and Valence Band Convergence.

PubMed

Banik, Ananya; Shenoy, U Sandhya; Saha, Sujoy; Waghmare, Umesh V; Biswas, Kanishka

2016-10-05

Understanding the basis of electronic transport and developing ideas to improve thermoelectric power factor are essential for production of efficient thermoelectric materials. Here, we report a significantly large thermoelectric power factor of ∼31.4 μW/cm·K 2 at 856 K in Ag and In co-doped SnTe (i.e., SnAg x In x Te 1+2x ). This is the highest power factor so far reported for SnTe-based material, which arises from the synergistic effects of Ag and In on the electronic structure and the improved electrical transport properties of SnTe. In and Ag play different but complementary roles in modifying the valence band structure of SnTe. In-doping introduces resonance levels inside the valence bands, leading to a significant improvement in the Seebeck coefficient at room temperature. On the other hand, Ag-doping reduces the energy separation between light- and heavy-hole valence bands by widening the principal band gap, which also results in an improved Seebeck coefficient. Additionally, Ag-doping in SnTe enhances the p-type carrier mobility. Co-doping of In and Ag in SnTe yields synergistically enhanced Seebeck coefficient and power factor over a broad temperature range because of the synergy of the introduction of resonance states and convergence of valence bands, which have been confirmed by first-principles density functional theory-based electronic structure calculations. As a consequence, we have achieved an improved thermoelectric figure of merit, zT ≈ 1, in SnAg 0.025 In 0.025 Te 1.05 at 856 K.

Broadband two-dimensional electronic spectroscopy in an actively phase stabilized pump-probe configuration.

PubMed

Zhu, Weida; Wang, Rui; Zhang, Chunfeng; Wang, Guodong; Liu, Yunlong; Zhao, Wei; Dai, Xingcan; Wang, Xiaoyong; Cerullo, Giulio; Cundiff, Steven; Xiao, Min

2017-09-04

We introduce a novel configuration for two-dimensional electronic spectroscopy (2DES) that combines the partially collinear pump-probe geometry with active phase locking. We demonstrate the method on a solution sample of CdSe/ZnS nanocrystals by employing two non-collinear optical parametric amplifiers as the pump and probe sources. The two collinear pump pulse replicas are created using a Mach-Zehnder interferometer phase stabilized by active feedback electronics. Taking the advantage of separated paths of the two pump pulses in the interferometer, we improve the signal-to-noise ratio with double modulation of the individual pump beams. In addition, a quartz wedge pair manipulates the phase difference between the two pump pulses, enabling the recovery of the rephasing and non-rephasing signals. Our setup integrates many advantages of available 2DES techniques with robust phase stabilization, ultrafast time resolution, two-color operation, long delay scan, individual polarization manipulation and the ease of implementation.

Structure-property relationships in cubic cuprous iodide: A novel view on stability, chemical bonding, and electronic properties

NASA Astrophysics Data System (ADS)

Pishtshev, A.; Karazhanov, S. Zh.

2017-02-01

Based on the combination of density functional theory and theory-group methods, we performed systematic modeling of γ-CuI structural design at the atomistic level. Being started from the metallic copper lattice, we treated a crystal assembly as a stepwise iodination process characterized in terms of a sequence of intermediate lattice geometries. These geometries were selected and validated via screening of possible structural transformations. The genesis of chemical bonding was studied for three structural transformations by analyzing the relevant changes in the topology of valence electron densities. We determined structural trends driven by metal-ligand coupling. This allowed us to suggest the improved scenario of chemical bonding in γ-CuI. In particular, the unconventional effect of spatial separation of metallic and covalent interactions was found to be very important with respect to the preferred arrangements of valence electrons in the iodination process. We rigorously showed that useful electronic and optical properties of γ-CuI originate from the combination of two separated bonding patterns—strong covalency established in I-Cu tetrahedral connections and noncovalent interactions of copper cores is caused by the 3d10 closed-shell electron configurations. The other finding of ours is that the self-consistency of the GW calculations is crucial for correctly determining the dynamic electronic correlations in γ-CuI. Detail reinvestigation of the quasi-particle energy structure by means of the self-consistent GW approach allowed us to explain how p-type electrical conductivity can be engineered in the material.

Evidence for anisotropic dielectric properties of monoclinic hafnia using valence electron energy-loss spectroscopy in high-resolution transmission electron microscopy and ab initio time-dependent density-functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guedj, C.; CEA, LETI, MINATEC Campus, F-38054 Grenoble; Hung, L.

2014-12-01

The effect of nanocrystal orientation on the energy loss spectra of monoclinic hafnia (m-HfO{sub 2}) is measured by high resolution transmission electron microscopy (HRTEM) and valence energy loss spectroscopy (VEELS) on high quality samples. For the same momentum-transfer directions, the dielectric properties are also calculated ab initio by time-dependent density-functional theory (TDDFT). Experiments and simulations evidence anisotropy in the dielectric properties of m-HfO{sub 2}, most notably with the direction-dependent oscillator strength of the main bulk plasmon. The anisotropic nature of m-HfO{sub 2} may contribute to the differences among VEELS spectra reported in literature. The good agreement between the complex dielectricmore » permittivity extracted from VEELS with nanometer spatial resolution, TDDFT modeling, and past literature demonstrates that the present HRTEM-VEELS device-oriented methodology is a possible solution to the difficult nanocharacterization challenges given in the International Technology Roadmap for Semiconductors.« less

Processing negative valence of word pairs that include a positive word.

PubMed

Itkes, Oksana; Mashal, Nira

2016-09-01

Previous research has suggested that cognitive performance is interrupted by negative relative to neutral or positive stimuli. We examined whether negative valence affects performance at the word or phrase level. Participants performed a semantic decision task on word pairs that included either a negative or a positive target word. In Experiment 1, the valence of the target word was congruent with the overall valence conveyed by the word pair (e.g., fat kid). As expected, response times were slower in the negative condition relative to the positive condition. Experiment 2 included target words that were incongruent with the overall valence of the word pair (e.g., fat salary). Response times were longer for word pairs whose overall valence was negative relative to positive, even though these word pairs included a positive word. Our findings support the Cognitive Primacy Hypothesis, according to which emotional valence is extracted after conceptual processing is complete.

Plasmon satellites in valence-band photoemission spectroscopy. Ab initio study of the photon-energy dependence in semiconductors

NASA Astrophysics Data System (ADS)

Guzzo, M.; Kas, J. J.; Sottile, F.; Silly, M. G.; Sirotti, F.; Rehr, J. J.; Reining, L.

2012-09-01

We present experimental data and theoretical results for valence-band satellites in semiconductors, using the prototypical example of bulk silicon. In a previous publication we introduced a new approach that allows us to describe satellites in valence photoemission spectroscopy, in good agreement with experiment. Here we give more details; we show how the the spectra change with photon energy, and how the theory explains this behaviour. We also describe how we include several effects which are important to obtain a correct comparison between theory and experiment, such as secondary electrons and photon cross sections. In particular the inclusion of extrinsic losses and their dependence on the photon energy are key to the description of the energy dependence of spectra.

The Eighteen-Electron Rule

ERIC Educational Resources Information Center

Mitchell, P. R.; Parish, R. V.

1969-01-01

Discusses the stability of the structures of transition metal complexes (primarily carbonyls and organometallic compounds) having 18 electrons or less in their valence shell. Presents molecular orbital diagrams for various structures involving alpha and pi bonding and describes the conditions under which the 18 electron rule applies. (RR)

A pilot training manual for the terminal configured vehicle electronic attitude director indicator

NASA Technical Reports Server (NTRS)

Gandelman, J.

1980-01-01

A hard copy version is presented of a 28-minute, 90 slide audiovisual program which provides the basic instructional format for introduction to the terminal configured vehicle electronic attitude director indicator (EADI) and the strategy for learning the symbols used on the EADI and their interpretation. The basic strategy is to start with known symbols and then introduce all new symbols with emphasis appropriate to their complexity and frequency of use. The upper half of each page of the manual contains a reproduction of the slide. The text associated with the slide is found on the lower half of each page and is recorded on audio tape.

Effect of magnetic exchange, double exchange, vibronic coupling, and asymmetry on magnetic properties in d2-d3 mixed-valence dimers

NASA Astrophysics Data System (ADS)

Yang, Xiaohua; Hu, Haiquan; Chen, Zhida

The effect of magnetic exchange, double exchange, vibronic coupling, and asymmetry on magnetic properties of d2-d3 systems is discussed. The temperature-dependent magnetic moment was calculated with the semiclassical adiabatic approach. The results show that the vibronic coupling from the out-of-phase breathing vibration on the metal sites (Piepho, Krausz, and Schatz [PKS] model) and the vibronic coupling from the stretching vibration between the metal sites (P model) favor the localization and delocalization of the "extra" electron in mixed-valence dimers, respectively. The magnetic properties are determined by the interplay among magnetic exchange, double exchange, and vibronic coupling. The results obtained by analyzing d2-d3 systems can be generalized to other full delocalized dinuclear mixed valence systems with a unique transferable electron.

The valence and Rydberg states of difluoromethane: A combined experimental vacuum ultraviolet spectrum absorption and theoretical study by ab initio configuration interaction and density functional computations

NASA Astrophysics Data System (ADS)

Palmer, Michael H.; Vrønning Hoffmann, Søren; Jones, Nykola C.; Coreno, Marcello; de Simone, Monica; Grazioli, Cesare

2018-06-01

The vacuum ultraviolet (VUV) spectrum for CH2F2 from a new synchrotron study has been combined with earlier data and subjected to detailed scrutiny. The onset of absorption, band I and also band IV, is resolved into broad vibrational peaks, which contrast with the continuous absorption previously claimed. A new theoretical analysis, using a combination of time dependent density functional theory (TDDFT) calculations and complete active space self-consistent field, leads to a major new interpretation. Adiabatic excitation energies (AEEs) and vertical excitation energies, evaluated by these methods, are used to interpret the spectra in unprecedented detail using theoretical vibronic analysis. This includes both Franck-Condon (FC) and Herzberg-Teller (HT) effects on cold and hot bands. These results lead to the re-assignment of several known excited states and the identification of new ones. The lowest calculated AEE sequence for singlet states is 11B1 ˜ 11A2 < 21B1 < 11A1 < 21A1 < 11B2 < 31A1 < 31B1. These, together with calculated higher energy states, give a satisfactory account of the principal maxima observed in the VUV spectrum. Basis sets up to quadruple zeta valence with extensive polarization are used. The diffuse functions within this type of basis generate both valence and low-lying Rydberg excited states. The optimum position for the site of further diffuse functions in the calculations of Rydberg states is shown to lie on the H-atoms. The routine choice on the F-atoms is shown to be inadequate for both CHF3 and CH2F2. The lowest excitation energy region has mixed valence and Rydberg character. TDDFT calculations show that the unusual structure of the onset arises from the near degeneracy of 11B1 and 11A2 valence states, which mix in symmetric and antisymmetric combinations. The absence of fluorescence in the 10.8-11 eV region contrasts with strong absorption. This is interpreted by the 21B1 and 11A1 states where no fluorescence is calculated for these

Explaining the effect of event valence on unrealistic optimism.

PubMed

Gold, Ron S; Brown, Mark G

2009-05-01

People typically exhibit 'unrealistic optimism' (UO): they believe they have a lower chance of experiencing negative events and a higher chance of experiencing positive events than does the average person. UO has been found to be greater for negative than positive events. This 'valence effect' has been explained in terms of motivational processes. An alternative explanation is provided by the 'numerosity model', which views the valence effect simply as a by-product of a tendency for likelihood estimates pertaining to the average member of a group to increase with the size of the group. Predictions made by the numerosity model were tested in two studies. In each, UO for a single event was assessed. In Study 1 (n = 115 students), valence was manipulated by framing the event either negatively or positively, and participants estimated their own likelihood and that of the average student at their university. In Study 2 (n = 139 students), valence was again manipulated and participants again estimated their own likelihood; additionally, group size was manipulated by having participants estimate the likelihood of the average student in a small, medium-sized, or large group. In each study, the valence effect was found, but was due to an effect on estimates of own likelihood, not the average person's likelihood. In Study 2, valence did not interact with group size. The findings contradict the numerosity model, but are in accord with the motivational explanation. Implications for health education are discussed.

Synthesis and spectral characterization of trinuclear, oxo-centered, carboxylate-bridged, mixed-valence iron complexes with Schiff bases.

PubMed

Singh, Atresh Kumar; Singh, Alok Kumar

2012-10-01

Some novel trinuclear, oxo-centered, carboxylate-bridged, mixed-valence iron complexes of the general formula [Fe(3)O(OOCR)(3)(SB)(3)L(3)] (where R=C(13)H(27), C(15)H(31) or C(17)H(35,) HSB=Schiff bases and L=Ethanol) have been synthesized by the stepwise substitutions of acetate ions from μ(3)-oxo-hexa(acetato)tri(aqua)iron(II)diiron(III), first with straight chain carboxylic acids and then with Schiff bases. The complexes were characterized by elemental analyses, molecular weight determinations and spectral (electronic, infrared, FAB mass, Mössbauer and powder XRD) studies. Molar conductance measurements indicated the complexes to be non-electrolytes in nitrobenzene. Bridging nature of carboxylate and Schiff base anions in the complexes was established by their infrared spectra. Mössbauer spectroscopic studies indicated two quadrupole-split doublets due to Fe(II) and Fe(III) ions at 80, 200 and 295K, confirming the complexes are mixed-valence species. This was also supported by the observed electronic spectra of the complexes. Magnetic susceptibility measurements displayed octahedral geometry around iron in mixed-valence state and a net antiferromagnetic exchange coupling via μ-oxo atom. Trinuclear nature of the complexes was confirmed by their molecular weight determination and FAB mass spectra. A plausible structure for these complexes has been established on the basis of spectral and magnetic moment data. Copyright © 2012 Elsevier B.V. All rights reserved.

Spectroscopic evidence for temperature-dependent convergence of light- and heavy-hole valence bands of PbQ (Q = Te, Se, S)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, J.; Malliakas, C. D.; Wijayaratne, K.

2017-01-01

We have conducted a temperature- dependent angle-resolved photoemission spectroscopy (ARPES) study of the electronic structures of PbTe, PbSe and PbS. Our ARPES data provide direct evidence for the light-hole upper valence bands (UVBs) and hitherto undetected heavy-hole lower valence bands (LVBs) in these materials. An unusual temperature-dependent relative movement between these bands leads to a monotonic decrease in the energy separation between their maxima with increasing temperature, which is known as band convergence and has long been believed to be the driving factor behind extraordinary thermoelectric performances of these compounds at elevated temperatures.

Spectroscopic evidence for temperature-dependent convergence of light- and heavy-hole valence bands of PbQ (Q = Te, Se, S)

NASA Astrophysics Data System (ADS)

Zhao, J.; Malliakas, C. D.; Wijayaratne, K.; Karlapati, V.; Appathurai, N.; Chung, D. Y.; Rosenkranz, S.; Kanatzidis, M. G.; Chatterjee, U.

2017-01-01

We have conducted a temperature-dependent angle-resolved photoemission spectroscopy (ARPES) study of the electronic structures of PbTe, PbSe and PbS. Our ARPES data provide direct evidence for the light-hole upper valence bands (UVBs) and hitherto undetected heavy-hole lower valence bands (LVBs) in these materials. An unusual temperature-dependent relative movement between these bands leads to a monotonic decrease in the energy separation between their maxima with increasing temperature, which is known as band convergence and has long been believed to be the driving factor behind extraordinary thermoelectric performances of these compounds at elevated temperatures.

Finding the hidden valence band of N  =  7 armchair graphene nanoribbons with angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Senkovskiy, Boris V.; Usachov, Dmitry Yu; Fedorov, Alexander V.; Haberer, Danny; Ehlen, Niels; Fischer, Felix R.; Grüneis, Alexander

2018-07-01

To understand the optical and transport properties of graphene nanoribbons, an unambiguous determination of their electronic band structure is needed. In this work we demonstrate that the photoemission intensity of each valence sub-band, formed due to the quantum confinement in quasi-one-dimensional (1D) graphene nanoribbons, is a peaked function of the two-dimensional (2D) momentum. We resolve the long-standing discrepancy regarding the valence band effective mass () of armchair graphene nanoribbons with a width of N  =  7 carbon atoms (7-AGNRs). In particular, angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling spectroscopy report   ≈0.2 and  ≈0.4 of the free electron mass (m e ), respectively. ARPES mapping in the full 2D momentum space identifies the experimental conditions for obtaining a large intensity for each of the three highest valence 1D sub-bands. Our detail map reveals that previous ARPES experiments have incorrectly assigned the second sub-band as the frontier one. The correct frontier valence sub-band for 7-AGNRs is only visible in a narrow range of emission angles. For this band we obtain an ARPES derived effective mass of 0.4 m e , a charge carrier velocity in the linear part of the band of 0.63  ×  106 m s‑1 and an energy separation of only  ≈60 meV to the second sub-band. Our results are of importance not only for the growing research field of graphene nanoribbons but also for the community, which studies quantum confined systems.

A Multireference Configuration Interaction Study of the Photodynamics of Nitroethylene

PubMed Central

2014-01-01

Extended multireference configuration interaction with singles and doubles (MR-CISD) calculations of nitroethylene (H2C=CHNO2) were carried out to investigate the photodynamical deactivation paths to the ground state. The ground (S0) and the first five valence excited electronic states (S1–S5) were investigated. In the first step, vertical excitations and potential energy curves for CH2 and NO2 torsions and CH2 out-of-plane bending starting from the ground state geometry were computed. Afterward, five conical intersections, one between each pair of adjacent states, were located. The vertical calculations mostly confirm the previous assignment of experimental spectrum and theoretical results using lower-level calculations. The conical intersections have as main features the torsion of the CH2 moiety, different distortions of the NO2 group and CC, CN, and NO bond stretchings. In these conical intersections, the NO2 group plays an important role, also seen in excited state investigations of other nitro molecules. Based on the conical intersections found, a photochemical nonradiative deactivation process after a π–π* excitation to the bright S5 state is proposed. In particular, the possibility of NO2 release in the ground state, an important property in nitro explosives, was found to be possible. PMID:25158277

Lying about the valence of affective pictures: an fMRI study.

PubMed

Lee, Tatia M C; Lee, Tiffany M Y; Raine, Adrian; Chan, Chetwyn C H

2010-08-25

The neural correlates of lying about affective information were studied using a functional magnetic resonance imaging (fMRI) methodology. Specifically, 13 healthy right-handed Chinese men were instructed to lie about the valence, positive or negative, of pictures selected from the International Affective Picture System (IAPS) while their brain activity was scanned by a 3T Philip Achieva scanner. The key finding is that the neural activity associated with deception is valence-related. Comparing to telling the truth, deception about the valence of the affectively positive pictures was associated with activity in the inferior frontal, cingulate, inferior parietal, precuneus, and middle temporal regions. Lying about the valence of the affectively negative pictures, on the other hand, was associated with activity in the orbital and medial frontal regions. While a clear valence-related effect on deception was observed, common neural regions were also recruited for the process of deception about the valence of the affective pictures. These regions included the lateral prefrontal and inferior parietal regions. Activity in these regions has been widely reported in fMRI studies on deception using affectively-neutral stimuli. The findings of this study reveal the effect of valence on the neural activity associated with deception. Furthermore, the data also help to illustrate the complexity of the neural mechanisms underlying deception.

Developmental Reversals in False Memory: Effects of Emotional Valence and Arousal

ERIC Educational Resources Information Center

Brainerd, C. J.; Holliday, R. E.; Reyna, V. F.; Yang, Y.; Toglia, M. P.

2010-01-01

Do the emotional valence and arousal of events distort children's memories? Do valence and arousal modulate counterintuitive age increases in false memory? We investigated those questions in children, adolescents, and adults using the Cornell/Cortland Emotion Lists, a word list pool that induces false memories and in which valence and arousal can…

Low-temperature spin dynamics of a valence bond glass in Ba2YMoO6

NASA Astrophysics Data System (ADS)

de Vries, M. A.; Piatek, J. O.; Misek, M.; Lord, J. S.; Rønnow, H. M.; Bos, J.-W. G.

2013-04-01

We carried out ac magnetic susceptibility measurements and muon spin relaxation spectroscopy on the cubic double perovskite Ba2YMoO6, down to 50 mK. Below ∼1 K the muon relaxation is typical of a magnetic insulator with a spin-liquid type ground state, i.e. without broken symmetries or frozen moments. However, the ac susceptibility revealed a dilute-spin-glass-like transition below ∼1 K. Antiferromagnetically coupled Mo5+ 4d1 electrons in triply degenerate t2g orbitals are in this material arranged in a geometrically frustrated fcc lattice. Bulk magnetic susceptibility data has previously been interpreted in terms of a freezing to a heterogeneous state with non-magnetic sites where 4d1 electrons have paired in spin-singlets dimers, and residual unpaired Mo5+ 4d1 electron spins. Based on the magnetic heat capacity data it has been suggested that this heterogeneity is the result of kinetic constraints intrinsic to the physics of the pure system (possibly due to topological overprotection) leading to a self-induced glass of valence bonds between neighbouring 4d1 electrons. The muon spin relaxation (μSR) unambiguously points to a heterogeneous state with a static arrangement of unpaired electrons in a background of (valence bond) dimers between the majority of Mo5+ 4d electrons. The ac susceptibility data indicate that the residual magnetic moments freeze into a dilute-spin-glass-like state. This is in apparent contradiction with the muon-spin decoupling at 50 mK in fields up to 200 mT, which indicates that, remarkably, the time scale of the field fluctuations from the residual moments is ∼5 ns. Comparable behaviour has been observed in other geometrically frustrated magnets with spin-liquid-like behaviour and the implications of our observations on Ba2YMoO6 are discussed in this context.

Lattice and Valence Electronic Structures of Crystalline Octahedral Molybdenum Halide Clusters-Based Compounds, Cs2[Mo6X14] (X = Cl, Br, I), Studied by Density Functional Theory Calculations.

PubMed

Saito, Norio; Cordier, Stéphane; Lemoine, Pierric; Ohsawa, Takeo; Wada, Yoshiki; Grasset, Fabien; Cross, Jeffrey S; Ohashi, Naoki

2017-06-05

The electronic and crystal structures of Cs 2 [Mo 6 X 14 ] (X = Cl, Br, I) cluster-based compounds were investigated by density functional theory (DFT) simulations and experimental methods such as powder X-ray diffraction, ultraviolet-visible spectroscopy, and X-ray photoemission spectroscopy (XPS). The experimentally determined lattice parameters were in good agreement with theoretically optimized ones, indicating the usefulness of DFT calculations for the structural investigation of these clusters. The calculated band gaps of these compounds reproduced those experimentally determined by UV-vis reflectance within an error of a few tenths of an eV. Core-level XPS and effective charge analyses indicated bonding states of the halogens changed according to their sites. The XPS valence spectra were fairly well reproduced by simulations based on the projected electron density of states weighted with cross sections of Al K α , suggesting that DFT calculations can predict the electronic properties of metal-cluster-based crystals with good accuracy.

Synthesis of High Valence Silver-Loaded Mesoporous Silica with Strong Antibacterial Properties

PubMed Central

Chen, Chun-Chi; Wu, Hsin-Hsien; Huang, Hsin-Yi; Liu, Chen-Wei; Chen, Yi-Ning

2016-01-01

A simple chemical method was developed for preparing high valence silver (Ag)-loaded mesoporous silica (Ag-ethylenediaminetetraacetic acid (EDTA)-SBA-15), which showed strong antibacterial activity. Ag-EDTA-SBA-15 exhibited stronger and more effective antibacterial activity than commercial Ag nanoparticles did, and it offered high stability of high valence silver in the porous matrix and long-lasting antibacterial activity. The synthesized materials were characterized using Fourier transform infrared spectroscopy, powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analysis, and transmission electron microscopy (TEM). Ag existed in both surface complexation and Ag particles. EDTA anchored within a porous structure chelated Ag ions in higher oxidation states and prevented their agglomeration and oxidation reduction. The XRD results showed that most Ag in the Ag-EDTA-SBA-15 existed in higher oxidation states such as Ag(II) and Ag(III). However, the XPS and TEM results showed that Ag easily reduced in lower oxidation states and agglomerated as Ag particles on the exterior layer of the SBA-15. PMID:26742050

Two-electron states of a group-V donor in silicon from atomistic full configuration interactions

NASA Astrophysics Data System (ADS)

Tankasala, Archana; Salfi, Joseph; Bocquel, Juanita; Voisin, Benoit; Usman, Muhammad; Klimeck, Gerhard; Simmons, Michelle Y.; Hollenberg, Lloyd C. L.; Rogge, Sven; Rahman, Rajib

2018-05-01

Two-electron states bound to donors in silicon are important for both two-qubit gates and spin readout. We present a full configuration interaction technique in the atomistic tight-binding basis to capture multielectron exchange and correlation effects taking into account the full band structure of silicon and the atomic-scale granularity of a nanoscale device. Excited s -like states of A1 symmetry are found to strongly influence the charging energy of a negative donor center. We apply the technique on subsurface dopants subjected to gate electric fields and show that bound triplet states appear in the spectrum as a result of decreased charging energy. The exchange energy, obtained for the two-electron states in various confinement regimes, may enable engineering electrical control of spins in donor-dot hybrid qubits.

Temperature-dependent electron paramagnetic resonance detect oxygen vacancy defects and Cr valence of tetragonal Ba(Ti1-xCrx)O3 ceramics

NASA Astrophysics Data System (ADS)

Han, Dan-Dan; Lu, Da-Yong; Meng, Fan-Ling; Yu, Xin-Yu

2018-03-01

Temperature-dependent electron paramagnetic resonance (EPR) study was employed to detect oxygen vacancy defects in the tetragonal Ba(Ti1-xCrx)O3 (x = 5%) ceramic for the first time. In the rhombohedral phase below -150 °C, an EPR signal at g = 1.955 appeared in the insulating Ba(Ti1-xCrx)O3 (x = 5%) ceramic with an electrical resistivity of 108 Ω cm and was assigned to ionized oxygen vacancy defects. Ba(Ti1-xCrx)O3 ceramics exhibited a tetragonal structure except Ba(Ti1-xCrx)O3 (x = 10%) with a tetragonal-hexagonal mixed phase and a first-order phase transition dielectric behavior (ε‧m > 11,000). Mixed valence Cr ions could coexist in ceramics, form CrTi‧-VOrad rad or CrTirad-TiTi‧ defect complexes and make no contribution to a dielectric peak shift towards low temperature.

Can the second order multireference perturbation theory be considered a reliable tool to study mixed-valence compounds?

PubMed

Pastore, Mariachiara; Helal, Wissam; Evangelisti, Stefano; Leininger, Thierry; Malrieu, Jean-Paul; Maynau, Daniel; Angeli, Celestino; Cimiraglia, Renzo

2008-05-07

In this paper, the problem of the calculation of the electronic structure of mixed-valence compounds is addressed in the frame of multireference perturbation theory (MRPT). Using a simple mixed-valence compound (the 5,5(') (4H,4H('))-spirobi[ciclopenta[c]pyrrole] 2,2('),6,6(') tetrahydro cation), and the n-electron valence state perturbation theory (NEVPT2) and CASPT2 approaches, it is shown that the ground state (GS) energy curve presents an unphysical "well" for nuclear coordinates close to the symmetric case, where a maximum is expected. For NEVPT, the correct shape of the energy curve is retrieved by applying the MPRT at the (computationally expensive) third order. This behavior is rationalized using a simple model (the ionized GS of two weakly interacting identical systems, each neutral system being described by two electrons in two orbitals), showing that the unphysical well is due to the canonical orbital energies which at the symmetric (delocalized) conformation lead to a sudden modification of the denominators in the perturbation expansion. In this model, the bias introduced in the second order correction to the energy is almost entirely removed going to the third order. With the results of the model in mind, one can predict that all MRPT methods in which the zero order Hamiltonian is based on canonical orbital energies are prone to present unreasonable energy profiles close to the symmetric situation. However, the model allows a strategy to be devised which can give a correct behavior even at the second order, by simply averaging the orbital energies of the two charge-localized electronic states. Such a strategy is adopted in a NEVPT2 scheme obtaining a good agreement with the third order results based on the canonical orbital energies. The answer to the question reported in the title (is this theoretical approach a reliable tool for a correct description of these systems?) is therefore positive, but care must be exercised, either in defining the orbital

Stabilization of lower hybrid drift modes by finite parallel wavenumber and electron temperature gradients in field-reversed configurations

NASA Astrophysics Data System (ADS)

Farengo, R.; Guzdar, P. N.; Lee, Y. C.

1989-08-01

The effect of finite parallel wavenumber and electron temperature gradients on the lower hybrid drift instability is studied in the parameter regime corresponding to the TRX-2 device [Fusion Technol. 9, 48 (1986)]. Perturbations in the electrostatic potential and all three components of the vector potential are considered and finite beta electron orbit modifications are included. The electron temperature gradient decreases the growth rate of the instability but, for kz=0, unstable modes exist for ηe(=T'en0/Ten0)>6. Since finite kz effects completely stabilize the mode at small values of kz/ky(≂5×10-3), magnetic shear could be responsible for stabilizing the lower hybrid drift instability in field-reversed configurations.

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,…

Actively controlling coolant-cooled cold plate configuration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chainer, Timothy J.; Parida, Pritish R.

A method is provided to facilitate active control of thermal and fluid dynamic performance of a coolant-cooled cold plate. The method includes: monitoring a variable associated with at least one of the coolant-cooled cold plate or one or more electronic components being cooled by the cold plate; and dynamically varying, based on the monitored variable, a physical configuration of the cold plate. By dynamically varying the physical configuration, the thermal and fluid dynamic performance of the cold plate are adjusted to, for example, optimally cool the one or more electronic components, and at the same time, reduce cooling power consumptionmore » used in cooling the electronic component(s). The physical configuration can be adjusted by providing one or more adjustable plates within the coolant-cooled cold plate, the positioning of which may be adjusted based on the monitored variable.« less

Motivation but not valence modulates neuroticism-dependent cingulate cortex and insula activity.

PubMed

Deng, Yaling; Li, Shijia; Zhou, Renlai; Walter, Martin

2018-04-01

Neuroticism has been found to specifically modulate amygdala activations during differential processing of valence and motivation while other brain networks yet are unexplored for associated effects. The main purpose of this study was to investigate whether neural mechanisms processing valence or motivation are prone to neuroticism in the salience network (SN), a network that is anchored in the anterior cingulate cortex (ACC) and the anterior insula. This study used functional magnetic resonance imaging (fMRI) and an approach/avoid emotional pictures task to investigate brain activations modulated by pictures' valence or motivational status between high and low neurotic individuals. We found that neuroticism-dependent SN and the parahippocampal-fusiform area activations were modulated by motivation but not valence. Valence in contrast interacted with neuroticism in the lateral orbitofrontal cortex. We suggested that neuroticism modulated valence and motivation processing, however, under the influence of the two distinct networks. Neuroticism modulated the motivation through the SN while it modulated the valence through the orbitofrontal networks. © 2018 Wiley Periodicals, Inc.

Startle modulation and explicit valence evaluations dissociate during backward fear conditioning.

PubMed

Luck, Camilla C; Lipp, Ottmar V

2017-05-01

Blink startle magnitude is linearly modulated by affect such that, relative to neutral stimuli, startle magnitude is inhibited during pleasant stimuli and potentiated during unpleasant stimuli. Andreatta, Mühlberger, Yarali, Gerber, and Pauli (2010), however, report a dissociation between startle modulation and explicit valence evaluations during backward conditioning, a procedure in which the unconditional stimulus precedes the conditional stimulus (CS). Relative to controls, startles elicited during the CS were inhibited, suggesting that the CS had acquired positive valence, but participants still evaluated the CS as unpleasant after the experiment. In Experiment 1, we aimed to replicate this dissociation using a trial-by-trial measure of CS valence to measure startle modulation and CS valence simultaneously during forward and backward differential fear conditioning. In Experiment 2, we examined whether early and late portions of the CS could acquire differential valence by presenting startle probes at early and late probe positions during the CS. In both experiments, the dissociation between startle modulation and explicit valence evaluations in backward conditioning replicated, with CS+ evaluated as less pleasant than CS-, but startles elicited during CS+ inhibited relative to CS-. In Experiment 2, we provide preliminary evidence that this inhibition was present early, but not late, during the CS+. The results replicate the dissociation between implicit and explicit CS valence reported by Andreatta et al. (2010) using a trial-by-trial measure of valence. We also provide preliminary evidence that this dissociation may occur because the implicit and explicit measures are recorded at different times during the CS presentation. © 2017 Society for Psychophysiological Research.

Valence-bond theory of linear Hubbard and Pariser-Parr-Pople models

NASA Astrophysics Data System (ADS)

Soos, Z. G.; Ramasesha, S.

1984-05-01

The ground and low-lying states of finite quantum-cell models with one state per site are obtained exactly through a real-space basis of valence-bond (VB) diagrams that explicitly conserve the total spin. Regular and alternating Hubbard and Pariser-Parr-Pople (PPP) chains and rings with Ne electrons on N(<=12) sites are extrapolated to infinite arrays. The ground-state energy and optical gap of regular U=4|t| Hubbard chains agree with exact results, suggesting comparable accuracy for alternating Hubbard and PPP models, but differ from mean-field results. Molecular PPP parameters describe well the excitations of finite polyenes, odd polyene ions, linear cyanine dyes, and slightly overestimate the absorption peaks in polyacetylene (CH)x. Molecular correlations contrast sharply with uncorrelated descriptions of topological solitons, which are modeled by regular polyene radicals and their ions for both wide and narrow alternation crossovers. Neutral solitons have no midgap absorption and negative spin densities, while the intensity of the in-gap excitation of charged solitons is not enhanced. The properties of correlated states in quantum-cell models with one valence state per site are discussed in the adiabatic limit for excited-state geometries and instabilities to dimerization.

Dramatic change of photoexcited quasiparticle relaxation dynamics across Yb valence state transition in YbInCu4

NASA Astrophysics Data System (ADS)

Zhang, M. Y.; Chen, R. Y.; Dong, T.; Wang, N. L.

2017-04-01

YbInCu4 undergoes a first-order structural phase transition near Tv=40 K associated with an abrupt change of Yb valence state. We perform an ultrafast pump-probe measurement on YbInCu4 and find that the expected heavy-fermion properties arising from the c -f hybridization exist only in a limited temperature range above Tv. Below Tv, the compound behaves as a normal metal though a prominent hybridization energy gap is still present in the infrared measurement. We elaborate that those seemingly controversial phenomena could be well explained by assuming that the Fermi level suddenly shifts up and moves away from the flat f -electron band as well as the indirect hybridization energy gap in the intermediate valence state below Tv.

Intramolecular interactions of L-phenylalanine: Valence ionization spectra and orbital momentum distributions of its fragment molecules.

PubMed

Ganesan, Aravindhan; Wang, Feng; Falzon, Chantal

2011-02-01

Intramolecular interactions between fragments of L-phenylalanine, i.e., phenyl and alaninyl, have been investigated using dual space analysis (DSA) quantum mechanically. Valence space photoelectron spectra (PES), orbital energy topology and correlation diagram, as well as orbital momentum distributions (MDs) of L-phenylalanine, benzene and L-alanine are studied using density functional theory methods. While fully resolved experimental PES of L-phenylalanine is not yet available, our simulated PES reproduces major features of the experimental measurement. For benzene, the simulated orbital MDs for 1e(1g) and 1a(2u) orbitals also agree well with those measured using electron momentum spectra. Our theoretical models are then applied to reveal intramolecular interactions of the species on an orbital base, using DSA. Valence orbitals of L-phenylalanine can be essentially deduced into contributions from its fragments such as phenyl and alaninyl as well as their interactions. The fragment orbitals inherit properties of their parent species in energy and shape (ie., MDs). Phenylalanine orbitals show strong bonding in the energy range of 14-20 eV, rather than outside of this region. This study presents a competent orbital based fragments-in-molecules picture in the valence space, which supports the fragment molecular orbital picture and building block principle in valence space. The optimized structures of the molecules are represented using the recently developed interactive 3D-PDF technique. Copyright © 2010 Wiley Periodicals, Inc.

From stable divalent to valence-fluctuating behaviour in Eu(Rh1-xIrx)2Si2 single crystals

NASA Astrophysics Data System (ADS)

Seiro, Silvia; Geibel, Christoph

2011-09-01

We have succeeded in growing high-quality single crystals of the valence-fluctuating system EuIr2Si2, the divalent Eu system EuRh2Si2 and the substitutional alloy Eu(Rh1-xIrx)2Si2 across the range 0 < x < 1, which we characterized by means of x-ray diffraction, energy-dispersive x-ray spectroscopy, specific heat, magnetization and resistivity measurements. On increasing x, the divalent Eu ground state subsists up to x = 0.25 with a slight increase in Néel temperature, while for 0.3≤x < 0.7 a sharp hysteretic change in susceptibility and resistivity marks the first-order valence transition. For x≳0.7 the broad feature observed in the physical properties is characteristic of the continuous valence evolution beyond the critical end point of the valence transition line, and the resistivity is reminiscent of Kondo-like behaviour while the Sommerfeld coefficient indicates a mass renormalization of at least a factor of 8. The resulting phase diagram is similar to those reported for polycrystalline Eu(Pd1-xAux)2Si2 and EuNi2(Si1-xGex)2, confirming its generic character for Eu systems, and markedly different to those of homologue Ce and Yb systems, which present a continuous suppression of the antiferromagnetism accompanied by a very smooth evolution of the valence. We discuss these differences and suggest them to be related to the large polarization energy of the Eu half-filled 4f shell. We further argue that the changes in the rare earth valence between RRh2Si2 and RIr2Si2 (R = Ce, Eu, Yb) are governed by a purely electronic effect and not by a volume effect.

Decay rates of inner-valence excitations in noble gas atoms.

PubMed

Gokhberg, K; Averbukh, V; Cederbaum, L S

2007-04-21

A Fano - algebraic diagrammatic construction - Stieltjes method has been recently developed for ab initio calculations of nonradiative decay rates [V. Averbukh and L. S. Cederbaum, J. Chem. Phys. 123, 204107 (2005)] of singly ionized states. In the present work this method is generalized for the case of electronic decay of excited states. The decay widths of autoionizing inner-valence-excited states of Ne, Ar, and Kr are calculated. Apart from the lowest excitation of Kr, they are found to be in good to excellent agreement with the experimental values. Comparison with the other theoretical studies shows that in many cases the new method performs better than the previously available techniques.

Effects of Emotion on Associative Recognition: Valence and Retention Interval Matter

PubMed Central

Pierce, Benton H.; Kensinger, Elizabeth A.

2011-01-01

In two experiments, we examined the effects of emotional valence and arousal on associative binding. Participants studied negative, positive, and neutral word pairs, followed by an associative recognition test. In Experiment 1, with a short-delayed test, accuracy for intact pairs was equivalent across valences, whereas accuracy for rearranged pairs was lower for negative than for positive and neutral pairs. In Experiment 2, we tested participants after a one-week delay and found that accuracy was greater for intact negative than for intact neutral pairs, whereas rearranged pair accuracy was equivalent across valences. These results suggest that, although negative emotional valence impairs associative binding after a short delay, it may improve binding after a longer delay. The results also suggest that valence, as well as arousal, needs to be considered when examining the effects of emotion on associative memory. PMID:21401233

Transferable pseudoclassical electrons for aufbau of atomic ions.

PubMed

Ekesan, Solen; Kale, Seyit; Herzfeld, Judith

2014-06-05

Generalizing the LEWIS reactive force field from electron pairs to single electrons, we present LEWIS• in which explicit valence electrons interact with each other and with nuclear cores via pairwise interactions. The valence electrons are independently mobile particles, following classical equations of motion according to potentials modified from Coulombic as required to capture quantum characteristics. As proof of principle, the aufbau of atomic ions is described for diverse main group elements from the first three rows of the periodic table, using a single potential for interactions between electrons of like spin and another for electrons of unlike spin. The electrons of each spin are found to distribute themselves in a fashion akin to the major lobes of the hybrid atomic orbitals, suggesting a pointillist description of the electron density. The broader validity of the LEWIS• force field is illustrated by predicting the vibrational frequencies of diatomic and triatomic hydrogen species. Copyright © 2014 Wiley Periodicals, Inc.

The electronic structure of lithium metagallate.

PubMed

Johnson, N W; McLeod, J A; Moewes, A

2011-11-09

Herein we present a study of the electronic structure of lithium metagallate (LiGaO(2)), a material of interest in the field of optoelectronics. We use soft x-ray spectroscopy to probe the electronic structure of both the valence and conduction bands and compare our measurements to ab initio density functional theory calculations. We use several different exchange-correlation functionals, but find that no single theoretical approach used herein accurately quantifies both the band gap and the Ga 3d(10) states in LiGaO(2). We derive a band gap of 5.6 eV, and characterize electron hybridization in both the valence and conduction bands. Our study of the x-ray spectra may prove useful in analysing spectra from more complicated LiGaO(2) heterostructures. © 2011 IOP Publishing Ltd

Electronic excitations in long polyenes revisited

NASA Astrophysics Data System (ADS)

Schmidt, Maximilian; Tavan, Paul

2012-03-01

We apply the valence shell model OM2 [W. Weber and W. Thiel, Theor. Chem. Acc. 103, 495, (2000), 10.1007/s002149900083] combined with multireference configuration interaction (MRCI) to compute the vertical excitation energies and transition dipole moments of the low-energy singlet excitations in the polyenes with 4 ⩽ N ⩽ 22π-electrons. We find that the OM2/MRCI descriptions closely resemble those of Pariser-Parr-Pople (PPP) π-electron models [P. Tavan and K. Schulten, Phys. Rev. B 36, 4337, (1987)], if equivalent MRCI procedures and regularly alternating model geometries are used. OM2/MRCI optimized geometries are shown to entail improved descriptions particularly for smaller polyenes (N ⩽ 12), for which sizeable deviations from the regular model geometries are found. With configuration interaction active spaces covering also the σ- in addition to the π-electrons, OM2/MRCI excitation energies turn out to become smaller by at most 0.35 eV for the ionic and 0.15 eV for the covalent excitations. The particle-hole (ph) symmetry, which in Pariser-Parr-Pople models arises from the zero-differential overlap approximation, is demonstrated to be only weakly broken in OM2 such that the oscillator strengths of the covalent 1B_u^- states, which artificially vanish in ph-symmetric models, are predicted to be very small. According to OM2/MRCI and experimental data the 1B_u^- state is the third excited singlet state for N < 12 and becomes the second for N ⩾ 14. By comparisons with results of other theoretical approaches and experimental evidence we argue that deficiencies of the particular MRCI method employed by us, which show up in a poor size consistency of the covalent excitations for N > 12, are caused by its restriction to at most doubly excited references.

New Advancements in the Study of the Uniform Electron Gas with Full Configuration Interaction Quantum Monte Carlo

NASA Astrophysics Data System (ADS)

Ruggeri, Michele; Luo, Hongjun; Alavi, Ali

Full Configuration Interaction Quantum Monte Carlo (FCIQMC) is able to give remarkably accurate results in the study of atoms and molecules. The study of the uniform electron gas (UEG) on the other hand has proven to be much harder, particularly in the low density regime. The source of this difficulty comes from the strong interparticle correlations that arise at low density, and essentially forbid the study of the electron gas in proximity of Wigner crystallization. We extend a previous study on the three dimensional electron gas computing the energy of a fully polarized gas for N=27 electrons at high and medium density (rS = 0 . 5 to 5 . 0). We show that even when dealing with a polarized UEG the computational cost of the study of systems with rS > 5 . 0 is prohibitive; in order to deal with correlations and to extend the density range that to be studied we introduce a basis of localized states and an effective transcorrelated Hamiltonian.

Secondary Electron Emission Spectroscopy of Diamond Surfaces

NASA Technical Reports Server (NTRS)

Krainsky, Isay L.; Asnin, Vladimir M.; Petukhov, Andre G.

1999-01-01

This report presents the results of the secondary electron emission spectroscopy study of hydrogenated diamond surfaces for single crystals and chemical vapor-deposited polycrystalline films. One-electron calculations of Auger spectra of diamond surfaces having various hydrogen coverages are presented, the major features of the experimental spectra are explained, and a theoretical model for Auger spectra of hydrogenated diamond surfaces is proposed. An energy shift and a change in the line shape of the carbon core-valence-valence (KVV) Auger spectra were observed for diamond surfaces after exposure to an electron beam or by annealing at temperatures higher than 950 C. This change is related to the redistribution of the valence-band local density of states caused by hydrogen desorption from the surface. A strong negative electron affinity (NEA) effect, which appeared as a large, narrow peak in the low-energy portion of the spectrum of the secondary electron energy distribution, was also observed on the diamond surfaces. A fine structure in this peak, which was found for the first time, reflected the energy structure of the bottom of the conduction band. Further, the breakup of the bulk excitons at the surface during secondary electron emission was attributed to one of the features of this structure. The study demonstrated that the NEA type depends on the extent of hydrogen coverage of the diamond surface, changing from the true type for the completely hydrogenated surface to the effective type for the partially hydrogenated surface.

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 mediate the…

The electronic structure of vanadium monochloride cation (VCl+): Tackling the complexities of transition metal species

NASA Astrophysics Data System (ADS)

DeYonker, Nathan J.; Halfen, DeWayne T.; Allen, Wesley D.; Ziurys, Lucy M.

2014-11-01

Six electronic states (X 4Σ-, A 4Π, B 4Δ, 2Φ, 2Δ, 2Σ+) of the vanadium monochloride cation (VCl+) are described using large basis set coupled cluster theory. For the two lowest quartet states (X 4Σ- and A 4Π), a focal point analysis (FPA) approach was used that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through pentuple (CCSDTQP) excitations. FPA adiabatic excitation energies (T0) and spectroscopic constants (re, r0, Be, B0, bar De, He, ωe, v0, αe, ωexe) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, and spin-orbit coupling. Due to the delicate interplay between dynamical and static electronic correlation, single reference coupled cluster theory is able to provide the correct ground electronic state (X 4Σ-), while multireference configuration interaction theory cannot. Perturbations from the first- and second-order spin orbit coupling of low-lying states with quartet spin multiplicity reveal an immensely complex rotational spectrum relative to the isovalent species VO, VS, and TiCl. Computational data on the doublet manifold suggest that the lowest-lying doublet state (2Γ) has a Te of ˜11 200 cm-1. Overall, this study shows that laboratory and theoretical rotational spectroscopists must work more closely in tandem to better understand the bonding and structure of molecules containing transition metals.

Emotions and false memories: valence or arousal?

PubMed

Corson, Yves; Verrier, Nadège

2007-03-01

The effects of mood on false memories have not been studied systematically until recently. Some results seem to indicate that negative mood may reduce false recall and thus suggest an influence of emotional valence on false memory. The present research tested the effects of both valence and arousal on recall and recognition and indicates that the effect is actually due to arousal. In fact, whether participants' mood is positive, negative, or neutral, false memories are significantly more frequent under conditions of high arousal than under conditions of low arousal.

Electronic spectrum of the UO and UO(+) molecules.

PubMed

Tyagi, Rajni; Zhang, Zhiyong; Pitzer, Russell M

2014-12-18

Electronic theory calculations are applied to the study of the UO molecule and the UO(+) ion. Relativistic effective core potentials are used along with the accompanying valence spin-orbit operators. Polarized double-ς and triple-ς basis sets are used. Molecular orbitals are obtained from state-averaged multiconfiguration self-consistent field calculations and then used in multireference spin-orbit configuration interaction calculations with a number of millions of terms. The ground state of UO has open shells of 5f(3)7s(1), angular momentum Ω = 4, and a spin-orbit-induced avoided crossing near the equilibrium internuclear distance. Many UO excited states are studied with rotational constants, intensities, and experimental comparisons. The ground state of UO(+) is of 5f(3) nature with Ω = 9/2. Many UO(+) excited states are also studied. The open-shell nature of both UO and UO(+) leads to many low-lying excited states.

Excitations of one-valence-proton, one-valence-neutron nucleus {sup 210}Bi from cold-neutron capture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cieplicka-Oryńczak, N.; Institute of Nuclear Physics, Polish Academy of Sciences, PL-31342 Kraków; Fornal, B.

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 ofmore » testing the calculations involving the core excitations.« less

Simulating Ru L3-edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.

2013-05-01

Ruthenium L2,3-edge X-ray absorption (XA) spectroscopy probes transitions from core 2p orbitals to the 4d levels of the atom and is a powerful tool for interrogating the local electronic and molecular structure around the metal atom. However, a molecular-level interpretation of the Ru L2,3-edge spectral lineshapes is often complicated by spin–orbit coupling (SOC) and multiplet effects. In this study, we develop spin-free time-dependent density functional theory (TDDFT) as a viable and predictive tool to simulate the Ru L3-edge spectra. We successfully simulate and analyze the ground state Ru L3-edge XA spectra of a series of RuII and RuIII complexes: [Ru(NH3)6]2+/3+,more » [Ru(CN)6]4-/3-, [RuCl6]4-/3-, and the ground (1A1) and photoexcited (3MLCT) transient states of [Ru(bpy)3]2+ and Ru(dcbpy)2(NCS)2 (termed N3). The TDDFT simulations reproduce all the experimentally observed features in Ru L3-edge XA spectra. The advantage of using TDDFT to assign complicated Ru L3-edge spectra is illustrated by its ability to identify ligand specific charge transfer features in complex molecules. We conclude that the B3LYP functional is the most reliable functional for accurately predicting the location of charge transfer features in these spectra. Experimental and simulated Ru L3-edge XA spectra are presented for the transition metal mixed-valence dimers [(NC)5MII-CN-RuIII(NH3)5]- (where M = Fe or Ru) dissolved in water. We explore the spectral signatures of electron delocalization in Ru L3-edge XA spectroscopy and our simulations reveal that the inclusion of explicit solvent molecules is crucial for reproducing the experimentally determined valencies, highlighting the importance of the role of the solvent in transition metal charge transfer chemistry.« less

An adiabatic spectroscopic investigation of the CsRb system in ground and numerous excited states

NASA Astrophysics Data System (ADS)

Souissi, Hanen; Jellali, Soulef; Maha, Chaieb; Habli, Héla; Oujia, Brahim; Gadéa, Florent Xavier

2017-10-01

Via ab-initio approximations, we investigate the electronic and structural features of the CsRb molecule. Adiabatic potential energy curves of 261,3Σ+, 181,3Π and 61,3Δ electronic states with their derived spectroscopic constants as well as vibrational levels spacing have been carried out and well explained. Our approach is founded on an Effective Core Potential (ECP) describing the valence electrons of the system. Using a large Gaussian basis set, the full valence Configuration Interaction can be applied easily on the two-effective valence electrons of the CsRb system. Furthermore, a detailed analysis of the electric dipolar properties has been made through the investigation of both permanent and transition dipole moments (PDM and TDM). It is significant that the ionic character connected with electron transfer that is linked to Cs+ Rb- state has been clearly illustrated in the adiabatic permanent dipole moment.

Transferable Pseudo-Classical Electrons for Aufbau of Atomic Ions

PubMed Central

Ekesan, Solen; Kale, Seyit; Herzfeld, Judith

2014-01-01

Generalizing the LEWIS reactive force field from electron pairs to single electrons, we present LEWIS• in which explicit valence electrons interact with each other and with nuclear cores via pairwise interactions. The valence electrons are independently mobile particles, following classical equations of motion according to potentials modified from Coulombic as required to capture quantum characteristics. As proof of principle, the aufbau of atomic ions is described for diverse main group elements from the first three rows of the periodic table, using a single potential for interactions between electrons of like spin and another for electrons of unlike spin. The electrons of each spin are found to distribute themselves in a fashion akin to the major lobes of the hybrid atomic orbitals, suggesting a pointillist description of the electron density. The broader validity of the LEWIS• force field is illustrated by predicting the vibrational frequencies of diatomic and triatomic hydrogen species. PMID:24752384

Development of Xi'an-CI package – applying the hole–particle symmetry in multi-reference electronic correlation calculations

NASA Astrophysics Data System (ADS)

Suo, Bingbing; Lei, Yibo; Han, Huixian; Wang, Yubin

2018-04-01

This mini-review introduces our works on the Xi'an-CI (configuration interaction) package using graphical unitary group approach (GUGA). Taking advantage of the hole-particle symmetry in GUGA, the Galfand states used to span the CI space are classified into CI subspaces according to the number of holes and particles, and the coupling coefficients used to calculate Hamiltonian matrix elements could be factorised into the segment factors in the hole, active and external spaces. An efficient multi-reference CI with single and double excitations (MRCISD) algorithm is thus developed that reduces the storage requirement and increases the number of correlated electrons significantly. The hole-particle symmetry also gives rise to a doubly contracted MRCISD approach. Moreover, the internally contracted Gelfand states are defined within the CI subspace arising from the hole-particle symmetry, which makes the implementation of internally contracted MRCISD in the framework of GUGA possible. In addition to MRCISD, the development of multi-reference second-order perturbation theory (MRPT2) also benefits from the hole-particle symmetry. A configuration-based MRPT2 algorithm is proposed and extended to the multi-state n-electron valence-state second-order perturbation theory.

Electron accommodation dynamics in the DNA base thymine

NASA Astrophysics Data System (ADS)

King, Sarah B.; Stephansen, Anne B.; Yokoi, Yuki; Yandell, Margaret A.; Kunin, Alice; Takayanagi, Toshiyuki; Neumark, Daniel M.

2015-07-01

The dynamics of electron attachment to the DNA base thymine are investigated using femtosecond time-resolved photoelectron imaging of the gas phase iodide-thymine (I-T) complex. An ultraviolet pump pulse ejects an electron from the iodide and prepares an iodine-thymine temporary negative ion that is photodetached with a near-IR probe pulse. The resulting photoelectrons are analyzed with velocity-map imaging. At excitation energies ranging from -120 meV to +90 meV with respect to the vertical detachment energy (VDE) of 4.05 eV for I-T, both the dipole-bound and valence-bound negative ions of thymine are observed. A slightly longer rise time for the valence-bound state than the dipole-bound state suggests that some of the dipole-bound anions convert to valence-bound species. No evidence is seen for a dipole-bound anion of thymine at higher excitation energies, in the range of 0.6 eV above the I-T VDE, which suggests that if the dipole-bound anion acts as a "doorway" to the valence-bound anion, it only does so at excitation energies near the VDE of the complex.

Electron accommodation dynamics in the DNA base thymine.

PubMed

King, Sarah B; Stephansen, Anne B; Yokoi, Yuki; Yandell, Margaret A; Kunin, Alice; Takayanagi, Toshiyuki; Neumark, Daniel M

2015-07-14

The dynamics of electron attachment to the DNA base thymine are investigated using femtosecond time-resolved photoelectron imaging of the gas phase iodide-thymine (I(-)T) complex. An ultraviolet pump pulse ejects an electron from the iodide and prepares an iodine-thymine temporary negative ion that is photodetached with a near-IR probe pulse. The resulting photoelectrons are analyzed with velocity-map imaging. At excitation energies ranging from -120 meV to +90 meV with respect to the vertical detachment energy (VDE) of 4.05 eV for I(-)T, both the dipole-bound and valence-bound negative ions of thymine are observed. A slightly longer rise time for the valence-bound state than the dipole-bound state suggests that some of the dipole-bound anions convert to valence-bound species. No evidence is seen for a dipole-bound anion of thymine at higher excitation energies, in the range of 0.6 eV above the I(-)T VDE, which suggests that if the dipole-bound anion acts as a "doorway" to the valence-bound anion, it only does so at excitation energies near the VDE of the complex.

NEVER forget: negative emotional valence enhances recapitulation.

PubMed

Bowen, Holly J; Kark, Sarah M; Kensinger, Elizabeth A

2018-06-01

A hallmark feature of episodic memory is that of "mental time travel," whereby an individual feels they have returned to a prior moment in time. Cognitive and behavioral neuroscience methods have revealed a neurobiological counterpart: Successful retrieval often is associated with reactivation of a prior brain state. We review the emerging literature on memory reactivation and recapitulation, and we describe evidence for the effects of emotion on these processes. Based on this review, we propose a new model: Negative Emotional Valence Enhances Recapitulation (NEVER). This model diverges from existing models of emotional memory in three key ways. First, it underscores the effects of emotion during retrieval. Second, it stresses the importance of sensory processing to emotional memory. Third, it emphasizes how emotional valence - whether an event is negative or positive - affects the way that information is remembered. The model specifically proposes that, as compared to positive events, negative events both trigger increased encoding of sensory detail and elicit a closer resemblance between the sensory encoding signature and the sensory retrieval signature. The model also proposes that negative valence enhances the reactivation and storage of sensory details over offline periods, leading to a greater divergence between the sensory recapitulation of negative and positive memories over time. Importantly, the model proposes that these valence-based differences occur even when events are equated for arousal, thus rendering an exclusively arousal-based theory of emotional memory insufficient. We conclude by discussing implications of the model and suggesting directions for future research to test the tenets of the model.

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

Polarity determination of polar and semipolar (112¯2) InN and GaN layers by valence band photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Skuridina, D.; Dinh, D. V.; Lacroix, B.; Ruterana, P.; Hoffmann, M.; Sitar, Z.; Pristovsek, M.; Kneissl, M.; Vogt, P.

2013-11-01

We demonstrate that the polarity of polar (0001), (0001¯) and semipolar (112¯2) InN and GaN thin layers can be determined by valence band X-ray photoemission spectroscopy (XPS). The polarity of the layers has been confirmed by wet etching and convergent beam electron diffraction. Unlike these two techniques, XPS is a non-destructive method and unaffected by surface oxidation or roughness. Different intensities of the valence band states in spectra recorded by using AlKα X-ray radiation are observed for N-polar and group-III-polar layers. The highest intensity of the valence band state at ≈3.5 eV for InN and ≈5.2 eV for GaN correlates with the group-III polarity, while the highest intensity at ≈6.7 eV for InN and ≈9.5 eV for GaN correlates with the N-polarity. The difference between the peaks for the group-III- and N-polar orientations was found to be statistically significant at the 0.05 significance level. The polarity of semipolar (112¯2) InN and GaN layers can be determined by recording valence band photoelectrons emitted along the [000 ± 1] direction.

Motivation and attention: Incongruent effects of feedback on the processing of valence.

PubMed

Rothermund, Klaus

2003-09-01

Four experiments investigated the relation between outcome-related motivational states and processes of automatic attention allocation. Experiments 1-3 analyzed influences of feedback on evaluative decisions. Words of opposite valence to the feedback were processed faster, indicating that it is easier to allocate attention to the valence of an affectively incongruent word. Experiment 4 replicated the incongruent effect with interference effects of word valence in a grammatical-categorization task, indicating that the effect reflects automatic attentional capture. In all experiments, incongruent effects of feedback emerged only in a situation involving an attentional shift between words that differed in valence.

Measurement of the first ionization potential of lawrencium, element 103.

PubMed

Sato, T K; Asai, M; Borschevsky, A; Stora, T; Sato, N; Kaneya, Y; Tsukada, K; Düllmann, Ch E; Eberhardt, K; Eliav, E; Ichikawa, S; Kaldor, U; Kratz, J V; Miyashita, S; Nagame, Y; Ooe, K; Osa, A; Renisch, D; Runke, J; Schädel, M; Thörle-Pospiech, P; Toyoshima, A; Trautmann, N

2015-04-09

The chemical properties of an element are primarily governed by the configuration of electrons in the valence shell. Relativistic effects influence the electronic structure of heavy elements in the sixth row of the periodic table, and these effects increase dramatically in the seventh row--including the actinides--even affecting ground-state configurations. Atomic s and p1/2 orbitals are stabilized by relativistic effects, whereas p3/2, d and f orbitals are destabilized, so that ground-state configurations of heavy elements may differ from those of lighter elements in the same group. The first ionization potential (IP1) is a measure of the energy required to remove one valence electron from a neutral atom, and is an atomic property that reflects the outermost electronic configuration. Precise and accurate experimental determination of IP1 gives information on the binding energy of valence electrons, and also, therefore, on the degree of relativistic stabilization. However, such measurements are hampered by the difficulty in obtaining the heaviest elements on scales of more than one atom at a time. Here we report that the experimentally obtained IP1 of the heaviest actinide, lawrencium (Lr, atomic number 103), is 4.96(+0.08)(-0.07) electronvolts. The IP1 of Lr was measured with (256)Lr (half-life 27 seconds) using an efficient surface ion-source and a radioisotope detection system coupled to a mass separator. The measured IP1 is in excellent agreement with the value of 4.963(15) electronvolts predicted here by state-of-the-art relativistic calculations. The present work provides a reliable benchmark for theoretical calculations and also opens the way for IP1 measurements of superheavy elements (that is, transactinides) on an atom-at-a-time scale.

Valence-band-edge shift due to doping in p + GaAs

NASA Astrophysics Data System (ADS)

Silberman, J. A.; de Lyon, T. J.; Woodall, J. M.

1991-05-01

Accurate knowledge of the shifts in valence- and conduction-band edges due to heavy doping effects is crucial in modeling GaAs device structures that utilize heavily doped layers. X-ray photoemission spectroscopy was used to deduce the shift in the valence-band-edge induced by carbon (p type) doping to a carrier density of 1×1020 cm-3 based on a determination of the bulk binding energy of the Ga and As core levels in this material. Analysis of the data indicates that the shift of the valence-band maximum into the gap and the penetration of the Fermi level into the valence bands exactly compensate at this degenerate carrier concentration, to give ΔEv =0.12±0.05 eV.

Trait valence and the better-than-average effect.

PubMed

Gold, Ron S; Brown, Mark G

2011-12-01

People tend to regard themselves as having superior personality traits compared to their average peer. To test whether this "better-than-average effect" varies with trait valence, participants (N = 154 students) rated both themselves and the average student on traits constituting either positive or negative poles of five trait dimensions. In each case, the better-than-average effect was found, but trait valence had no effect. Results were discussed in terms of Kahneman and Tversky's prospect theory.

Valence bond and von Neumann entanglement entropy in Heisenberg ladders.

PubMed

Kallin, Ann B; González, Iván; Hastings, Matthew B; Melko, Roger G

2009-09-11

We present a direct comparison of the recently proposed valence bond entanglement entropy and the von Neumann entanglement entropy on spin-1/2 Heisenberg systems using quantum Monte Carlo and density-matrix renormalization group simulations. For one-dimensional chains we show that the valence bond entropy can be either less or greater than the von Neumann entropy; hence, it cannot provide a bound on the latter. On ladder geometries, simulations with up to seven legs are sufficient to indicate that the von Neumann entropy in two dimensions obeys an area law, even though the valence bond entanglement entropy has a multiplicative logarithmic correction.

Human Amygdala Tracks a Feature-Based Valence Signal Embedded within the Facial Expression of Surprise.

PubMed

Kim, M Justin; Mattek, Alison M; Bennett, Randi H; Solomon, Kimberly M; Shin, Jin; Whalen, Paul J

2017-09-27

Human amygdala function has been traditionally associated with processing the affective valence (negative vs positive) of an emotionally charged event, especially those that signal fear or threat. However, this account of human amygdala function can be explained by alternative views, which posit that the amygdala might be tuned to either (1) general emotional arousal (activation vs deactivation) or (2) specific emotion categories (fear vs happy). Delineating the pure effects of valence independent of arousal or emotion category is a challenging task, given that these variables naturally covary under many circumstances. To circumvent this issue and test the sensitivity of the human amygdala to valence values specifically, we measured the dimension of valence within the single facial expression category of surprise. Given the inherent valence ambiguity of this category, we show that surprised expression exemplars are attributed valence and arousal values that are uniquely and naturally uncorrelated. We then present fMRI data from both sexes, showing that the amygdala tracks these consensus valence values. Finally, we provide evidence that these valence values are linked to specific visual features of the mouth region, isolating the signal by which the amygdala detects this valence information. SIGNIFICANCE STATEMENT There is an open question as to whether human amygdala function tracks the valence value of cues in the environment, as opposed to either a more general emotional arousal value or a more specific emotion category distinction. Here, we demonstrate the utility of surprised facial expressions because exemplars within this emotion category take on valence values spanning the dimension of bipolar valence (positive to negative) at a consistent level of emotional arousal. Functional neuroimaging data showed that amygdala responses tracked the valence of surprised facial expressions, unconfounded by arousal. Furthermore, a machine learning classifier identified

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

Effects of valence and divided attention on cognitive reappraisal processes.

PubMed

Morris, John A; Leclerc, Christina M; Kensinger, Elizabeth A

2014-12-01

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. © The Author (2014). Published by Oxford University Press. For Permissions, please email: journals.permissions@oup.com.

Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Bonding in O3 and SO2.

PubMed

Takeshita, Tyler Y; Lindquist, Beth A; Dunning, Thom H

2015-07-16

There are many well-known differences in the physical and chemical properties of ozone (O3) and sulfur dioxide (SO2). O3 has longer and weaker bonds than O2, whereas SO2 has shorter and stronger bonds than SO. The O-O2 bond is dramatically weaker than the O-SO bond, and the singlet-triplet gap in SO2 is more than double that in O3. In addition, O3 is a very reactive species, while SO2 is far less so. These disparities have been attributed to variations in the amount of diradical character in the two molecules. In this work, we use generalized valence bond (GVB) theory to characterize the electronic structure of ozone and sulfur dioxide, showing O3 does indeed possess significant diradical character, whereas SO2 is effectively a closed shell molecule. The GVB results provide critical insights into the genesis of the observed difference in these two isoelectronic species. SO2 possesses a recoupled pair bond dyad in the a"(π) system, resulting in SO double bonds. The π system of O3, on the other hand, has a lone pair on the central oxygen atom plus a pair of electrons in orbitals on the terminal oxygen atoms that give rise to a relatively weak π interaction.

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

DOE PAGES

Chi, Hang; Tan, Gangjian; Kanatzidis, Mercouri G.; ...

2016-05-02

In this study, 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 μ B (Bohr magneton) of magnetic moment to Sn 1–xMn xTe. The Curie temperatureTC reaches ~14K 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 R H andmore » a favorably enhanced Seebeck coefficient S at the same time. With the thermal conductivityκ 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

Mixed-valence molecular four-dot unit for quantum cellular automata: Vibronic self-trapping and cell-cell response.

PubMed

Tsukerblat, Boris; Palii, Andrew; Clemente-Juan, Juan Modesto; Coronado, Eugenio

2015-10-07

Our interest in this article is prompted by the vibronic problem of charge polarized states in the four-dot molecular quantum cellular automata (mQCA), a paradigm for nanoelectronics, in which binary information is encoded in charge configuration of the mQCA cell. Here, we report the evaluation of the electronic levels and adiabatic potentials of mixed-valence (MV) tetra-ruthenium (2Ru(ii) + 2Ru(iii)) derivatives (assembled as two coupled Creutz-Taube complexes) for which molecular implementations of quantum cellular automata (QCA) was proposed. The cell based on this molecule includes two holes shared among four spinless sites and correspondingly we employ the model which takes into account the two relevant electron transfer processes (through the side and through the diagonal of the square) as well as the difference in Coulomb energies for different instant positions of localization of the hole pair. The combined Jahn-Teller (JT) and pseudo JT vibronic coupling is treated within the conventional Piepho-Krauzs-Schatz model adapted to a bi-electronic MV species with the square-planar topology. The adiabatic potentials are evaluated for the low lying Coulomb levels in which the antipodal sites are occupied, the case just actual for utilization in mQCA. The conditions for the vibronic self-trapping in spin-singlet and spin-triplet states are revealed in terms of the two actual transfer pathways parameters and the strength of the vibronic coupling. Spin related effects in degrees of the localization which are found for spin-singlet and spin-triplet states are discussed. The polarization of the cell is evaluated and we demonstrate how the partial delocalization caused by the joint action of the vibronic coupling and electron transfer processes influences polarization of a four-dot cell. The results obtained within the adiabatic approach are compared with those based on the numerical solution of the dynamic vibronic problem. Finally, the Coulomb interaction between

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.

Memory effects of sleep, emotional valence, arousal and novelty in children.

PubMed

Vermeulen, Marije C M; van der Heijden, Kristiaan B; Benjamins, Jeroen S; Swaab, Hanna; van Someren, Eus J W

2017-06-01

Effectiveness of memory consolidation is determined by multiple factors, including sleep after learning, emotional valence, arousal and novelty. Few studies investigated how the effect of sleep compares with (and interacts with) these other factors, of which virtually none are in children. The present study did so by repeated assessment of declarative memory in 386 children (45% boys) aged 9-11 years through an online word-pair task. Children were randomly assigned to either a morning or evening learning session of 30 unrelated word-pairs with positive, neutral or negative valenced cues and neutral targets. After immediately assessing baseline recognition, delayed recognition was recorded either 12 or 24 h later, resulting in four different assessment schedules. One week later, the procedure was repeated with exactly the same word-pairs to evaluate whether effects differed for relearning versus original novel learning. Mixed-effect logistic regression models were used to evaluate how the probability of correct recognition was affected by sleep, valence, arousal, novelty and their interactions. Both immediate and delayed recognition were worse for pairs with negatively valenced or less arousing cue words. Relearning improved immediate and delayed word-pair recognition. In contrast to these effects, sleep did not affect recognition, nor did sleep moderate the effects of arousal, valence and novelty. The findings suggest a robust inclination of children to specifically forget the pairing of words to negatively valenced cue words. In agreement with a recent meta-analysis, children seem to depend less on sleep for the consolidation of information than has been reported for adults, irrespective of the emotional valence, arousal and novelty of word-pairs. © 2017 European Sleep Research Society.

On pleasure and thrill: the interplay between arousal and valence during visual word recognition.

PubMed

Recio, Guillermo; Conrad, Markus; Hansen, Laura B; Jacobs, Arthur M

2014-07-01

We investigated the interplay between arousal and valence in the early processing of affective words. Event-related potentials (ERPs) were recorded while participants read words organized in an orthogonal design with the factors valence (positive, negative, neutral) and arousal (low, medium, high) in a lexical decision task. We observed faster reaction times for words of positive valence and for those of high arousal. Data from ERPs showed increased early posterior negativity (EPN) suggesting improved visual processing of these conditions. Valence effects appeared for medium and low arousal and were absent for high arousal. Arousal effects were obtained for neutral and negative words but were absent for positive words. These results suggest independent contributions of arousal and valence at early attentional stages of processing. Arousal effects preceded valence effects in the ERP data suggesting that arousal serves as an early alert system preparing a subsequent evaluation in terms of valence. Copyright © 2014 Elsevier Inc. All rights reserved.

Power converter connection configuration

DOEpatents

Beihoff, Bruce C.; Kehl, Dennis L.; Gettelfinger, Lee A.; Kaishian, Steven C.; Phillips, Mark G.; Radosevich, Lawrence D.

2008-11-11

EMI shielding is provided for power electronics circuits and the like via a direct-mount reference plane support and shielding structure. The thermal support may receive one or more power electronic circuits. The support may aid in removing heat from the circuits through fluid circulating through the support. The support forms a shield from both external EMI/RFI and from interference generated by operation of the power electronic circuits. Features may be provided to permit and enhance connection of the circuitry to external circuitry, such as improved terminal configurations. Modular units may be assembled that may be coupled to electronic circuitry via plug-in arrangements or through interface with a backplane or similar mounting and interconnecting structures.

Atomic data and line intensities for the S V ion

NASA Astrophysics Data System (ADS)

Iorga, C.; Stancalie, V.

2017-05-01

The energy levels, oscillator strengths, spontaneous radiative decay rates, lifetimes and electron impact collision strengths have been obtained for the [ Ne ] 3s nl, [ Ne ] 3p nl, [ Ne ] 3d nl configurations belonging to S V ion, with n ≤ 7 and l ≤ 4, resulting in 567 fine-structure levels. The calculations have been performed within the fully relativistic Flexible Atomic Code (FAC, Gu, 2008) framework and the distorted wave approximation. To attain the desired accuracy for the levels energy, the valence-valence and valence-core correlations have been taken care of by including 96 configuration state functions (CSFs) in the model, reaching a total of 3147 fine-structure levels. Two separate calculations have been performed with the local central potential computed for two different average configurations. A third calculation is also performed without the addition of the core-excited states in the atomic model for completeness. The effects of slightly different mean configurations and valence-core correlations on the energy levels and decay rates are investigated. The collision data have been computed employing the relativistic distorted-wave method along with the atomic model containing the 96 CSFs and corresponding to the ground state mean configuration. The collision strengths corresponding to excitation from the first four fine-structure levels are given for five energy values of the scattered electron 2.65, 6.18, 11.02, 17.36, 25.43 Rydberg, plus an additional variable small energy value near the threshold. A collisional-radiative model has been employed to solve the rate equations for the populations of the 567 fine-structure levels, for a temperature of LogTE(K) = 5.2 corresponding to the maximum abundance of S V, and at densities 106-1016cm-3, assuming a Maxwellian electron energy distribution function and black body radiation of temperature 6000 K and dilution factor 0.35 for the photon distribution function. The main processes responsible for the

Investigating Valence and Autonomy in Children's Relationships with Imaginary Companions

ERIC Educational Resources Information Center

McInnis, Melissa A.; Pierucci, Jillian M.; Gilpin, Ansley Tullos

2013-01-01

Little research has explored valence and autonomy in children's imaginary relationships. In the present study, a new interview (modeled after an existing measure for real relationships) was designed to elicit descriptions of both positive and negative interactions with imaginary companions and to provide a measure of relationship valence and…

A Unified Approach to Electron Counting in Main-Group Clusters

ERIC Educational Resources Information Center

McGrady, John E.

2004-01-01

A presentation of an extensive review of traditional approaches to teaching electron counting is given. The electron-precise clusters are usually taken as a reference point for rationalizing the structures of their electron-rich counterparts, which are characterized by valence electron counts greater than 5n.

Electrostatic drift instability in a magnetotail configuration: The role of bouncing electrons

NASA Astrophysics Data System (ADS)

Fruit, G.; Louarn, P.; Tur, A.

2017-03-01

To understand the possible destabilization of two-dimensional current sheets, a kinetic model is proposed to describe the resonant interaction between electrostatic modes and trapped electrons that bounce within the sheet. This work follows the initial investigation by Tur, Louarn, and Yanovsky [Phys. Plasmas 17, 102905 (2010)] and Fruit, Louarn, and Tur [Phys. Plasmas 20, 022113 (2013)] that is revised and extended. Using a quasi-dipolar equilibrium state, the linearized gyro-kinetic Vlasov equation is solved for electrostatic fluctuations with a period of the order of the electron bounce period. Using an appropriated Fourier expansion of the particle motion along the magnetic field, the complete time integration of the non-local perturbed distribution functions is performed. The dispersion relation for electrostatic modes is then obtained through the quasineutrality condition. It is found that for a mildly stretched configuration ( L ˜8 ), strongly unstable electrostatic modes may develop in the current sheet with the growth rate of the order of a few seconds provided that the background density gradient responsible for the diamagnetic drift effects is sharp enough: typical length scale over one Earth radius or less. However, when this condition in the density gradient is not met, these electrostatic modes grow too slowly to be accountable for a rapid destabilization of the magnetic structure. This strong but finely tuned instability may offer opportunities to explain features in magnetospheric substorms.

Valence and arousal-based affective evaluations of foods.

PubMed

Woodward, Halley E; Treat, Teresa A; Cameron, C Daryl; Yegorova, Vitaliya

2017-01-01

We investigated the nutrient-specific and individual-specific validity of dual-process models of valenced and arousal-based affective evaluations of foods across the disordered eating spectrum. 283 undergraduate women provided implicit and explicit valence and arousal-based evaluations of 120 food photos with known nutritional information on structurally similar indirect and direct affect misattribution procedures (AMP; Payne et al., 2005, 2008), and completed questionnaires assessing body mass index (BMI), hunger, restriction, and binge eating. Nomothetically, added fat and added sugar enhance evaluations of foods. Idiographically, hunger and binge eating enhance activation, whereas BMI and restriction enhance pleasantness. Added fat is salient for women who are heavier, hungrier, or who restrict; added sugar is influential for less hungry women. Restriction relates only to valence, whereas binge eating relates only to arousal. Findings are similar across implicit and explicit affective evaluations, albeit stronger for explicit, providing modest support for dual-process models of affective evaluation of foods. Copyright © 2016 Elsevier Ltd. All rights reserved.

Right hemisphere or valence hypothesis, or both? The processing of hybrid faces in the intact and callosotomized brain.

PubMed

Prete, Giulia; Laeng, Bruno; Fabri, Mara; Foschi, Nicoletta; Tommasi, Luca

2015-02-01

The valence hypothesis and the right hemisphere hypothesis in emotion processing have been alternatively supported. To better disentangle the two accounts, we carried out two studies, presenting healthy participants and an anterior callosotomized patient with 'hybrid faces', stimuli created by superimposing the low spatial frequencies of an emotional face to the high spatial frequencies of the same face in a neutral expression. In both studies we asked participants to judge the friendliness level of stimuli, which is an indirect measure of the processing of emotional information, despite this remaining "invisible". In Experiment 1 we presented hybrid faces in a divided visual field paradigm using different tachistoscopic presentation times; in Experiment 2 we presented hybrid chimeric faces in canonical view and upside-down. In Experiments 3 and 4 we tested a callosotomized patient, with spared splenium, in similar paradigms as those used in Experiments 1 and 2. Results from Experiments 1 and 3 were consistent with the valence hypothesis, whereas results of Experiments 2 and 4 were consistent with the right hemisphere hypothesis. This study confirms that the low spatial frequencies of emotional faces influence the social judgments of observers, even when seen for 28 ms (Experiment 1), possibly by means of configural analysis (Experiment 2). The possible roles of the cortical and subcortical emotional routes in these tasks are discussed in the light of the results obtained in the callosotomized patient. We propose that the right hemisphere and the valence accounts are not mutually exclusive, at least in the case of subliminal emotion processing. Copyright © 2015 Elsevier Ltd. All rights reserved.

Arousal (but not valence) amplifies the impact of salience.

PubMed

Sutherland, Matthew R; Mather, Mara

2018-05-01

Previous findings indicate that negative arousal enhances bottom-up attention biases favouring perceptual salient stimuli over less salient stimuli. The current study tests whether those effects were driven by emotional arousal or by negative valence by comparing how well participants could identify visually presented letters after hearing either a negative arousing, positive arousing or neutral sound. On each trial, some letters were presented in a high contrast font and some in a low contrast font, creating a set of targets that differed in perceptual salience. Sounds rated as more emotionally arousing led to more identification of highly salient letters but not of less salient letters, whereas sounds' valence ratings did not impact salience biases. Thus, arousal, rather than valence, is a key factor enhancing visual processing of perceptually salient targets.

The range and valence of a real Smirnov function

NASA Astrophysics Data System (ADS)

Ferguson, Timothy; Ross, William T.

2018-02-01

We give a complete description of the possible ranges of real Smirnov functions (quotients of two bounded analytic functions on the open unit disk where the denominator is outer and such that the radial boundary values are real almost everywhere on the unit circle). Our techniques use the theory of unbounded symmetric Toeplitz operators, some general theory of unbounded symmetric operators, classical Hardy spaces, and an application of the uniformization theorem. In addition, we completely characterize the possible valences for these real Smirnov functions when the valence is finite. To do so we construct Riemann surfaces we call disk trees by welding together copies of the unit disk and its complement in the Riemann sphere. We also make use of certain trees we call valence trees that mirror the structure of disk trees.

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.

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

The role of the 5f valence orbitals of early actinides in chemical bonding

PubMed Central

Vitova, T.; Pidchenko, I.; Fellhauer, D.; Bagus, P. S.; Joly, Y.; Pruessmann, T.; Bahl, S.; Gonzalez-Robles, E.; Rothe, J.; Altmaier, M.; Denecke, M. A.; Geckeis, H.

2017-01-01

One of the long standing debates in actinide chemistry is the level of localization and participation of the actinide 5f valence orbitals in covalent bonds across the actinide series. Here we illuminate the role of the 5f valence orbitals of uranium, neptunium and plutonium in chemical bonding using advanced spectroscopies: actinide M4,5 HR-XANES and 3d4f RIXS. Results reveal that the 5f orbitals are active in the chemical bonding for uranium and neptunium, shown by significant variations in the level of their localization evidenced in the spectra. In contrast, the 5f orbitals of plutonium appear localized and surprisingly insensitive to different bonding environments. We envisage that this report of using relative energy differences between the 5fδ/ϕ and 5fπ*/5fσ* orbitals as a qualitative measure of overlap-driven actinyl bond covalency will spark activity, and extend to numerous applications of RIXS and HR-XANES to gain new insights into the electronic structures of the actinide elements. PMID:28681848

The role of the 5f valence orbitals of early actinides in chemical bonding

NASA Astrophysics Data System (ADS)

Vitova, T.; Pidchenko, I.; Fellhauer, D.; Bagus, P. S.; Joly, Y.; Pruessmann, T.; Bahl, S.; Gonzalez-Robles, E.; Rothe, J.; Altmaier, M.; Denecke, M. A.; Geckeis, H.

2017-07-01

One of the long standing debates in actinide chemistry is the level of localization and participation of the actinide 5f valence orbitals in covalent bonds across the actinide series. Here we illuminate the role of the 5f valence orbitals of uranium, neptunium and plutonium in chemical bonding using advanced spectroscopies: actinide M4,5 HR-XANES and 3d4f RIXS. Results reveal that the 5f orbitals are active in the chemical bonding for uranium and neptunium, shown by significant variations in the level of their localization evidenced in the spectra. In contrast, the 5f orbitals of plutonium appear localized and surprisingly insensitive to different bonding environments. We envisage that this report of using relative energy differences between the 5fδ/φ and 5fπ*/5fσ* orbitals as a qualitative measure of overlap-driven actinyl bond covalency will spark activity, and extend to numerous applications of RIXS and HR-XANES to gain new insights into the electronic structures of the actinide elements.

An open-source framework for analyzing N-electron dynamics. II. Hybrid density functional theory/configuration interaction methodology.

PubMed

Hermann, Gunter; Pohl, Vincent; Tremblay, Jean Christophe

2017-10-30

In this contribution, we extend our framework for analyzing and visualizing correlated many-electron dynamics to non-variational, highly scalable electronic structure method. Specifically, an explicitly time-dependent electronic wave packet is written as a linear combination of N-electron wave functions at the configuration interaction singles (CIS) level, which are obtained from a reference time-dependent density functional theory (TDDFT) calculation. The procedure is implemented in the open-source Python program detCI@ORBKIT, which extends the capabilities of our recently published post-processing toolbox (Hermann et al., J. Comput. Chem. 2016, 37, 1511). From the output of standard quantum chemistry packages using atom-centered Gaussian-type basis functions, the framework exploits the multideterminental structure of the hybrid TDDFT/CIS wave packet to compute fundamental one-electron quantities such as difference electronic densities, transient electronic flux densities, and transition dipole moments. The hybrid scheme is benchmarked against wave function data for the laser-driven state selective excitation in LiH. It is shown that all features of the electron dynamics are in good quantitative agreement with the higher-level method provided a judicious choice of functional is made. Broadband excitation of a medium-sized organic chromophore further demonstrates the scalability of the method. In addition, the time-dependent flux densities unravel the mechanistic details of the simulated charge migration process at a glance. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Valence-band structure of organic radical p-CF3PNN investigated by angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Anzai, Hiroaki; Takakura, Ryosuke; Ono, Yusuke; Ishihara, Suzuna; Sato, Hitoshi; Namatame, Hirofumi; Taniguchi, Masaki; Matsui, Toshiyuki; Noguchi, Satoru; Hosokoshi, Yuko

2018-05-01

We study the electronic structure of p-trifluoromethylphenyl nitronyl nitroxide (p-CF3PNN), which forms a one-dimensional alternating antiferromagnetic chain of molecules, using angle-resolved photoemission spectroscopy. A singly occupied molecular orbital (SOMO) is observed clearly at ∼ 2 eV in the valence-band spectra. The small band gap and the overlap between the SOMO orbitals in the NO groups are associated with the antiferromagnetic interaction between neighboring spins.

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…

Valence electronic structure of Ni in Ni Si alloys from relative K X-ray intensity studies

NASA Astrophysics Data System (ADS)

Kalayci, Y.; Aydinuraz, A.; Tugluoglu, B.; Mutlu, R. H.

2007-02-01

The Kβ-to-Kα X-ray intensity ratio of Ni in Ni 3Si, Ni 2Si and NiSi has been determined by energy dispersive X-ray fluorescence technique. It is found that the intensity ratio of Ni decreases from pure Ni to Ni 2Si and then increases from Ni 2Si to NiSi, in good agreement with the electronic structure calculations cited in the literature. We have also performed band structure calculations for pure Ni in various atomic configurations by means of linear muffin-tin orbital method and used this data with the normalized theoretical intensity ratios cited in the literature to estimate the 3d-occupation numbers of Ni in Ni-Si alloys. It is emphasized that investigation of alloying effect in terms of X-ray intensity ratios should be carried out for the stoichiometric alloys in order to make reliable and quantitative comparisons between theory and experiment in transition metal alloys.

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…

Studies of Copper, Silver, and Gold Cluster Anions: Evidence of Electronic Shell Structure.

NASA Astrophysics Data System (ADS)

Pettiette, Claire Lynn

A new Ultraviolet Magnetic Time-of-Flight Photoelectron Spectrometer (MTOFPES) has been developed for the study of the electronic structure of clusters produced in a pulsed supersonic molecular beam. This is the first technique which has been successful in probing the valence electronic states of metal clusters. The ultraviolet photoelectron spectra of negative cluster ions of the noble metals have been taken at several different photon energies. These are presented along with the electron affinity and HOMO-LUMO gap measurements for Cu_6^- to Cu_ {41}^-, using 4.66 eV and 6.42 eV detachment energies; Ag_3^- to Ag_{21}^-, using 6.42 eV detachment energy; and Au_3^ - to Au_{21}^-, using 6.42 eV and 7.89 eV detachment energies. The spectra provide the first detailed probes of the s valence electrons of the noble metal clusters. In addition, the 6.42 eV and 7.89 eV spectra probe the first one to two electron volts of the molecular orbitals of the d valence electrons of copper and gold clusters. The electron affinity and HOMO-LUMO gap measurements of the noble metal clusters agree with the predictions of the ellipsoidal shell model for mono-valent metal clusters. In particular, cluster numbers 8, 20, and 40--which correspond to the spherical shell closings of this model--have low electron affinities and large HOMO-LUMO gaps. The spectra of the gold cluster ions indicate that the molecular orbital energies of the cluster valence electrons are more widely spaced for gold than for copper or silver. This is to be expected for the heavy atom clusters when relativistic effects are taken into account.

Electronic structure and electron energy-loss spectroscopy of ZrO2 zirconia

NASA Astrophysics Data System (ADS)

Dash, L. K.; Vast, Nathalie; Baranek, Philippe; Cheynet, Marie-Claude; Reining, Lucia

2004-12-01

The atomic and electronic structures of zirconia are calculated within density functional theory, and their evolution is analyzed as the crystal-field symmetry changes from tetrahedral [cubic (c-ZrO2) and tetragonal (t-ZrO2) phases] to octahedral (hypothetical rutile ZrO2 ), to a mixing of these symmetries (monoclinic phase, m-ZrO2 ). We find that the theoretical bulk modulus in c-ZrO2 is 30% larger than the experimental value, showing that the introduction of yttria in zirconia has a significant effect. Electronic structure fingerprints which characterize each phase from their electronic spectra are identified. We have carried out electron energy-loss spectroscopy experiments at low momentum transfer and compared these results to the theoretical spectra calculated within the random phase approximation. We show a dependence of the valence and 4p ( N2,3 edge) plasmons on the crystal structure, the dependence of the latter being brought into the spectra by local-field effects. Last, we attribute low energy excitations observed in EELS of m-ZrO2 to defect states 2eV above the top of the intrinsic valence band, and the EELS fundamental band gap value is reconciled with the 5.2 or 5.8eV gaps determined by vacuum ultraviolet spectroscopy.

Itsy bitsy spider?: Valence and self-relevance predict size estimation.

PubMed

Leibovich, Tali; Cohen, Noga; Henik, Avishai

2016-12-01

The current study explored the role of valence and self-relevance in size estimation of neutral and aversive animals. In Experiment 1, participants who were highly fearful of spiders and participants with low fear of spiders rated the size and unpleasantness of spiders and other neutral animals (birds and butterflies). We found that although individuals with both high and low fear of spiders rated spiders as highly unpleasant, only the highly fearful participants rated spiders as larger than butterflies. Experiment 2 included additional pictures of wasps (not self-relevant, but unpleasant) and beetles. The results of this experiment replicated those of Experiment 1 and showed a similar bias in size estimation for beetles, but not for wasps. Mediation analysis revealed that in the high-fear group both relevance and valence influenced perceived size, whereas in the low-fear group only valence affected perceived size. These findings suggest that the effect of highly relevant stimuli on size perception is both direct and mediated by valence. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Arc-evaporated carbon films: optical properties and electron mean free paths

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, M.W.; Arakawa, E.T.; Dolfini, S.M.

1984-01-01

This paper describes briefly a method which can be used to calculate inelastic mean free paths for electrons with energies in the range of interest for the interpretation of surface phenomena. This method requires a knowledge of the optical properties of the material for the photon energies associated with the oscillator strength of the valence electrons. However, in general it is easier to obtain accurate values of the required properties than it is to measure the electron attenuation lengths in the energy region of interest. This technique, demonstrated here for arc-evaporated carbon, can be used for any material for whichmore » the optical properties can be measured over essentially the whole energy range corresponding to the valence electron response.« less

Europium mixed-valence, long-range magnetic order, and dynamic magnetic response in EuCu 2 ( Si x Ge 1 - x ) 2

DOE PAGES

Nemkovski, Krill S.; Kozlenko, D. P.; Alekseev, Pavel A.; ...

2016-11-01

In mixed-valence or heavy-fermion systems, the hybridization between local f orbitals and conduction band states can cause the suppression of long-range magnetic order, which competes with strong spin uctuations. Ce- and Yb-based systems have been found to exhibit fascinating physical properties (heavy-fermion superconductivity, non-Fermi-liquid states, etc.) when tuned to the vicinity of magnetic quantum critical points by use of various external control parameters (temperature, magnetic eld, chemical composition). Recently, similar effects (mixed-valence, Kondo uctuations, heavy Fermi liquid) have been reported to exist in some Eu-based compounds. Unlike Ce (Yb), Eu has a multiple electron (hole) occupancy of its 4f shell,more » and the magnetic Eu 2+ state (4f 7) has no orbital component in the usual LS coupling scheme, which can lead to a quite different and interesting physics. In the EuCu 2(Si xGe 1-x) 2 series, where the valence can be tuned by varying the Si/Ge ratio, it has been reported that a significant valence uctuation can exist even in the magnetic order regime. This paper presents a detailed study of the latter material using different microscopic probes (XANES, Mossbauer spectroscopy, elastic and inelastic neutron scattering), in which the composition dependence of the magnetic order and dynamics across the series is traced back to the change in the Eu valence state. In particular, the results support the persistence of valence uctuations into the antiferromagnetic state over a sizable composition range below the critical Si concentration x c ≈ 0:65. In conclusion, the sequence of magnetic ground states in the series is shown to re ect the evolution of the magnetic spectral response.« less

Density functional study of the structural, electronic, and magnetic properties of Mo n and Mo n S ( n = 1 - 10) clusters

NASA Astrophysics Data System (ADS)

Ziane, M.; Amitouche, F.; Bouarab, S.; Vega, A.

2017-12-01

Structural and electronic properties of pure molybdenum Mo n and molybdenum-sulfide Mo n S ( n = 1 - 10) clusters were investigated in the framework of the density functional theory within the generalized gradient approximation to exchange and correlation with the aim of addressing how doping with a single S atom affects the geometries, magnetic properties, and reactivity of pure molybdenum clusters. These clusters exhibit a less marked tendency to dimerization than their isoelectronic Cr counterparts despite sharing their half-filled valence shell configuration. Doping with a single S impurity is enough to change the structure of the host molybdenum cluster to a large extent, as well as to modify the bonding pattern, the magnetic state and the magnetic moment distribution in the Mo host. Vertical ionization potentials and electron affinities are calculated to determine global reactivity indicators like the electronegativity and the chemical hardness. The results are discussed in terms of the thermodynamical and relative stabilities, charge transfer effects, and spin-polarized densities of electronic states.

Investigation of the Impact of Different Terms in the Second Order Hamiltonian on Excitation Energies of Valence and Rydberg States.

PubMed

Tajti, Attila; Szalay, Péter G

2016-11-08

Describing electronically excited states of molecules accurately poses a challenging problem for theoretical methods. Popular second order techniques like Linear Response CC2 (CC2-LR), Partitioned Equation-of-Motion MBPT(2) (P-EOM-MBPT(2)), or Equation-of-Motion CCSD(2) (EOM-CCSD(2)) often produce results that are controversial and are ill-balanced with their accuracy on valence and Rydberg type states. In this study, we connect the theory of these methods and, to investigate the origin of their different behavior, establish a series of intermediate variants. The accuracy of these on excitation energies of singlet valence and Rydberg electronic states is benchmarked on a large sample against high-accuracy Linear Response CC3 references. The results reveal the role of individual terms of the second order similarity transformed Hamiltonian, and the reason for the bad performance of CC2-LR in the description of Rydberg states. We also clarify the importance of the T̂ 1 transformation employed in the CC2 procedure, which is found to be very small for vertical excitation energies.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Banik, Ananya; Biswas, Kanishka, E-mail: kanishka@jncasr.ac.in

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 themore » 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 Sn{sub 1−x}Ag{sub x}Te{sub 1−x}I{sub x} samples. A maximum thermoelectric figure of merit, zT, of ~1.05 was achieved at 860 K in high quality crystalline ingot of p-type Sn{sub 0.95}Ag{sub 0.05}Te{sub 0.95}I{sub 0.05}. - Graphical abstract: Significant decrease in hole concentration and reduction of the energy separation between light and heavy hole valence bands resulted in a maximum thermoelectric figure of merit, zT, of ~1.05 at 860 K in high quality crystalline ingot of p-type Sn{sub 0.95}Ag{sub 0.05}Te{sub 0.95}I{sub 0.05}. - Highlights: • AgI alloying in SnTe increases the principle band gap. • Hole concentration reduction and valence band convergence enhances thermopower of SnTe-AgI. • A maximum zT of ~1.05 was achieved at 860 K in p-type Sn{sub 0.95}Ag{sub 0.05}Te{sub 0.95}I{sub 0.05}.« less

Change of Nuclear Configurations in the Neutrinoless Double-β Decay of 130Te → 130Xe and 136Xe → 136Ba

DOE PAGES

Entwisle, J. P.; Kay, B. P.; Tamii, A.; ...

2016-06-13

The change in the configuration of valence protons between the initial and final states in the neutrinoless double-beta decay of Te-130 -> Xe-130 and of Xe-136 -> Ba-136 has been determined by measuring the cross sections of the (d,He-3) reaction with 101-MeV deuterons. Together with our recent determination of the relevant neutron configurations involved in the process, a quantitative comparison with the latest shell-model and interacting-boson-model calculations reveals significant discrepancies. These are the same calculations used to determine the nuclear matrix elements governing the rate of neutrinoless double-beta decay in these systems.

Negatively valenced expectancy violation predicts emotionality: A longitudinal analysis.

PubMed

Bettencourt, B Ann; Manning, Mark

2016-09-01

We hypothesized that negatively valenced expectancy violations about the quality of 1's life would predict negative emotionality. We tested this hypothesis in a 4-wave longitudinal study of breast cancer survivors. The findings showed that higher levels of negatively valenced expectancy violation, at earlier time points, were associated with greater negative emotionality, at later time points. Implications of the findings are discussed. (PsycINFO Database Record (c) 2016 APA, all rights reserved).

Analytic Energy Gradients for Variational Two-Electron Reduced-Density-Matrix-Driven Complete Active Space Self-Consistent Field Theory.

PubMed

Maradzike, Elvis; Gidofalvi, Gergely; Turney, Justin M; Schaefer, Henry F; DePrince, A Eugene

2017-09-12

Analytic energy gradients are presented for a variational two-electron reduced-density-matrix (2-RDM)-driven complete active space self-consistent field (CASSCF) method. The active-space 2-RDM is determined using a semidefinite programing (SDP) algorithm built upon an augmented Lagrangian formalism. Expressions for analytic gradients are simplified by the fact that the Lagrangian is stationary with respect to variations in both the primal and the dual solutions to the SDP problem. Orbital response contributions to the gradient are identical to those that arise in conventional CASSCF methods in which the electronic structure of the active space is described by a full configuration interaction (CI) wave function. We explore the relative performance of variational 2-RDM (v2RDM)- and CI-driven CASSCF for the equilibrium geometries of 20 small molecules. When enforcing two-particle N-representability conditions, full-valence v2RDM-CASSCF-optimized bond lengths display a mean unsigned error of 0.0060 Å and a maximum unsigned error of 0.0265 Å, relative to those obtained from full-valence CI-CASSCF. When enforcing partial three-particle N-representability conditions, the mean and maximum unsigned errors are reduced to only 0.0006 and 0.0054 Å, respectively. For these same molecules, full-valence v2RDM-CASSCF bond lengths computed in the cc-pVQZ basis set deviate from experimentally determined ones on average by 0.017 and 0.011 Å when enforcing two- and three-particle conditions, respectively, whereas CI-CASSCF displays an average deviation of 0.010 Å. The v2RDM-CASSCF approach with two-particle conditions is also applied to the equilibrium geometry of pentacene; optimized bond lengths deviate from those derived from experiment, on average, by 0.015 Å when using a cc-pVDZ basis set and a (22e,22o) active space.

Characterization of photo-induced valence tautomerism in a cobalt-dioxolene complex by ultrafast spectroscopy

NASA Astrophysics Data System (ADS)

Beni, A.; Bogani, L.; Bussotti, L.; Dei, A.; Gentili, P. L.; Righini, R.

2005-01-01

The valence tautomerism of low-spin CoIII(Cat-N-BQ)(Cat-N-SQ) was investigated by means of UV-vis pump-probe transient absorption spectroscopy in chloroform. By exciting the CT transition of the complex at 480 nm, an intramolecular electron transfer process is selectively triggered. The photo-induced charge transfer is pursued by a cascade of two main molecular events characterized by the ultrafast transient absorption spectroscopy: the first gives rise to the metastable high-spin CoII(Cat-N-BQ)2 that, secondly, reaches the chemical equilibrium with the reactant species.

Electron interference effects in energetic photoelectrons from C60@C240 probed by the Fourier spectroscopy

NASA Astrophysics Data System (ADS)

McCreary, Meghan; Chakraborty, Himadri

2013-05-01

The ground state structure of the simplest two-fullerene onion system, the C60@C240 molecule, is solved in the Kohn-Sham framework of local density approximation (LDA). Calculations are carried out with delocalized carbon valence electrons after modeling the onion ion-core of sixty C4+ ions from C60 and two hundred and forty of those from C240 in a smeared out jellium-type double-shell structure. Ionization cross sections of all the levels are then calculated in both independent particle LDA and many-particle time dependent LDA approaches at photon energies above the plasmon resonances. These high-energy results exhibit rich structures of energy dependent oscillations from the quantum interference of electron waves produced at the edges of the fullerene layers. A detailed scrutiny of these structures is conducted by Fourier transforming the spectra to the configuration space that relates the oscillations to the onion geometry. Supported by NSF and DOE.

Structural and electronic properties of the transition layer at the SiO{sub 2}/4H-SiC interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Wenbo; Wang, Dejun, E-mail: dwang121@dlut.edu.cn; Zhao, Jijun

Using first-principles methods, we generate an amorphous SiO{sub 2}/4H-SiC interface with a transition layer. Based this interface model, we investigate the structural and electronic properties of the interfacial transition layer. The calculated Si 2p core-level shifts for this interface are comparable to the experimental data, indicating that various SiC{sub x}O{sub y} species should be present in this interface transition layer. The analysis of the electronic structures reveals that the tetrahedral SiC{sub x}O{sub y} structures cannot introduce any of the defect states at the interface. Interestingly, our transition layer also includes a C-C=C trimer and SiO{sub 5} configurations, which lead tomore » the generation of interface states. The accurate positions of Kohn-Sham energy levels associated with these defects are further calculated within the hybrid functional scheme. The Kohn-Sham energy levels of the carbon trimer and SiO{sub 5} configurations are located near the conduction and valence band of bulk 4H-SiC, respectively. The result indicates that the carbon trimer occurred in the transition layer may be a possible origin of near interface traps. These findings provide novel insight into the structural and electronic properties of the realistic SiO{sub 2}/SiC interface.« less

Effect of Molecular Guest Binding on the d-d Transitions of Ni2+ of CPO-27-Ni: A Combined UV-Vis, Resonant-Valence-to-Core X-ray Emission Spectroscopy, and Theoretical Study.

PubMed

Gallo, Erik; Gorelov, Evgeny; Guda, Alexander A; Bugaev, Aram L; Bonino, Francesca; Borfecchia, Elisa; Ricchiardi, Gabriele; Gianolio, Diego; Chavan, Sachin; Lamberti, Carlo

2017-12-04

We used Ni K-edge resonant-valence-to-core X-ray emission spectroscopy (RVtC-XES, also referred to as direct RIXS), an element-selective bulk-sensitive synchrotron-based technique, to investigate the electronic structure of the CPO-27-Ni metal-organic framework (MOF) upon molecular adsorption of significant molecular probes: H 2 O, CO, H 2 S, and NO. We compare RVtC-XES with UV-vis spectroscopy, and we show that the element selectivity of RVtC-XES is of strategic significance to observe the full set of d-d excitations in Ni 2+ , which are partially overshadowed by the low-energy π-π* transitions of the Ni ligands in standard diffuse-reflectance UV-vis experiments. Our combined RVtC-XES/UV-vis approach provides access to the whole set of d-d excitations, allowing us a complete discussion of the changes undergone by the electronic configuration of the Ni 2+ sites hosted within the MOF upon molecular adsorption. The experimental data have been interpreted by multiplet ligand-field theory calculations based on Wannier orbitals. This study represents a step further in understanding the ability of the CPO-27-Ni MOFs in molecular sorption and separation applications.

Structural stability and electronic properties of β-tetragonal boron: A first-principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayami, Wataru, E-mail: hayami.wataru@nims.go.jp

2015-01-15

It is known that elemental boron has five polymorphs: α- and β-rhombohedral, α- and β-tetragonal, and the high-pressure γ phase. β-tetragonal (β-t) boron was first discovered in 1960, but there have been only a few studies since then. We have thoroughly investigated, using first-principles calculations, the atomic and electronic structures of β-t boron, the details of which were not known previously. The difficulty of calculation arises from the fact that β-t boron has a large unit cell that contains between 184 and 196 atoms, with 12 partially-occupied interstitial sites. This makes the number of configurations of interstitial atoms too greatmore » to calculate them all. By introducing assumptions based on symmetry and preliminary calculations, the number of configurations to calculate can be greatly reduced. It was eventually found that β-t boron has the lowest total energy, with 192 atoms (8 interstitial atoms) in an orthorhombic lattice. The total energy per atom was between those of α- and β-rhombohedral boron. Another tetragonal structure with 192 atoms was found to have a very close energy. The valence bands were fully filled and the gaps were about 1.16 to 1.54 eV, making it comparable to that of β-rhombohedral boron. - Graphical abstract: Electronic density distribution for the lowest-energy configuration (N=192) viewed from the 〈1 0 0〉 direction. Left: isosurface (yellow) at d=0.09 electrons/a.u.{sup 3} Right: isosurface (orange) at d=0.12 electrons/a.u.{sup 3}. - Highlights: • β-tetragonal boron was thoroughly investigated using first-principles calculations. • The lowest energy structure contains 192 atoms in an orthorhombic lattice. • Another tetragonal structure with 192 atoms has a very close energy. • The total energy per atom is between those of α- and β-rhombohedral boron. • The band gap of the lowest energy structure is about 1.16 to 1.54 eV.« less

Valence-Specific Laterality Effects in Vocal Emotion: Interactions with Stimulus Type, Blocking and Sex

ERIC Educational Resources Information Center

Schepman, Astrid; Rodway, Paul; Geddes, Pauline

2012-01-01

Valence-specific laterality effects have been frequently obtained in facial emotion perception but not in vocal emotion perception. We report a dichotic listening study further examining whether valence-specific laterality effects generalise to vocal emotions. Based on previous literature, we tested whether valence-specific laterality effects were…

Geometric Electron Models.

ERIC Educational Resources Information Center

Nika, G. Gerald; Parameswaran, R.

1997-01-01

Describes a visual approach for explaining the filling of electrons in the shells, subshells, and orbitals of the chemical elements. Enables students to apply the principles of atomic electron configuration while using manipulatives to model the building up of electron configurations as the atomic numbers of elements increase on the periodic…

The power of emotional valence-from cognitive to affective processes in reading.

PubMed

Altmann, Ulrike; Bohrn, Isabel C; Lubrich, Oliver; Menninghaus, Winfried; Jacobs, Arthur M

2012-01-01

The comprehension of stories requires the reader to imagine the cognitive and affective states of the characters. The content of many stories is unpleasant, as they often deal with conflict, disturbance or crisis. Nevertheless, unpleasant stories can be liked and enjoyed. In this fMRI study, we used a parametric approach to examine (1) the capacity of increasing negative valence of story contents to activate the mentalizing network (cognitive and affective theory of mind, ToM), and (2) the neural substrate of liking negatively valenced narratives. A set of 80 short narratives was compiled, ranging from neutral to negative emotional valence. For each story mean rating values on valence and liking were obtained from a group of 32 participants in a prestudy, and later included as parametric regressors in the fMRI analysis. Another group of 24 participants passively read the narratives in a three Tesla MRI scanner. Results revealed a stronger engagement of affective ToM-related brain areas with increasingly negative story valence. Stories that were unpleasant, but simultaneously liked, engaged the medial prefrontal cortex (mPFC), which might reflect the moral exploration of the story content. Further analysis showed that the more the mPFC becomes engaged during the reading of negatively valenced stories, the more coactivation can be observed in other brain areas related to the neural processing of affective ToM and empathy.

Advanced Electronics

DTIC Science & Technology

2017-07-21

Technology Branch (RVSW) is conducting a first time experimental and theoretical investigation focused on evaluating new physical phenomena in the quasi ...bandgap energy, are formulated in our microscopic model for explaining the experimentally observed enhancements in both conduction- and valence... experimental and theoretical study on the nature of carrier transport, of both electrons and holes, through narrow constricted crystalline Si “wall

Beam tracking with micromegas & wire chambers in secondary electron detection configuration

NASA Astrophysics Data System (ADS)

Voštinar, M.; Fernández, B.; Pancin, J.; Alvarez, M. A. G.; Chaminade, T.; Damoy, S.; Doré, D.; Drouart, A.; Druillole, F.; Frémont, G.; Kebbiri, M.; Materna, T.; Monmarthe, E.; Panebianco, S.; Papaevangelou, T.; Riallot, M.; Savajols, H.; Spitaels, C.

2013-12-01

The focal plane of S3 (Super Separator Spectrometer), a new experimental area of SPIRAL2 at GANIL, will be used for identification of nuclei, and requires the reconstruction of their trajectories and velocities by the Time Of Flight (TOF) method. Classical tracking detectors used in-beam would generate a lot of angular and energy straggling due to their thickness. One solution is the use of a SED (Secondary Electron Detection), which consists of a thin emissive foil in beam coupled to a low pressure gaseous detector out of the beam, for the detection of secondary electrons ejected from the foil. Moreover, this type of detector can be used for classical beam tracking at low energies, or for example at NFS (GANIL) for the FALSTAFF experiment for the reconstruction of fission fragments trajectories. Several low pressure gaseous detectors such as wire chambers and Micromegas have been constructed and tested since 2008. High counting rate capabilities and good time resolution obtained in previous tests motivated the construction of a new real-size 2D prototype wire chamber and a 2D bulk Micromegas at low pressure. For the first time, spatial resolution of the Micromegas at low pressure (below 20 mbar) in the SED configuration was measured. Different tests have been performed in order to characterize time and spatial properties of both prototypes, giving spatial resolution in the horizontal (X) direction of 0.90(0.02) mm FWHM for the real size prototype and 0.72(0.08) mm FWHM for Micromegas, and a time resolution of ~ 110(25) ps for the real size prototype.

Influence of emotional valence and arousal on the spread of activation in memory.

PubMed

Jhean-Larose, Sandra; Leveau, Nicolas; Denhière, Guy

2014-11-01

Controversy still persists on whether emotional valence and arousal influence cognitive activities. Our study sought to compare how these two factors foster the spread of activation within the semantic network. In a lexical decision task, prime words were varied depending on the valence (pleasant or unpleasant) or on the level of emotional arousal (high or low). Target words were carefully selected to avoid semantic priming effects, as well as to avoid arousing specific emotions (neutral). Three SOA durations (220, 420 and 720 ms) were applied across three independent groups. Results indicate that at 220 ms, the effect of arousal is significantly higher than the effect of valence in facilitating spreading activation while at 420 ms, the effect of valence is significantly higher than the effect of arousal in facilitating spreading activation. These findings suggest that affect is a sequential process involving the successive intervention of arousal and valence.

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…

How much does emotional valence of action outcomes affect temporal binding?

PubMed

Moreton, Joshua; Callan, Mitchell J; Hughes, Gethin

2017-03-01

Temporal binding refers to the compression of the perceived time interval between voluntary actions and their sensory consequences. Research suggests that the emotional content of an action outcome can modulate the effects of temporal binding. We attempted to conceptually replicate these findings using a time interval estimation task and different emotionally-valenced action outcomes (Experiments 1 and 2) than used in previous research. Contrary to previous findings, we found no evidence that temporal binding was affected by the emotional valence of action outcomes. After validating our stimuli for equivalence of perceived emotional valence and arousal (Experiment 3), in Experiment 4 we directly replicated Yoshie and Haggard's (2013) original experiment using sound vocalizations as action outcomes and failed to detect a significant effect of emotion on temporal binding. These studies suggest that the emotional valence of action outcomes exerts little influence on temporal binding. The potential implications of these findings are discussed. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Molybdenum Valence in Basaltic Silicate Melts: Effects of Temperature and Pressure

NASA Technical Reports Server (NTRS)

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

2011-01-01

The metal-silicate partitioning behavior of molybdenum has been used as a test for equilibrium core formation hypotheses [for example, 1-6]. However, current models that apply experimental data to equilibrium core-mantle differentiation infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Molybdenum, a multi-valent element with a valence transition near the fO2 of interest for core formation (approx.IW-2) will be sensitive to changes in fO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo(6+) can be either octahedrally or tetrahedrally coordinated. Here we present X-ray absorption near edge structure (XANES) measurements of Mo valence in basaltic run products at a range of P, T, and fO2 and further quantify the valence transition of Mo.

Values, Valences, and Course Enrollment: Testing the Role of Personal Values within an Expectancy-Valence Framework.

ERIC Educational Resources Information Center

Feather, N. T.

1988-01-01

The enrollment decisions of 444 (183 male, 260 female, and 1 unspecified) university students at Flinders University (South Australia) were investigated. Results shed light on gender differences in achievement patterns in mathematics and English and in relation to assumptions about relations between expectations and valences. (TJH)

Doping induced modifications in the electronic structure and magnetism of ZnO films: Valence band and conduction band studies

NASA Astrophysics Data System (ADS)

Katba, Savan; Jethva, Sadaf; Udeshi, Malay; Trivedi, Priyanka; Vagadia, Megha; Shukla, D. K.; Choudhary, R. J.; Phase, D. M.; Kuberkar, D. G.

2017-11-01

The electronic structure of Pulsed Laser Deposited (PLD) ZnO, Zn0.95Fe0.05O (ZFO), Zn0.98Al0.02O (ZAO) and Zn0.93Fe0.05Al0.02O (ZFAO) films were investigated by Photoelectron spectroscopy and X-ray absorption spectroscopy. X-ray diffraction and ϕ-scan measurements show epitaxial c-directional growth of the films. Temperature dependent magnetization and M-H loop measurements show the presence of room temperature magnetic ordering in all the films. Fittings of Fe 2p XPS and Fe L3,2 -edge XAS of ZFO and ZFAO films show the presence of Fe, in both, Fe+2 and Fe+3 states in tetrahedral symmetry. Valence band spectra in resonance mode show resonance photon energy at 56 eV showing the presence of Fe2+ state (∼2 eV) near the Fermi level. A significant effect of Fe and Al doping on the spectral shape of O K-edge XAS was observed. Results of the Spectroscopic studies reveal that, ferromagnetism in the films is due to the contribution of oxygen deficiency which increases the number of charge carriers that take part in the exchange interaction. Al co-doping with Fe (in ZFAO) results in the enhancement of saturation magnetization by increase in the carrier-mediated ferromagnetic exchange interaction.

Electron localization in a mixed-valence diniobium benzene complex

DOE PAGES

Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.; ...

2014-11-11

Reaction of the neutral diniobium benzene complex {[Nb(BDI)N tBu] 2(μ-C 6H 6)} (BDI = N,N'-diisopropylbenzene-β-diketiminate) with Ag[B(C 6F 5) 4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N tBu] 2(μ-C 6H 6)}{B(C 6F 5) 4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L 3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment ofmore » a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.« less

Change of nuclear configurations in the neutrinoless double-β decay of 130Te →130Be and 136Xe136Ba

NASA Astrophysics Data System (ADS)

Entwisle, J. P.; Kay, B. P.; Tamii, A.; Adachi, S.; Aoi, N.; Clark, J. A.; Freeman, S. J.; Fujita, H.; Fujita, Y.; Furuno, T.; Hashimoto, T.; Hoffman, C. R.; Ideguchi, E.; Ito, T.; Iwamoto, C.; Kawabata, T.; Liu, B.; Miura, M.; Ong, H. J.; Schiffer, J. P.; Sharp, D. K.; Süsoy, G.; Suzuki, T.; Szwec, S. V.; Takaki, M.; Tsumura, M.; Yamamoto, T.

2016-06-01

The change in the configuration of valence protons between the initial and final states in the neutrinoless double-β decay of 130Te → 130Be and of 136Xe136Ba has been determined by measuring the cross sections of the (d ,3He) reaction with 101-MeV deuterons. Together with our recent determination of the relevant neutron configurations involved in the process, a quantitative comparison with the latest shell-model and interacting-boson-model calculations reveals significant discrepancies. These are the same calculations used to determine the nuclear matrix elements governing the rate of neutrinoless double-β decay in these systems.

Age-related emotional bias in processing two emotionally valenced tasks.

PubMed

Allen, Philip A; Lien, Mei-Ching; Jardin, Elliott

2017-01-01

Previous studies suggest that older adults process positive emotions more efficiently than negative emotions, whereas younger adults show the reverse effect. We examined whether this age-related difference in emotional bias still occurs when attention is engaged in two emotional tasks. We used a psychological refractory period paradigm and varied the emotional valence of Task 1 and Task 2. In both experiments, Task 1 was emotional face discrimination (happy vs. angry faces) and Task 2 was sound discrimination (laugh, punch, vs. cork pop in Experiment 1 and laugh vs. scream in Experiment 2). The backward emotional correspondence effect for positively and negatively valenced Task 2 on Task 1 was measured. In both experiments, younger adults showed a backward correspondence effect from a negatively valenced Task 2, suggesting parallel processing of negatively valenced stimuli. Older adults showed similar negativity bias in Experiment 2 with a more salient negative sound ("scream" relative to "punch"). These results are consistent with an arousal-bias competition model [Mather and Sutherland (Perspectives in Psychological Sciences 6:114-133, 2011)], suggesting that emotional arousal modulates top-down attentional control settings (emotional regulation) with age.

X-Ray Sum Frequency Diffraction for Direct Imaging of Ultrafast Electron Dynamics

NASA Astrophysics Data System (ADS)

Rouxel, Jérémy R.; Kowalewski, Markus; Bennett, Kochise; Mukamel, Shaul

2018-06-01

X-ray diffraction from molecules in the ground state produces an image of their charge density, and time-resolved x-ray diffraction can thus monitor the motion of the nuclei. However, the density change of excited valence electrons upon optical excitation can barely be monitored with regular diffraction techniques due to the overwhelming background contribution of the core electrons. We present a nonlinear x-ray technique made possible by novel free electron laser sources, which provides a spatial electron density image of valence electron excitations. The technique, sum frequency generation carried out with a visible pump and a broadband x-ray diffraction pulse, yields snapshots of the transition charge densities, which represent the electron density variations upon optical excitation. The technique is illustrated by ab initio simulations of transition charge density imaging for the optically induced electronic dynamics in a donor or acceptor substituted stilbene.

Valency-Controlled Framework Nucleic Acid Signal Amplifiers.

PubMed

Liu, Qi; Ge, Zhilei; Mao, Xiuhai; Zhou, Guobao; Zuo, Xiaolei; Shen, Juwen; Shi, Jiye; Li, Jiang; Wang, Lihua; Chen, Xiaoqing; Fan, Chunhai

2018-06-11

Weak ligand-receptor recognition events are often amplified by recruiting multiple regulatory biomolecules to the action site in biological systems. However, signal amplification in in vitro biomimetic systems generally lack the spatiotemporal regulation in vivo. Herein we report a framework nucleic acid (FNA)-programmed strategy to develop valence-controlled signal amplifiers with high modularity for ultrasensitive biosensing. We demonstrated that the FNA-programmed signal amplifiers could recruit nucleic acids, proteins, and inorganic nanoparticles in a stoichiometric manner. The valence-controlled signal amplifier enhanced the quantification ability of electrochemical biosensors, and enabled ultrasensitive detection of tumor-relevant circulating free DNA (cfDNA) with sensitivity enhancement of 3-5 orders of magnitude and improved dynamic range. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bidirectional switch of the valence associated with a hippocampal contextual memory engram.

PubMed

Redondo, Roger L; Kim, Joshua; Arons, Autumn L; Ramirez, Steve; Liu, Xu; Tonegawa, Susumu

2014-09-18

The valence of memories is malleable because of their intrinsic reconstructive property. This property of memory has been used clinically to treat maladaptive behaviours. However, the neuronal mechanisms and brain circuits that enable the switching of the valence of memories remain largely unknown. Here we investigated these mechanisms by applying the recently developed memory engram cell- manipulation technique. We labelled with channelrhodopsin-2 (ChR2) a population of cells in either the dorsal dentate gyrus (DG) of the hippocampus or the basolateral complex of the amygdala (BLA) that were specifically activated during contextual fear or reward conditioning. Both groups of fear-conditioned mice displayed aversive light-dependent responses in an optogenetic place avoidance test, whereas both DG- and BLA-labelled mice that underwent reward conditioning exhibited an appetitive response in an optogenetic place preference test. Next, in an attempt to reverse the valence of memory within a subject, mice whose DG or BLA engram had initially been labelled by contextual fear or reward conditioning were subjected to a second conditioning of the opposite valence while their original DG or BLA engram was reactivated by blue light. Subsequent optogenetic place avoidance and preference tests revealed that although the DG-engram group displayed a response indicating a switch of the memory valence, the BLA-engram group did not. This switch was also evident at the cellular level by a change in functional connectivity between DG engram-bearing cells and BLA engram-bearing cells. Thus, we found that in the DG, the neurons carrying the memory engram of a given neutral context have plasticity such that the valence of a conditioned response evoked by their reactivation can be reversed by re-associating this contextual memory engram with a new unconditioned stimulus of an opposite valence. Our present work provides new insight into the functional neural circuits underlying the

Basic features of the pion valence-quark distribution function

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, Lei; Mezrag, Cédric; Moutarde, Hervé

2014-10-07

The impulse-approximation expression used hitherto to define the pion's valence-quark distribution function is flawed because it omits contributions from the gluons which bind quarks into the pion. A corrected leading-order expression produces the model-independent result that quarks dressed via the rainbow–ladder truncation, or any practical analogue, carry all the pion's light-front momentum at a characteristic hadronic scale. Corrections to the leading contribution may be divided into two classes, responsible for shifting dressed-quark momentum into glue and sea-quarks. Working with available empirical information, we use an algebraic model to express the principal impact of both classes of corrections. This enables amore » realistic comparison with experiment that allows us to highlight the basic features of the pion's measurable valence-quark distribution, q π(x); namely, at a characteristic hadronic scale, q π(x)~(1-x) 2 for x≳0.85; and the valence-quarks carry approximately two-thirds of the pion's light-front momentum.« less

Excited electronic states of the methyl radical. Ab initio molecular orbital study of geometries, excitation energies and vibronic spectra

NASA Astrophysics Data System (ADS)

Mebel, Alexander M.; Lin, Sheng-Hsien

1997-03-01

The geometries, vibrational frequencies and vertical and adiabatic excitation energies of the excited valence and Rydberg 3s, 3p, 3d, and 4s electronic states of CH 3 have been studied using ab initio molecular orbital multiconfigurational SCF (CASSCF), internally contracted multireference configuration interaction (MRCI) and equation-of-motion coupled cluster (EOM-CCSD) methods. The vibronic spectra are determined through the calculation of Franck-Condon factors. Close agreement between theory and experiment has been found for the excitation energies, vibrational frequencies and vibronic spectra. The adiabatic excitation energies of the Rydberg 3s B˜ 2A' 1 and 3p 2 2A″ 2 states are calculated to be 46435 and 60065 cm -1 compared to the experimental values of 46300 and 59972 cm -1, respectively. The valence 2A″ excited state of CH 3 has been found to have a pyramidal geometry within C s symmetry and to be adiabatically by 97 kcal/mol higher in energy than the ground state. The 2A″ state is predicted to be stable by 9 and 13 kcal/mol with respect to H 2 and H elimination.

Ab initio effective core potentials including relativistic effects and their application to the electronic structure calculations of heavy atoms and molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Y.S.

1977-11-01

The effects of the 4f shell of electrons and the relativity of valence electrons are compared. The effect of 4f shell (lanthanide contraction) is estimated from the numerical Hartree-Fock (HF) calculations of pseudo-atoms corresponding to Hf, Re, Au, Hg, Tl, Pb and Bi without 4f electrons and with atomic numbers reduced by 14. The relativistic effect estimated from the numerical Dirac-Hartree-Fock (DHF) calculations of those atoms is comparable in the magnitude with that of the 4f shell of electrons. Both are larger for 6s than for 5d or 6p electrons. The various relativistic effects on valence electrons are discussed inmore » detail to determine the proper level of the approximation for the valence electron calculations of systems with heavy elements. An effective core potential system has been developed for heavy atoms in which relativistic effects are included in the effective potentials.« less

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…

Density functional study for crystalline structures and electronic properties of Si1- x Sn x binary alloys

NASA Astrophysics Data System (ADS)

Nagae, Yuki; Kurosawa, Masashi; Shibayama, Shigehisa; Araidai, Masaaki; Sakashita, Mitsuo; Nakatsuka, Osamu; Shiraishi, Kenji; Zaima, Shigeaki

2016-08-01

We have carried out density functional theory (DFT) calculation for Si1- x Sn x alloy and investigated the effect of the displacement of Si and Sn atoms with strain relaxation on the lattice constant and E- k dispersion. We calculated the formation probabilities for all atomic configurations of Si1- x Sn x according to the Boltzmann distribution. The average lattice constant and E- k dispersion were weighted by the formation probability of each configuration of Si1- x Sn x . We estimated the displacement of Si and Sn atoms from the initial tetrahedral site in the Si1- x Sn x unit cell considering structural relaxation under hydrostatic pressure, and we found that the breaking of the degenerated electronic levels of the valence band edge could be caused by the breaking of the tetrahedral symmetry. We also calculated the E- k dispersion of the Si1- x Sn x alloy by the DFT+U method and found that a Sn content above 50% would be required for the indirect-direct transition.

Breakdown of ionic character of molecular alkali bromides in inner-valence photoionization

NASA Astrophysics Data System (ADS)

Karpenko, A.; Iablonskyi, D.; Urpelainen, S.; Kettunen, J. A.; Cao, W.; Huttula, M.; Aksela, H.

2014-05-01

The inner-valence region of alkali bromide XBr (X=Li, Na, K, Rb) vapours has been studied experimentally by means of synchrotron radiation excited photoelectron spectroscopy. Experimental spectra were analyzed by comparing them with available theoretical results and previous experiments. Ionic character of alkali bromides is seen to change in the inner-valence region with increasing atomic number of the alkali atom. A mechanism involving mixing between Br 4s and Rb 4p orbitals has been suggested to account for the fine structure observed in inner-valence ionization region of RbBr.

Physics of Resonating Valence Bond Spin Liquids

NASA Astrophysics Data System (ADS)

Wildeboer, Julia Saskia

This thesis will investigate various aspects of the physics of resonating valence bond spin liquids. After giving an introduction to the world that lies beyond Landau's priciple of symmetry breaking, e.g. giving an overview of exotic magnetic phases and how they can be described and (possibly) found, we will study a spin-rotationally invariant model system with a known parent Hamiltonian, and argue its ground state to lie within a highly sought after exotic phase, namely the Z2 quantum spin liquid phase. A newly developed numerical procedure --Pfaffian Monte Carlo-- will be introduced to amass evidence that our model Hamiltonian indeed exhibits a Z2 quantum spin liquid phase. Subsequently, we will prove a useful mathematical property of the resonating valence bond states: these states are shown to be linearly independent. Various lattices are investigated concerning this property, and its applications and usefullness are discussed. Eventually, we present a simplified model system describing the interplay of the well known Heisenberg interaction and the Dzyaloshinskii-Moriya (DM) interaction term acting on a sawtooth chain. The effect of the interplay between the two interaction couplings on the phase diagram is investigated. To do so, we employ modern techniques such as the density matrix renormalization group (DMRG) scheme. We find that for weak DM interaction the system exhibits valence bond order. However, a strong enough DM coupling destroys this order.

Influence of affective valence on working memory processes.

PubMed

Gotoh, Fumiko

2008-02-01

Recent research has revealed widespread effects of emotion on cognitive function and memory. However, the influence of affective valence on working or short-term memory remains largely unexplored. In two experiments, the present study examined the predictions that negative words would capture attention, that attention would be difficult to disengage from such negative words, and that the cost of attention switching would increase the time required to update information in working memory. Participants switched between two concurrent working memory tasks: word recognition and a working memory digit updating task. Experiment 1 showed substantial switching cost for negative words, relative to neutral words. Experiment 2 replicated the first experiment, using a self-report measure of anxiety to examine if switching cost is a function of an anxiety-related attention bias. Results did not support this hypothesis. In addition, Experiment 2 revealed switch costs for positive words without the effect of the attention bias from anxiety. The present study demonstrates the effect of affective valence on a specific component of working memory. Moreover, findings suggest why affective valence effects on working memory have not been found in previous research.

Non-classical behaviour of higher valence dopants in chromium (III) oxide by a Cr vacancy compensation mechanism

NASA Astrophysics Data System (ADS)

Carey, John J.; Nolan, Michael

2017-10-01

Modification of metal oxides with dopants that have a stable oxidation in their parent oxides which is higher than the host system is expected to introduce extra electrons into the material to improve carrier mobility. This is essential for applications in catalysis, SOFCs and solar energy materials. Density functional theory calculations are used to investigate the change in electronic and geometric structure of chromium (III) oxide by higher valence dopants, namely; Ce, Ti, V and Zr. For single metal doping, we find that the dopants with variable oxidation states, Ce, Ti and V, adopt a valence state of  +3, while Zr dopant has a  +4 oxidation state and reduces a neighbouring Cr cation. Chromium vacancy formation is greatly enhanced for all dopants, and favoured over oxygen vacancy formation. The Cr vacancies generate holes which oxidise Ce, Ti and V from  +3 to  +4, while also oxidising lattice oxygen sites. For Zr doping, the generated holes oxidise the reduced Cr2+ cation back to Cr3+ and also two lattice oxygen atoms. Three metal atoms in the bulk lattice facilitate spontaneous Cr vacancy from charge compensation. A non-classical compensation mechanism is observed for Ce, Ti and V; all three metals are oxidised from  +3 to  +4, which explains experimental observations that these metals have a  +4 oxidation state in Cr2O3. Charge compensation of the three Zr metals proceeds by a classical higher valence doping mechanism; the three dopants reduce three Cr cations, which are subsequently charge compensated by a Cr vacancy oxidising three Cr2+ to Cr3+. The compensated structures are the correct ground state electronic structure for these doped systems, and used as a platform to investigate cation/anion vacancy formation. Unlike the single metal doped bulks, preference is now given for oxygen vacancy formation over Cr vacancy formation, indicating that the dopants increase the reducibility of Cr2O3 with Ce doping showing the strongest

Automatic blocking for complex three-dimensional configurations

NASA Technical Reports Server (NTRS)

Dannenhoffer, John F., III

1995-01-01

A new blocking technique for complex three-dimensional configurations is described. This new technique is based upon the concept of an abstraction, or squared-up representation, of the configuration and the associated grid. By allowing the user to describe blocking requirements in natural terms (such as 'wrap a grid around this leading edge' or 'make all grid lines emanating from this wall orthogonal to it'), users can quickly generate complex grids around complex configurations, while still maintaining a high level of control where desired. An added advantage of the abstraction concept is that once a blocking is defined for a class of configurations, it can be automatically applied to other configurations of the same class, making the new technique particularly well suited for the parametric variations which typically occur during design processes. Grids have been generated for a variety of real-world, two- and three-dimensional configurations. In all cases, the time required to generate the grid, given just an electronic form of the configuration, was at most a few days. Hence with this new technique, the generation of a block-structured grid is only slightly more expensive than the generation of an unstructured grid for the same configuration.

Influence of valence electron concentration on Laves phases: Structures and phase stability of pseudo-binary MgZn 2-xPd x

DOE PAGES

Thimmaiah, Srinivasa; Miller, Gordon J.

2015-06-03

A series of pseudo-binary compounds MgZn 2-xPd x (0.15 ≤ x ≤ 1.0) were synthesized and structurally characterized to understand the role of valence electron concentration (vec) on the prototype Laves phase MgZn 2 with Pd-substitution. Three distinctive phase regions were observed with respect to Pd content, all exhibiting fundamental Laves phase structures: 0.1 ≤ x ≤ 0.3 (MgNi 2-type, hP24; MgZn 1.80Pd 0.20(2)), 0.4 ≤ x ≤ 0.6 (MgCu 2-type, cF24; MgZn 1.59Pd 0.41(2)), and 0.62 ≤ x ≤ 0.8 (MgZn 2-type, hP12: MgZn 1.37Pd 0.63(2)). Refinements from single-crystal X-ray diffraction indicated nearly statistical distributions of Pd and Znmore » atoms among the majority atom sites in these structures. Interestingly, the MgZn 2-type structure re-emerges in MgZn 2–xPd x at x ≈ 0.7 with the refined composition MgZn 1.37(2)Pd 0.63 and a c/a ratio of 1.59 compared to 1.64 for binary MgZn 2. Electronic structure calculations on a model “MgZn 1.25Pd 0.75” yielded a density of states (DOS) curve showing enhancement of a pseudogap at the Fermi level as a result of electronic stabilization due to the Pd addition. Moreover, integrated crystal orbital Hamilton population values show significant increases of orbital interactions for (Zn,Pd)–(Zn,Pd) atom pairs within the majority atom substructure, i.e., within the Kagomé nets as well as between a Kagomé net and an apical site, from binary MgZn 2 to the ternary “MgZn 1.25Pd 0.75”. Multi-centered bonding is evident from electron localization function plots for “MgZn 1.25Pd 0.75”, an outcome which is in accordance with analysis of other Laves phases.« less

Clustering of low-valence particles: structure and kinetics.

PubMed

Markova, Olga; Alberts, Jonathan; Munro, Edwin; Lenne, Pierre-François

2014-08-01

We compute the structure and kinetics of two systems of low-valence particles with three or six freely oriented bonds in two dimensions. The structure of clusters formed by trivalent particles is complex with loops and holes, while hexavalent particles self-organize into regular and compact structures. We identify the elementary structures which compose the clusters of trivalent particles. At initial stages of clustering, the clusters of trivalent particles grow with a power-law time dependence. Yet at longer times fusion and fission of clusters equilibrates and clusters form a heterogeneous phase with polydispersed sizes. These results emphasize the role of valence in the kinetics and stability of finite-size clusters.

Valence-band states in Bi2(Ca,Sr,La)3Cu2O8

NASA Astrophysics Data System (ADS)

Wells, B. O.; Lindberg, P. A. P.; Shen, Z.-X.; Dessau, D. S.; Spicer, W. E.; Lindau, I.; Mitzi, D. B.; Kapitulnik, A.

1989-09-01

We have used photoemission spectroscopy to examine the symmetry of the occupied states of the valence band for the La-doped superconductor Bi2(Ca,Sr,La)3Cu2O8. While the oxygen states near the bottom of the 7-eV wide valence band exhibit predominantly O 2pz symmetry, the states at the top of the valence band extending to the Fermi level are found to have primarily O 2px and O 2py character. We have also examined anomalous intensity enhancements in the valence-band features for photon energies near 18 eV. These enhancements, which occur at photon energies ranging from 15.8 to 18.0 eV for the different valence-band features, are not consistent with either simple final-state effects or direct O 2s transitions to unoccupied O 2p states.

New results on thermalization of electrons in GaAs

NASA Astrophysics Data System (ADS)

Hannak, Reinhard M.; Ruehle, Wolfgang W.

1994-05-01

The transition from a nonthermal into a thermal distribution of electrons at low densities (< 1014 cm-3) is traced on a picosecond time-scale by the time evolution of a band-to-acceptor transition in GaAs:Be. Two narrow, nonthermal electron distributions are detected during the first picoseconds originating from the heavy- and light-hole valence band, respectively. Measurements with circular polarization of excitation and luminescence confirm this assignment. The variation of their energetic peak-positions with excitation energy allows the experimental determination of the valence band dispersions for very small wave vectors near k equals 0, where only parabolic energy terms contribute to the dispersions. The results are consistent with the commonly used effective hole masses.

Stabilization of very rare tautomers of uracil by an excess electron.

PubMed

Bachorz, Rafał A; Rak, Janusz; Gutowski, Maciej

2005-05-21

We characterized valence-type and dipole-bound anionic states of uracil using various electronic structure methods. We found that the most stable anion is related to neither the canonical 2,4-dioxo nor a rare imino-hydroxy tautomer. Instead, it is related to an imino-oxo tautomer, in which the N1H proton is transferred to the C5 atom. This valence anion is characterized by an electron vertical detachment energy (VDE) of 1267 meV and it is adiabatically stable with respect to the canonical neutral by 3.93 kcal mol(-1). It is also more stable by 2.32 and 5.10 kcal mol(-1) than the dipole-bound and valence anion, respectively, of the canonical tautomer. The VDE values for the former and the latter are 73 and 506 meV, respectively. Another, anionic, low-lying imino-oxo tautomer with a VDE of 2499 meV has a proton transferred from N3H to C5. It is less stable than the neutral canonical tautomer by 1.38 kcal mol(-1). The mechanism of formation of anionic tautomers with the carbon C5 protonated may involve intermolecular proton transfer or dissociative electron attachment to the canonical neutral tautomer followed by a barrier-free attachment of a hydrogen atom to C5. The six-member ring structure of anionic tautomers with carbon atoms protonated might be unstable upon an excess electron detachment. Indeed, the neutral systems resulting from electron detachment from anionic tautomers with carbon atoms protonated evolve along barrier-free decomposition pathways to a linear or a bicyclo structure, which might be viewed as lesions to RNA. Within the PCM hydration model, the low-lying valence anions become adiabatically bound with respect to the canonical neutral and the two most stable tautomers have carbon atoms protonated.

Qualitative analysis of the helical electronic energy of inherently chiral calix[4]arenes: an approach to effectively assign their absolute configuration.

PubMed

Zheng, Shuang; Chang, Ming-Liang; Zhou, Jing; Fu, Jing-Wei; Zhang, Qing-Wei; Li, Shao-Yong; Qiao, Wei; Liu, Jun-Min

2014-06-03

For all microhelices on aromatic rings of inherently chiral calix[4]arene, an expression was derived from one approximation and one hypothesis on the basis of the electron-on-a-helix model of Tinoco and Woody as follows: 1/E = μ(H - KΔα2), where μ = 1 for the right-handed microhelix and μ = -1 for the left-handed microhelix; and H and K are constant and greater than zero. The expression correlates microhelical electronic energy (E) with the atom polarizability difference (Δα) on both microhelix ends, which intuitively and clearly shows the impact of helical substituent polarizability on helical electronic energy. The case analysis almost entirely proves that the qualitative analysis of the helical electronic energy of inherently chiral calix[4]arenes with the expression is scientific and can be used to effectively assign their absolute configuration.

Dissociating motivational direction and affective valence: specific emotions alter central motor processes.

PubMed

Coombes, Stephen A; Cauraugh, James H; Janelle, Christopher M

2007-11-01

We aimed to clarify the relation between affective valence and motivational direction by specifying how central and peripheral components of extension movements are altered according to specific unpleasant affective states. As predicted, premotor reaction time was quicker for extension movements initiated during exposure to attack than for extension movements initiated during exposure to all other valence categories (mutilation, erotic couples, opposite-sex nudes, neutral humans, household objects, blank). Exposure to erotic couples and mutilations yielded greater peak force than exposure to images of attack, neutral humans, and household objects. Finally, motor reaction time and peak electromyographic amplitude were not altered by valence. These findings indicate that unpleasant states do not unilaterally prime withdrawal movements, and that the quick execution of extension movements during exposure to threatening images is due to rapid premotor, rather than motor, reaction time. Collectively, our findings support the call for dissociating motivational direction and affective valence.

The bidirectional congruency effect of brightness-valence metaphoric association in the Stroop-like and priming paradigms.

PubMed

Huang, Yanli; Tse, Chi-Shing; Xie, Jiushu

2017-11-04

The conceptual metaphor theory (Lakoff & Johnson, 1980, 1999) postulates a unidirectional metaphoric association between abstract and concrete concepts: sensorimotor experience activated by concrete concepts facilitates the processing of abstract concepts, but not the other way around. However, this unidirectional view has been challenged by studies that reported a bidirectional metaphoric association. In three experiments, we tested the directionality of the brightness-valence metaphoric association, using Stroop-like paradigm, priming paradigm, and Stroop-like paradigm with a go/no-go manipulation. Both mean and vincentile analyses of reaction time data were performed. We showed that the directionality of brightness-valence metaphoric congruency effect could be modulated by the activation level of the brightness/valence information. Both brightness-to-valence and valence-to-brightness metaphoric congruency effects occurred in the priming paradigm, which could be attributed to the presentation of prime that pre-activated the brightness or valence information. However, in the Stroop-like paradigm the metaphoric congruency effect was only observed in the brightness-to-valence direction, but not in the valence-to-brightness direction. When the go/no-go manipulation was used to boost the activation of word meaning in the Stroop-like paradigm, the valence-to-brightness metaphoric congruency effect was observed. Vincentile analyses further revealed that valence-to-brightness metaphoric congruency effect approached significance in the Stroop-like paradigm when participants' reaction times were slower (at around 490ms). The implications of the current findings on the conceptual metaphor theory and embodied cognition are discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Comprehensive derivation of bond-valence parameters for ion pairs involving oxygen

PubMed Central

Gagné, Olivier Charles; Hawthorne, Frank Christopher

2015-01-01

Published two-body bond-valence parameters for cation–oxygen bonds have been evaluated via the root mean-square deviation (RMSD) from the valence-sum rule for 128 cations, using 180 194 filtered bond lengths from 31 489 coordination polyhedra. Values of the RMSD range from 0.033–2.451 v.u. (1.1–40.9% per unit of charge) with a weighted mean of 0.174 v.u. (7.34% per unit of charge). The set of best published parameters has been determined for 128 ions and used as a benchmark for the determination of new bond-valence parameters in this paper. Two common methods for the derivation of bond-valence parameters have been evaluated: (1) fixing B and solving for R o; (2) the graphical method. On a subset of 90 ions observed in more than one coordination, fixing B at 0.37 Å leads to a mean weighted-RMSD of 0.139 v.u. (6.7% per unit of charge), while graphical derivation gives 0.161 v.u. (8.0% per unit of charge). The advantages and disadvantages of these (and other) methods of derivation have been considered, leading to the conclusion that current methods of derivation of bond-valence parameters are not satisfactory. A new method of derivation is introduced, the GRG (generalized reduced gradient) method, which leads to a mean weighted-RMSD of 0.128 v.u. (6.1% per unit of charge) over the same sample of 90 multiple-coordination ions. The evaluation of 19 two-parameter equations and 7 three-parameter equations to model the bond-valence–bond-length relation indicates that: (1) many equations can adequately describe the relation; (2) a plateau has been reached in the fit for two-parameter equations; (3) the equation of Brown & Altermatt (1985 ▸) is sufficiently good that use of any of the other equations tested is not warranted. Improved bond-valence parameters have been derived for 135 ions for the equation of Brown & Altermatt (1985 ▸) in terms of both the cation and anion bond-valence sums using the GRG method and our complete data set. PMID

Probing molecular dynamics in solution with x-ray valence-to-core spectroscopy

NASA Astrophysics Data System (ADS)

Doumy, Gilles; March, Anne Marie; Tu, Ming-Feng; Al Haddad, Andre; Southworth, Stephen; Young, Linda; Walko, Donald; Bostedt, Christoph

2017-04-01

Hard X-ray spectroscopies are powerful tools for probing the electronic and geometric structure of molecules in complex or disordered systems and have been particularly useful for studying molecules in the solution phase. They are element specific, sensitive to the electronic structure and the local arrangements of surrounding atoms of the element being selectively probed. When combined in a pump-probe scheme with ultrafast lasers, X-ray spectroscopies can be used to track the evolution of structural changes that occur after photoexcitation. Efficient use of hard x-ray radiation coming from high brilliance synchrotrons and upcoming high repetition rate X-ray Free Electron Lasers requires MHz repetition rate lasers and data acquisition systems. High information content Valence-to-Core x-ray emission is directly sensitive to the molecular orbitals involved in photochemistry. We report on recent progress towards fully enabling this photon-hungry technique for the study of time-resolved molecular dynamics, including efficient detection and use of polychromatic x-ray micro-probe at the Advanced Photon Source. Work was supported by the U.S. Department of Energy, Office of Science, Chemical Sciences, Geosciences, and Biosciences Division.

Representational similarity of social and valence information in the medial pFC.

PubMed

Chavez, Robert S; Heatherton, Todd F

2015-01-01

The human brain is remarkably adept at integrating complex information to form unified psychological representations of agents, objects, and events in the environment. Two domains in which this ability is particularly salient are the processing of social and valence information and are supported by common cortical areas in the medial pFC (MPFC). Because social information is often embedded within valenced emotional contexts, it is possible that activation patterns within the MPFC may represent both of these types of cognitive processes when presented simultaneously. The current study tested this possibility by employing a large-scale automated meta-analysis tool, together with multivoxel pattern analysis to investigate the representational similarity of social and valence information in the MPFC during fMRI. Using a representational similarity analysis, we found a high degree of representational similarity both within social dimensions and within valence dimensions, but not across them (e.g., positive social information was highly dissimilar to negative nonsocial information), in a ventral portion of the MPFC. These results were significantly correlated with a behaviorally measured similarity structure of the same stimuli, suggesting that a psychologically meaningful representation of social and valence information is reflected by multivoxel activation patterns in the ventral MPFC.

Controlling Valence of DNA-Coated Emulsion Droplets with Multiple Flavors of DNA

NASA Astrophysics Data System (ADS)

McMullen, Angus; Bargteil, Dylan; Pine, David; Brujic, Jasna

We explore the control of valence of DNA-coated emulsion droplets as a first step in developing DNA-directed self-assembly of emulsions. Emulsion droplets differ from solid colloids in that they are deformable and the DNA strands attached to them are free to move along the emulsion surface. The balance of binding energy and droplet deformation provides control over a droplet's valence via its ligand density. After binding, some DNA often remains unbound due to the entropic cost of DNA recruitment. In practice, therefore, the assembly kinetics yield a distribution in valence. Our goal is to control valence by altering the binding kinetics with multiple flavors of DNA. We coat one set of droplets with two DNA types, A and B, and two other sets with one complementary strand, A' or B'. When an AB droplet binds to an A' droplet, the adhesion patch depletes A strands, leaving the rest of the droplet coated with more B than A strands. This increases the chance that the next droplet to bind will be a B' rather than an A'. Controlling valence will allow us to build a wide array of soft structures, such as emulsion polymers or networks with a determined coordination number. This work was supported by the NSF MRSEC Program (DMR-0820341).

Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. I. Hamiltonian matrix elements between internally contracted excited valence bond wave functions

NASA Astrophysics Data System (ADS)

Chen, Zhenhua; Chen, Xun; Wu, Wei

2013-04-01

In this series, the n-body reduced density matrix (n-RDM) approach for nonorthogonal orbitals and their applications to ab initio valence bond (VB) methods are presented. As the first paper of this series, Hamiltonian matrix elements between internally contracted VB wave functions are explicitly provided by means of nonorthogonal orbital based RDM approach. To this end, a more generalized Wick's theorem, called enhanced Wick's theorem, is presented both in arithmetical and in graphical forms, by which the deduction of expressions for the matrix elements between internally contracted VB wave functions is dramatically simplified, and the matrix elements are finally expressed in terms of tensor contractions of electronic integrals and n-RDMs of the reference VB self-consistent field wave function. A string-based algorithm is developed for the purpose of evaluating n-RDMs in an efficient way. Using the techniques presented in this paper, one is able to develop new methods and efficient algorithms for nonorthogonal orbital based many-electron theory much easier than by use of the first quantized formulism.

Incipient class II mixed valency in a plutonium solid-state compound

NASA Astrophysics Data System (ADS)

Cary, Samantha K.; Galley, Shane S.; Marsh, Matthew L.; Hobart, David L.; Baumbach, Ryan E.; Cross, Justin N.; Stritzinger, Jared T.; Polinski, Matthew J.; Maron, Laurent; Albrecht-Schmitt, Thomas E.

2017-09-01

Electron transfer in mixed-valent transition-metal complexes, clusters and materials is ubiquitous in both natural and synthetic systems. The degree to which intervalence charge transfer (IVCT) occurs, dependent on the degree of delocalization, places these within class II or III of the Robin-Day system. In contrast to the d-block, compounds of f-block elements typically exhibit class I behaviour (no IVCT) because of localization of the valence electrons and poor spatial overlap between metal and ligand orbitals. Here, we report experimental and computational evidence for delocalization of 5f electrons in the mixed-valent PuIII/PuIV solid-state compound, Pu3(DPA)5(H2O)2 (DPA = 2,6-pyridinedicarboxylate). The properties of this compound are benchmarked by the pure PuIII and PuIV dipicolinate complexes, [PuIII(DPA)(H2O)4]Br and PuIV(DPA)2(H2O)3·3H2O, as well as by a second mixed-valent compound, PuIII[PuIV(DPA)3H0.5]2, that falls into class I instead. Metal-to-ligand charge transfer is involved in both the formation of Pu3(DPA)5(H2O)2 and in the IVCT.

Mixed-valence molecular four-dot unit for quantum cellular automata: Vibronic self-trapping and cell-cell response

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsukerblat, Boris, E-mail: tsuker@bgu.ac.il, E-mail: andrew.palii@uv.es; Palii, Andrew, E-mail: tsuker@bgu.ac.il, E-mail: andrew.palii@uv.es; Clemente-Juan, Juan Modesto

2015-10-07

Our interest in this article is prompted by the vibronic problem of charge polarized states in the four-dot molecular quantum cellular automata (mQCA), a paradigm for nanoelectronics, in which binary information is encoded in charge configuration of the mQCA cell. Here, we report the evaluation of the electronic levels and adiabatic potentials of mixed-valence (MV) tetra-ruthenium (2Ru(II) + 2Ru(III)) derivatives (assembled as two coupled Creutz-Taube complexes) for which molecular implementations of quantum cellular automata (QCA) was proposed. The cell based on this molecule includes two holes shared among four spinless sites and correspondingly we employ the model which takes into accountmore » the two relevant electron transfer processes (through the side and through the diagonal of the square) as well as the difference in Coulomb energies for different instant positions of localization of the hole pair. The combined Jahn-Teller (JT) and pseudo JT vibronic coupling is treated within the conventional Piepho-Krauzs-Schatz model adapted to a bi-electronic MV species with the square-planar topology. The adiabatic potentials are evaluated for the low lying Coulomb levels in which the antipodal sites are occupied, the case just actual for utilization in mQCA. The conditions for the vibronic self-trapping in spin-singlet and spin-triplet states are revealed in terms of the two actual transfer pathways parameters and the strength of the vibronic coupling. Spin related effects in degrees of the localization which are found for spin-singlet and spin-triplet states are discussed. The polarization of the cell is evaluated and we demonstrate how the partial delocalization caused by the joint action of the vibronic coupling and electron transfer processes influences polarization of a four-dot cell. The results obtained within the adiabatic approach are compared with those based on the numerical solution of the dynamic vibronic problem. Finally, the Coulomb interaction

Resonant inelastic x-ray scattering and photoemission measurement of O2: Direct evidence for dependence of Rydberg-valence mixing on vibrational states in O 1s → Rydberg states

NASA Astrophysics Data System (ADS)

Gejo, T.; Oura, M.; Tokushima, T.; Horikawa, Y.; Arai, H.; Shin, S.; Kimberg, V.; Kosugi, N.

2017-07-01

High-resolution resonant inelastic x-ray scattering (RIXS) and low-energy photoemission spectra of oxygen molecules have been measured for investigating the electronic structure of Rydberg states in the O 1s → σ* energy region. The electronic characteristics of each Rydberg state have been successfully observed, and new assignments are made for several states. The RIXS spectra clearly show that vibrational excitation is very sensitive to the electronic characteristics because of Rydberg-valence mixing and vibronic coupling in O2. This observation constitutes direct experimental evidence that the Rydberg-valence mixing characteristic depends on the vibrational excitation near the avoided crossing of potential surfaces. We also measured the photoemission spectra of metastable oxygen atoms (O*) from O2 excited to 1s → Rydberg states. The broadening of the 4p Rydberg states of O* has been found with isotropic behavior, implying that excited oxygen molecules undergo dissociation with a lifetime of the order of 10 fs in 1s → Rydberg states.

Changing the conversation: the influence of emotions on conversational valence and alcohol consumption.

PubMed

Hendriks, Hanneke; van den Putte, Bas; de Bruijn, Gert-Jan

2014-10-01

Health campaign effects may be improved by taking interpersonal communication processes into account. The current study, which employed an experimental, pretest-posttest, randomized exposure design (N = 208), investigated whether the emotions induced by anti-alcohol messages influence conversational valence about alcohol and subsequent persuasion outcomes. The study produced three main findings. First, an increase in the emotion fear induced a negative conversational valence about alcohol. Second, fear was most strongly induced by a disgusting message, whereas a humorous appeal induced the least fear. Third, a negative conversational valence elicited healthier binge drinking attitudes, subjective norms, perceived behavioral control, intentions, and behaviors. Thus, health campaign planners and health researchers should pay special attention to the emotional characteristics of health messages and should focus on inducing a healthy conversational valence.

Tuning of quantum entanglement in molecular quantum cellular automata based on mixed-valence tetrameric units.

PubMed

Palii, Andrew; Tsukerblat, Boris

2016-10-25

In this article we consider two coupled tetrameric mixed-valence (MV) units accommodating electron pairs, which play the role of cells in molecular quantum cellular automata. It is supposed that the Coulombic interaction between instantly localized electrons within the cell markedly inhibits the transfer processes between the redox centers. Under this condition, as well as due to the vibronic localization of the electron pair, the cell can encode binary information, which is controlled by neighboring cells. We show that under certain conditions the two low-lying vibronic spin levels of the cell (ground and first excited states) can be regarded as originating from an effective spin-spin interaction. This is shown to depend on the internal parameters of the cell as well as on the induced polarization. Within this simplified two-level picture we evaluate the quantum entanglement in the system represented by the two electrons in the cell and show how the entanglement within the cell and concurrence can be controlled via polarization of the neighboring cells and temperature.

Electronic excitation of molecules in solution calculated using the symmetry-adapted cluster–configuration interaction method in the polarizable continuum model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fukuda, Ryoichi, E-mail: fukuda@ims.ac.jp; Ehara, Masahiro; Elements Strategy Initiative for Catalysts and Batteries

2015-12-31

The effects from solvent environment are specific to the electronic states; therefore, a computational scheme for solvent effects consistent with the electronic states is necessary to discuss electronic excitation of molecules in solution. The PCM (polarizable continuum model) SAC (symmetry-adapted cluster) and SAC-CI (configuration interaction) methods are developed for such purposes. The PCM SAC-CI adopts the state-specific (SS) solvation scheme where solvent effects are self-consistently considered for every ground and excited states. For efficient computations of many excited states, we develop a perturbative approximation for the PCM SAC-CI method, which is called corrected linear response (cLR) scheme. Our test calculationsmore » show that the cLR PCM SAC-CI is a very good approximation of the SS PCM SAC-CI method for polar and nonpolar solvents.« less

Bidirectional switch of the valence associated with a hippocampal contextual memory engram

PubMed Central

Redondo, Roger L; Kim, Joshua; Arons, Autumn L; Ramirez, Steve; Liu, Xu; Tonegawa, Susumu

2014-01-01

The valence of memories is malleable because of their intrinsic reconstructive property1. This property of memory has been used clinically to treat maladaptive behaviours2. However, the neuronal mechanisms and brain circuits that enable the switching of the valence of memories remain largely unknown. Here, we investigated these mechanisms by applying the recently developed memory engram cell-labelling and -manipulation technique 3,4. We labelled, with Channelrhodopsin-2 (ChR2), a population of cells in either the dorsal dentate gyrus (DG) of the hippocampus or the basolateral complex of the amygdala (BLA) that were specifically activated during contextual fear or reward conditioning. Both groups of fear-conditioned mice displayed aversive light-dependent responses in an optogenetic place avoidance test, whereas both DG- and BLA-labelled mice that underwent reward conditioning exhibited an appetitive response in an optogenetic place preference test. Next, in an attempt to reverse the valence of memory within a subject, mice whose DG or BLA engram had initially been labelled by contextual fear or reward conditioning were subjected to a second conditioning of the opposite valence while their original DG or BLA engram was reactivated by blue light. Subsequent optogenetic place avoidance and preference tests revealed that while the DG-engram group displayed a response indicating a switch of the memory valence, the BLA-engram group did not. This switch was also evident at the cellular level by a change in functional connectivity between DG engram-bearing cells and BLA engram-bearing cells. Thus, we found that in the DG, the neurons carrying the memory engram of a given neutral context have plasticity such that the valence of a conditioned response evoked by their reactivation can be reversed by re-associating this contextual memory engram with a new US of an opposite valence. Our present work provides new insight into the functional neural circuit underlying the

High pressure and synchrotron radiation studies of solid state electronic instabilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pifer, J.H.; Croft, M.C.

This report discusses Eu and General Valence Instabilities; Ce Problem: L{sub 3} Spectroscopy Emphasis; Bulk Property Emphasis; Transition Metal Compound Electronic Structure; Electronic Structure-Phonon Coupling Studies; High Temperature Superconductivity and Oxide Materials; and Novel Materials Collaboration with Chemistry.

Synthesis of a Neutral Mixed-Valence Diferrocenyl Carborane for Molecular Quantum-Dot Cellular Automata Applications.

PubMed

Christie, John A; Forrest, Ryan P; Corcelli, Steven A; Wasio, Natalie A; Quardokus, Rebecca C; Brown, Ryan; Kandel, S Alex; Lu, Yuhui; Lent, Craig S; Henderson, Kenneth W

2015-12-14

The preparation of 7-Fc(+) -8-Fc-7,8-nido-[C2 B9 H10 ](-) (Fc(+) FcC2 B9 (-) ) demonstrates the successful incorporation of a carborane cage as an internal counteranion bridging between ferrocene and ferrocenium units. This neutral mixed-valence Fe(II) /Fe(III) complex overcomes the proximal electronic bias imposed by external counterions, a practical limitation in the use of molecular switches. A combination of UV/Vis-NIR spectroscopic and TD-DFT computational studies indicate that electron transfer within Fc(+) FcC2 B9 (-) is achieved through a bridge-mediated mechanism. This electronic framework therefore provides the possibility of an all-neutral null state, a key requirement for the implementation of quantum-dot cellular automata (QCA) molecular computing. The adhesion, ordering, and characterization of Fc(+) FcC2 B9 (-) on Au(111) has been observed by scanning tunneling microscopy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

AB INITIO calculation of the electromigration wind valence of interstitial hydrogen in f.c.c metals

NASA Astrophysics Data System (ADS)

van Ek, J.; Lodder, A.

1990-02-01

Calculated electromigration wind valences, obtained within a KKR-Green function description, are presented. It is shown that the electromigration wind valence of hydrogen along different migration paths in Cu, Ag and Pd can be calculated including charge transfer effects in the impurity cluster. A nice procedure for retrieving the scalar character of the wind valence in an f.c.c metal introduces an explanation for the isotope effect in the wind valence.

A facilitative effect of negative affective valence on working memory.

PubMed

Gotoh, Fumiko; Kikuchi, Tadashi; Olofsson, Ulrich

2010-06-01

Previous studies have shown that negatively valenced information impaired working memory performance due to an attention-capturing effect. The present study examined whether negative valence could also facilitate working memory. Affective words (negative, neutral, positive) were used as retro-cues in a working memory task that required participants to remember colors at different spatial locations on a computer screen. Following the cue, a target detection task was used to either shift attention to a different location or keep attention at the same location as the retro-cue. Finally, participants were required to discriminate the cued color from a set of distractors. It was found that negative cues yielded shorter response times (RTs) in the attention-shift condition and longer RTs in the attention-stay condition, compared with neutral and positive cues. The results suggest that negative affective valence may enhance working memory performance (RTs), provided that attention can be disengaged.

Effects of valence and arousal on written word recognition: time course and ERP correlates.

PubMed

Citron, Francesca M M; Weekes, Brendan S; Ferstl, Evelyn C

2013-01-15

Models of affect assume a two-dimensional framework, composed of emotional valence and arousal. Although neuroimaging evidence supports a neuro-functional distinction of their effects during single word processing, electrophysiological studies have not yet compared the effects of arousal within the same category of valence (positive and negative). Here we investigate effects of arousal and valence on written lexical decision. Amplitude differences between emotion and neutral words were seen in the early posterior negativity (EPN), the late positive complex and in a sustained slow positivity. In addition, trends towards interactive effects of valence and arousal were observed in the EPN, showing larger amplitude for positive, high-arousal and negative, low-arousal words. The results provide initial evidence for interactions between arousal and valence during processing of positive words and highlight the importance of both variables in studies of emotional stimulus processing. Crown Copyright © 2012. Published by Elsevier Ireland Ltd. All rights reserved.

Quantum oscillations in a two-dimensional electron gas at the rocksalt/zincblende interface of PbTe/CdTe (111) heterostructures

DOE PAGES

Zhang, Bingpo; Lu, Ping; Liu, Henan; ...

2015-06-05

Quantum oscillations are observed in the 2DEG system at the interface of novel heterostructures, PbTe/CdTe (111), with nearly identical lattice parameters (a PbTe = 0.6462 nm, a CdTe = 0.648 nm) but very different lattice structures (PbTe: rock salt, CdTe: zinc blende). The 2DEG formation mechanism, a mismatch in the bonding configurations of the valence electrons at the interface, is uniquely different from the other known 2DEG systems. The aberration-corrected scanning transmission electron microscope (AC-STEM) characterization indicates an abrupt interface without cation interdiffusion due to a large miscibility gap between the two constituent materials. As a result, electronic transport measurementsmore » under magnetic field up to 60 T, with the observation of Landau level filling factor ν = 1, unambiguously reveal a π Berry phase, suggesting the Dirac Fermion nature of the 2DEG at the heterostructure interface, and the PbTe/CdTe heterostructure being a new candidate for 2D topological crystalline insulators.« less

Measuring multi-configurational character by orbital entanglement

NASA Astrophysics Data System (ADS)

Stein, Christopher J.; Reiher, Markus

2017-09-01

One of the most critical tasks at the very beginning of a quantum chemical investigation is the choice of either a multi- or single-configurational method. Naturally, many proposals exist to define a suitable diagnostic of the multi-configurational character for various types of wave functions in order to assist this crucial decision. Here, we present a new orbital-entanglement-based multi-configurational diagnostic termed Zs(1). The correspondence of orbital entanglement and static (or non-dynamic) electron correlation permits the definition of such a diagnostic. We chose our diagnostic to meet important requirements such as well-defined limits for pure single-configurational and multi-configurational wave functions. The Zs(1) diagnostic can be evaluated from a partially converged, but qualitatively correct, and therefore inexpensive density matrix renormalisation group wave function as in our recently presented automated active orbital selection protocol. Its robustness and the fact that it can be evaluated at low cost make this diagnostic a practical tool for routine applications.

Empirical valence bond models for reactive potential energy surfaces: a parallel multilevel genetic program approach.

PubMed

Bellucci, Michael A; Coker, David F

2011-07-28

We describe a new method for constructing empirical valence bond potential energy surfaces using a parallel multilevel genetic program (PMLGP). Genetic programs can be used to perform an efficient search through function space and parameter space to find the best functions and sets of parameters that fit energies obtained by ab initio electronic structure calculations. Building on the traditional genetic program approach, the PMLGP utilizes a hierarchy of genetic programming on two different levels. The lower level genetic programs are used to optimize coevolving populations in parallel while the higher level genetic program (HLGP) is used to optimize the genetic operator probabilities of the lower level genetic programs. The HLGP allows the algorithm to dynamically learn the mutation or combination of mutations that most effectively increase the fitness of the populations, causing a significant increase in the algorithm's accuracy and efficiency. The algorithm's accuracy and efficiency is tested against a standard parallel genetic program with a variety of one-dimensional test cases. Subsequently, the PMLGP is utilized to obtain an accurate empirical valence bond model for proton transfer in 3-hydroxy-gamma-pyrone in gas phase and protic solvent. © 2011 American Institute of Physics

Pressure and magnetic field effects on the valence transition of EuRh2Si2

NASA Astrophysics Data System (ADS)

Mitsuda, Akihiro; Kishaba, Eigo; Fujimoto, Takumi; Oyama, Kohei; Wada, Hirofumi; Mizumaki, Masaichiro; Kawamura, Naomi; Ishimatsu, Naoki

2018-05-01

We have measured the X-ray absorption spectra (XAS), electrical resistivity and magnetic susceptibility of EuRh2Si2, which undergoes a valence transition under high pressures. A sharp decrease in the Eu valence determined from the XAS was observed at around 70 K in the temperature dependence at P = 1.2-1.9 GPa. In the temperature dependence of electrical resistivity and magnetic susceptibility, we observed jumps associated with the temperature-induced valence transition under high pressures. The magnetoresistance detected a field-induced valence transition. The results are discussed from the thermodynamic point of view.

Accuracy of embedded fragment calculation for evaluating electron interactions in mixed valence magnetic systems: study of 2e-reduced lindqvist polyoxometalates.

PubMed

Suaud, Nicolas; López, Xavier; Ben Amor, Nadia; Bandeira, Nuno A G; de Graaf, Coen; Poblet, Josep M

2015-02-10

Accurate quantum chemical calculations on real-world magnetic systems are challenging, the inclusion of electron correlation being the bottleneck of such task. One method proposed to overcome this difficulty is the embedded fragment approach. It tackles a chemical problem by dividing it into small fragments, which are treated in a highly accurate way, surrounded by an embedding included at an approximate level. For the vast family of medium-to-large sized polyoxometalates, two-electron-reduced systems are habitual and their magnetic properties are interesting. In this paper, we aim at assessing the quality of embedded fragment calculations by checking their ability to reproduce the electronic spectra of a complete system, here the mixed-metal series [MoxW6-xO19](4-) (x = 0-6). The microscopic parameters extracted from fragment calculations (electron hopping, intersite electrostatic repulsion, local orbital energy, etc.) have been used to reproduce the spectra through model Hamiltonian calculations. These energies are compared to the results of the highly accurate ab initio difference dedicated configuration interaction (DDCI) method on the complete system. In general, the model Hamiltonian calculations using parameters extracted from embedded fragments nearly exactly reproduce the DDCI spectra. This is quite an important result since it can be generalized to any inorganic magnetic system. Finally, the occurrence of singlet or triplet ground states in the series of molecules studied is rationalized upon the interplay of the parameters extracted.

Electron-spectroscopy and -diffraction study of the conductivity of CVD diamond ( 0 0 1 )2×1 surface

NASA Astrophysics Data System (ADS)

Kono, S.; Takano, T.; Shimomura, M.; Goto, T.; Sato, K.; Abukawa, T.; Tachiki, M.; Kawarada, H.

2003-04-01

A chemical vapor deposition as-grown diamond (0 0 1) single-domain 2 × 1 surface was studied by electron-spectroscopy and electron-diffraction in ultrahigh vacuum (UHV). In order to change the surface conductivity (SC) of the diamond in UHV, three annealing stages were used; without annealing, annealing at 300 °C and annealing at 550 °C. From low energy electron diffraction and X-ray photoelectron spectroscopic (XPS) studies, an existence of SC was suggested for the first two stages of annealing and an absence of SC was suggested for the last stage of annealing. Changes in C KVV Auger electron spectroscopic spectra, C KVV Auger electron diffraction (AED) patterns and C 1s XPS peak positions were noticed between the annealing stages at 300 and 550 °C. These changes are interpreted as such that the state of hydrogen involvement in a subsurface of diamond (0 0 1)2 × 1 changes as SC changes. In particular, the presence of local disorder in diamond configuration in SC subsurface is pointed out from C KVV AED. From C 1s XPS peak shifts, a lower bound for the Fermi-level for SC layers from the valence band top is presented to be ˜0.5 eV.

Electronic structure and the origin of the Dzyaloshinskii-Moriya interaction in MnSi

DOE PAGES

Satpathy, S.; Shanavas, K. V.

2016-05-02

Here, the metallic helimagnet MnSi has been found to exhibit skyrmionic spin textures when subjected to magnetic fields at low temperatures. The Dzyaloshinskii-Moriya (DM) interaction plays a key role in stabilizing the skyrmion state. With the help of first-principles calculations, crystal field theory and a tight-binding model we study the electronic structure and the origin of the DM interaction in the B20 phase of MnSi. The strength ofmore » $$\\vec{D}$$ parameter is determined by the magnitude of the spin-orbit interaction and the degree of orbital mixing, induced by the symmetry-breaking distortions in the B20 phase. We find that, strong coupling between Mn-$d$ and Si-$p$ states lead to a mixed valence ground state $$|d^{7-x}p^{2+x}\\rangle$$ configuration. The experimental magnetic moment of $$0.4~\\mu_B$$ is consistent with the Coulomb-corrected DFT+$U$ calculations, which redistributes electrons between the majority and minority spin channels. We derive the magnetic interaction parameters $J$ and $$\\vec{D}$$ for Mn-Si-Mn superexchange paths using Moriya's theory assuming the interaction to be mediated by $$e_g$$ electrons near the Fermi level. Finally, using parameters from our calculations, we get reasonable agreement with the observations.« less

Accurate Valence Ionization Energies from Kohn-Sham Eigenvalues with the Help of Potential Adjustors.

PubMed

Thierbach, Adrian; Neiss, Christian; Gallandi, Lukas; Marom, Noa; Körzdörfer, Thomas; Görling, Andreas

2017-10-10

An accurate yet computationally very efficient and formally well justified approach to calculate molecular ionization potentials is presented and tested. The first as well as higher ionization potentials are obtained as the negatives of the Kohn-Sham eigenvalues of the neutral molecule after adjusting the eigenvalues by a recently [ Görling Phys. Rev. B 2015 , 91 , 245120 ] introduced potential adjustor for exchange-correlation potentials. Technically the method is very simple. Besides a Kohn-Sham calculation of the neutral molecule, only a second Kohn-Sham calculation of the cation is required. The eigenvalue spectrum of the neutral molecule is shifted such that the negative of the eigenvalue of the highest occupied molecular orbital equals the energy difference of the total electronic energies of the cation minus the neutral molecule. For the first ionization potential this simply amounts to a ΔSCF calculation. Then, the higher ionization potentials are obtained as the negatives of the correspondingly shifted Kohn-Sham eigenvalues. Importantly, this shift of the Kohn-Sham eigenvalue spectrum is not just ad hoc. In fact, it is formally necessary for the physically correct energetic adjustment of the eigenvalue spectrum as it results from ensemble density-functional theory. An analogous approach for electron affinities is equally well obtained and justified. To illustrate the practical benefits of the approach, we calculate the valence ionization energies of test sets of small- and medium-sized molecules and photoelectron spectra of medium-sized electron acceptor molecules using a typical semilocal (PBE) and two typical global hybrid functionals (B3LYP and PBE0). The potential adjusted B3LYP and PBE0 eigenvalues yield valence ionization potentials that are in very good agreement with experimental values, reaching an accuracy that is as good as the best G 0 W 0 methods, however, at much lower computational costs. The potential adjusted PBE eigenvalues result in

Time-resolved spectroscopic characterization of photo-induced valence tautomerism for a cobalt dioxolene complex

NASA Astrophysics Data System (ADS)

Gentili, Pier Luigi; Bussotti, Laura; Righini, Roberto; Beni, Alessandra; Bogani, Lapo; Dei, Andrea

2005-07-01

The valence tautomerism of low-spin Co III(Cat-N-BQ)(Cat-N-SQ) (where Cat-N-BQ is 2-(2-hydroxy-3,5-di- tert-butylphenylimino)-4,6-di- tert-butylcyclohexa-3,5-dienone and Cat-N-SQ is the dianionic radical analogue) was investigated by means of UV-vis pump-probe transient absorption spectroscopy and 1H NMR technique in chloroform and dichloromethane. By exciting the CT transition of the complex at 480 nm, an intramolecular electron transfer process is selectively triggered. The photo-induced charge transfer is pursued by a cascade of two main molecular events characterized by the ultrafast transient absorption spectroscopy: the first gives rise to the metastable high-spin Co II(Cat-N-BQ) 2 that, secondly, reaches the chemical equilibrium with the reactant species. The rate constant of back valence tautomerization estimated by measuring the lifetime of high-spin Co II(Cat-N-BQ) 2 species and the equilibrium constant for the Co III(Cat-N-BQ)(Cat-N-SQ) ⇄ Co II(Cat-N-BQ) 2 interconversion, is significantly large (on the order of 10 9 s -1). It is interpreted under the point of view of the theory formulated by Jortner and Buhks et al. for non-adiabatic radiationless processes.

Beyond Valence and Magnitude: a Flexible Evaluative Coding System in the Brain

PubMed Central

Gu, Ruolei; Lei, Zhihui; Broster, Lucas; Wu, Tingting; Jiang, Yang; Luo, Yue-jia

2013-01-01

Outcome evaluation is a cognitive process that plays an important role in our daily lives. In most paradigms utilized in the field of experimental psychology, outcome valence and outcome magnitude are the two major features investigated. The classical “independent coding model” suggest that outcome valence and outcome magnitude are evaluated by separate neural mechanisms that may be mapped onto discrete event-related potential (ERP) components: feedback-related negativity (FRN) and the P3, respectively. To examine this model, we presented outcome valence and magnitude sequentially rather than simultaneously. The results reveal that when only outcome valence or magnitude is known, both the FRN and the P3 encode that outcome feature; when both aspects of outcome are known, the cognitive functions of the two components dissociate: the FRN responds to the information available in the current context, while the P3 pattern depends on outcome presentation sequence. The current study indicates that the human evaluative system, indexed in part by the FRN and the P3, is more flexible than previous theories suggested. PMID:22019775

Adolescents' responses to the gender valence of cigarette advertising imagery: the role of affect and the self-concept.

PubMed

Shadel, William G; Niaura, Raymond; Abrams, David B

2004-12-01

The studies presented in this manuscript evaluated the role that affect and the self-concept play in adolescent never smokers' reactions to the gender valence of cigarette advertising imagery. Study 1 (n=29; 59% female) revealed that adolescent females have more positive affective reactions to female-valenced cigarette advertising imagery compared to male-valenced cigarette advertising imagery. Study 2 (n=101; 56% female) revealed that adolescent females viewed female-valenced cigarette advertising imagery as more relevant to their self-concepts compared to male-valenced cigarette advertising imagery. Across both studies, male adolescents did not respond differently as a function of the gender valence of cigarette advertising imagery. Thus, female-valenced cigarette advertising imagery may have specific effects on never smoking female adolescents by enhancing positive affect and suggesting that women who smoke hold the same characteristics as do the young women themselves.

Valence and arousal of emotional stimuli impact cognitive-motor performance in an oddball task.

PubMed

Lu, Yingzhi; Jaquess, Kyle J; Hatfield, Bradley D; Zhou, Chenglin; Li, Hong

2017-04-01

It is widely recognized that emotions impact an individual's ability to perform in a given task. However, little is known about how emotion impacts the various aspects of cognitive -motor performance. We recorded event-related potentials (ERPs) and chronometric responses from twenty-six participants while they performed a cognitive-motor oddball task in regard to four categories of emotional stimuli (high-arousing positive-valence, low-arousing positive-valence, high-arousing negative-valence, and low-arousing negative-valence) as "deviant" stimuli. Six chronometric responses (reaction time, press time, return time, choice time, movement time, and total time) and three ERP components (P2, N2 and late positive potential) were measured. Results indicated that reaction time was significantly affected by the presentation of emotional stimuli. Also observed was a negative relationship between N2 amplitude and elements of performance featuring reaction time in the low-arousing positive-valence condition. This study provides further evidence that emotional stimuli influence cognitive-motor performance in a specific manner. Copyright © 2017 Elsevier B.V. All rights reserved.

Age effects in emotional prospective memory: cue valence differentially affects the prospective and retrospective component.

PubMed

Schnitzspahn, Katharina M; Horn, Sebastian S; Bayen, Ute J; Kliegel, Matthias

2012-06-01

While first studies suggested that emotional task material may enhance prospective memory performance in young and older adults, the extent and mechanisms of this effect are under debate. The authors explored possible differential effects of cue valence on the prospective and retrospective component of prospective memory in young and older adults. Forty-five young and 41 older adults performed a prospective memory task in which emotional valence of the prospective memory cue was manipulated (positive, negative, neutral). The multinomial model of event-based prospective memory was used to analyze effects of valence and age on the two prospective memory components separately. Results revealed an interaction indicating that age differences were smaller in both emotional valence conditions. For older adults positive cues improved the prospective component, while negative cues improved the retrospective component. No main effect of valence was found for younger adults on an overt accuracy measure, but model-based analyses showed that the retrospective component was enhanced in the positive compared with the negative cue condition. The study extends the literature in demonstrating that processes underlying emotional effects on prospective memory may differ depending on valence and age. PsycINFO Database Record (c) 2012 APA, all rights reserved

Electron and Nucleon Localization Functions of Oganesson: Approaching the Thomas-Fermi Limit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jerabek, Paul; Schuetrumpf, Bastian; Schwerdtfeger, Peter

Fermion localization functions are used to discuss electronic and nucleonic shell structure effects in the superheavy element oganesson, the heaviest element discovered to date. Spin-orbit splitting in the 7p electronic shell becomes so large (~10 eV) that Og is expected to show uniform-gas-like behavior in the valence region with a rather large dipole polarizability compared to the lighter rare gas elements. The nucleon localization in Og is also predicted to undergo a transition to the Thomas-Fermi gas behavior in the valence region. Finally, this effect, particularly strong for neutrons, is due to the high density of single-particle orbitals.

Electron and Nucleon Localization Functions of Oganesson: Approaching the Thomas-Fermi Limit

DOE PAGES

Jerabek, Paul; Schuetrumpf, Bastian; Schwerdtfeger, Peter; ...

2018-01-31

Fermion localization functions are used to discuss electronic and nucleonic shell structure effects in the superheavy element oganesson, the heaviest element discovered to date. Spin-orbit splitting in the 7p electronic shell becomes so large (~10 eV) that Og is expected to show uniform-gas-like behavior in the valence region with a rather large dipole polarizability compared to the lighter rare gas elements. The nucleon localization in Og is also predicted to undergo a transition to the Thomas-Fermi gas behavior in the valence region. Finally, this effect, particularly strong for neutrons, is due to the high density of single-particle orbitals.

Electron and Nucleon Localization Functions of Oganesson: Approaching the Thomas-Fermi Limit

NASA Astrophysics Data System (ADS)

Jerabek, Paul; Schuetrumpf, Bastian; Schwerdtfeger, Peter; Nazarewicz, Witold

2018-02-01

Fermion localization functions are used to discuss electronic and nucleonic shell structure effects in the superheavy element oganesson, the heaviest element discovered to date. Spin-orbit splitting in the 7 p electronic shell becomes so large (˜10 eV ) that Og is expected to show uniform-gas-like behavior in the valence region with a rather large dipole polarizability compared to the lighter rare gas elements. The nucleon localization in Og is also predicted to undergo a transition to the Thomas-Fermi gas behavior in the valence region. This effect, particularly strong for neutrons, is due to the high density of single-particle orbitals.

The Electronic Structure of the Cs/ n-GaN(0001) Nano-Interface

NASA Astrophysics Data System (ADS)

Benemanskaya, G. V.; Lapushkin, M. N.; Marchenko, D. E.; Timoshnev, S. N.

2018-03-01

Electronic structures of the n-GaN(0001) surface and Cs/ n-GaN(0001) interface with submonolayer Cs coverages were studied for the first time in situ by the photoelectron spectroscopy (PES) method. The spectra of photoemission from the valence band, surface electron states, and core levels (Ga 3 d, Cs 4 d, Cs 5 p) under synchrotron excitation were measured in a range of photon energies within 50-150 eV. Evolution of the spectrum of surface states near the valence-band maximum was revealed by PES during the adsorption of Cs atoms. A metallic character of the Cs/ n-GaN(0001) nano-interface is demonstrated.

Ab initio calculations of potential energy curves of Hg/sub 2/ and TlHg

DOE Office of Scientific and Technical Information (OSTI.GOV)

Celestino, K.C.; Ermler, W.C.

1984-08-15

Potential energy curves for electronic states of Hg/sub 2/ and TlHg are presented and analyzed. They are derived using large scale configuration interaction procedures for the valence electrons, with the core electrons represented by ab initio relativistic effective potentials. The effect of spin-orbit coupling are investigated for the low-lying excimer states. It is determined that neither system possesses strongly bound electronic states for which transitions to the repulsive ground states are optically allowed.

Configuration management program plan for Hanford site systems engineering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffman, A.G.

This plan establishes the integrated configuration management program for the evolving technical baseline developed through the systems engineering process. This configuration management program aligns with the criteria identified in the DOE Standard, DOE-STD-1073-93. Included are specific requirements for control of the systems engineering RDD-100 database, and electronic data incorporated in the database that establishes the Hanford site technical baseline.

Contextual blending of ingroup/outgroup face stimuli and word valence: LPP modulation and convergence of measures.

PubMed

Hurtado, Esteban; Haye, Andrés; González, Ramiro; Manes, Facundo; Ibáñez, Agustiń

2009-06-26

Several event related potential (ERP) studies have investigated the time course of different aspects of evaluative processing in social bias research. Various reports suggest that the late positive potential (LPP) is modulated by basic evaluative processes, and some reports suggest that in-/outgroup relative position affects ERP responses. In order to study possible LPP blending between facial race processing and semantic valence (positive or negative words), we recorded ERPs while indigenous and non-indigenous participants who were matched by age and gender performed an implicit association test (IAT). The task involved categorizing faces (ingroup and outgroup) and words (positive and negative). Since our paradigm implies an evaluative task with positive and negative valence association, a frontal distribution of LPPs similar to that found in previous reports was expected. At the same time, we predicted that LPP valence lateralization would be modulated not only by positive/negative associations but also by particular combinations of valence, face stimuli and participant relative position. Results showed that, during an IAT, indigenous participants with greater behavioral ingroup bias displayed a frontal LPP that was modulated in terms of complex contextual associations involving ethnic group and valence. The LPP was lateralized to the right for negative valence stimuli and to the left for positive valence stimuli. This valence lateralization was influenced by the combination of valence and membership type relevant to compatibility with prejudice toward a minority. Behavioral data from the IAT and an explicit attitudes questionnaire were used to clarify this finding and showed that ingroup bias plays an important role. Both ingroup favoritism and indigenous/non-indigenous differences were consistently present in the data. Our results suggest that frontal LPP is elicited by contextual blending of evaluative judgments of in-/outgroup information and positive vs

Analysis of the bond-valence method for calculating (29) Si and (31) P magnetic shielding in covalent network solids.

PubMed

Holmes, Sean T; Alkan, Fahri; Iuliucci, Robbie J; Mueller, Karl T; Dybowski, Cecil

2016-07-05

(29) Si and (31) P magnetic-shielding tensors in covalent network solids have been evaluated using periodic and cluster-based calculations. The cluster-based computational methodology employs pseudoatoms to reduce the net charge (resulting from missing co-ordination on the terminal atoms) through valence modification of terminal atoms using bond-valence theory (VMTA/BV). The magnetic-shielding tensors computed with the VMTA/BV method are compared to magnetic-shielding tensors determined with the periodic GIPAW approach. The cluster-based all-electron calculations agree with experiment better than the GIPAW calculations, particularly for predicting absolute magnetic shielding and for predicting chemical shifts. The performance of the DFT functionals CA-PZ, PW91, PBE, rPBE, PBEsol, WC, and PBE0 are assessed for the prediction of (29) Si and (31) P magnetic-shielding constants. Calculations using the hybrid functional PBE0, in combination with the VMTA/BV approach, result in excellent agreement with experiment. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

The site occupation and valence of Mn ions in the crystal lattice of Sr{sub 4}Al{sub 14}O{sub 25} and its deep red emission for high color-rendering white light-emitting diodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Lei, E-mail: shanggan2009@qq.com; Xue, Shaochan; Chen, Xiuling

2014-12-15

Highlights: • Different valences of Mn ions in Sr{sub 4}Al{sub 14}O{sub 25} were identified using XANES and EPR. • Red luminescence was attributed to Mn{sup 4+} occupying the center of AlO{sub 6} octahedron. • The Mn{sup 3+} incorporated in the center of AlO{sub 4} tetrahedron was non-luminescent. • The bond-valence theory was used to analyze the effective valences of cations. • A white LED device with CRI up to Ra 93.23 was packaged by using the red phosphor. - Abstract: The synthesis and component of red phosphor, Sr{sub 4}Al{sub 14}O{sub 25}: Mn, were optimized for application in white light-emitting diodes.more » The microstructure and morphology were investigated by the X-ray diffraction and scanning electron microscopy. Different valences of Mn ions in Sr{sub 4}Al{sub 14}O{sub 25} were discriminated using the electron paramagnetic resonance and X-ray absorption near-edge structure spectroscopy techniques. The bond-valence theory was used to analyze the effective valences of Sr{sup 2+} and Al{sup 3+} in Sr{sub 4}Al{sub 14}O{sub 25}. As a result, the strong covalence of Al{sup 3+} in the AlO{sub 4} tetrahedron other than in the AlO{sub 6} octahedron is disclosed. The deep red emission is attributed to Mn{sup 4+} occupying the center of AlO{sub 6} octahedron. The mechanism of energy transfer is mainly through dipole–dipole interaction, revealed by the analyses of critical distance and concentration quench. A high color rendering white LED prototype with color-rendering index up to Ra 93.23 packaged by using the red phosphor demonstrates its applicability.« less

Inter-Layer Coupling Induced Valence Band Edge Shift in Mono- to Few-Layer MoS2

PubMed Central

Trainer, Daniel J.; Putilov, Aleksei V.; Di Giorgio, Cinzia; Saari, Timo; Wang, Baokai; Wolak, Mattheus; Chandrasena, Ravini U.; Lane, Christopher; Chang, Tay-Rong; Jeng, Horng-Tay; Lin, Hsin; Kronast, Florian; Gray, Alexander X.; Xi, Xiaoxing X.; Nieminen, Jouko; Bansil, Arun; Iavarone, Maria

2017-01-01

Recent progress in the synthesis of monolayer MoS2, a two-dimensional direct band-gap semiconductor, is paving new pathways toward atomically thin electronics. Despite the large amount of literature, fundamental gaps remain in understanding electronic properties at the nanoscale. Here, we report a study of highly crystalline islands of MoS2 grown via a refined chemical vapor deposition synthesis technique. Using high resolution scanning tunneling microscopy and spectroscopy (STM/STS), photoemission electron microscopy/spectroscopy (PEEM) and μ-ARPES we investigate the electronic properties of MoS2 as a function of the number of layers at the nanoscale and show in-depth how the band gap is affected by a shift of the valence band edge as a function of the layer number. Green’s function based electronic structure calculations were carried out in order to shed light on the mechanism underlying the observed bandgap reduction with increasing thickness, and the role of the interfacial Sulphur atoms is clarified. Our study, which gives new insight into the variation of electronic properties of MoS2 films with thickness bears directly on junction properties of MoS2, and thus impacts electronics application of MoS2. PMID:28084465

Inter-layer coupling induced valence band edge shift in mono- to few-layer MoS 2

DOE PAGES

Trainer, Daniel J.; Putilov, Aleksei V.; Di Giorgio, Cinzia; ...

2017-01-13

In this study, recent progress in the synthesis of monolayer MoS 2, a two-dimensional direct band-gap semiconductor, is paving new pathways toward atomically thin electronics. Despite the large amount of literature, fundamental gaps remain in understanding electronic properties at the nanoscale. Here,we report a study of highly crystalline islands of MoS 2 grown via a refined chemical vapor deposition synthesis technique. Using high resolution scanning tunneling microscopy and spectroscopy (STM/STS), photoemission electron microscopy/spectroscopy (PEEM) and μ-ARPES we investigate the electronic properties of MoS 2 as a function of the number of layers at the nanoscale and show in-depth how themore » band gap is affected by a shift of the valence band edge as a function of the layer number. Green’s function based electronic structure calculations were carried out in order to shed light on the mechanism underlying the observed bandgap reduction with increasing thickness, and the role of the interfacial Sulphur atoms is clarified. Our study, which gives new insight into the variation of electronic properties of MoS 2 films with thickness bears directly on junction properties of MoS2, and thus impacts electronics application of MoS 2.« less

Formation, spin-up, and stability of field-reversed configurations

DOE PAGES

Omelchenko, Yuri A.

2015-08-24

Formation, spontaneous spin-up and stability of theta-pinch formed field-reversed configurations are studied self-consistently in three dimensions with a multiscale hybrid model that treats all plasma ions as full-orbit collisional macro-particles and the electrons as a massless quasineutral fluid. The end-to-end hybrid simulations for the first time reveal poloidal profiles of implosion-driven fast toroidal plasma rotation and demonstrate three well-known discharge regimes as a function of experimental parameters: the decaying stable configuration, the tilt unstable configuration and the nonlinear evolution of a fast growing tearing mode.

Approach and Withdrawal Tendencies during Written Word Processing: Effects of Task, Emotional Valence, and Emotional Arousal.

PubMed

Citron, Francesca M M; Abugaber, David; Herbert, Cornelia

2015-01-01

The affective dimensions of emotional valence and emotional arousal affect processing of verbal and pictorial stimuli. Traditional emotional theories assume a linear relationship between these dimensions, with valence determining the direction of a behavior (approach vs. withdrawal) and arousal its intensity or strength. In contrast, according to the valence-arousal conflict theory, both dimensions are interactively related: positive valence and low arousal (PL) are associated with an implicit tendency to approach a stimulus, whereas negative valence and high arousal (NH) are associated with withdrawal. Hence, positive, high-arousal (PH) and negative, low-arousal (NL) stimuli elicit conflicting action tendencies. By extending previous research that used several tasks and methods, the present study investigated whether and how emotional valence and arousal affect subjective approach vs. withdrawal tendencies toward emotional words during two novel tasks. In Study 1, participants had to decide whether they would approach or withdraw from concepts expressed by written words. In Studies 2 and 3 participants had to respond to each word by pressing one of two keys labeled with an arrow pointing upward or downward. Across experiments, positive and negative words, high or low in arousal, were presented. In Study 1 (explicit task), in line with the valence-arousal conflict theory, PH and NL words were responded to more slowly than PL and NH words. In addition, participants decided to approach positive words more often than negative words. In Studies 2 and 3, participants responded faster to positive than negative words, irrespective of their level of arousal. Furthermore, positive words were significantly more often associated with "up" responses than negative words, thus supporting the existence of implicit associations between stimulus valence and response coding (positive is up and negative is down). Hence, in contexts in which participants' spontaneous responses are