Kondo and mixed-valence regimes in multilevel quantum dots

International Nuclear Information System (INIS)

Chudnovskiy, A. L.; Ulloa, S. E.

2001-01-01

We investigate the dependence of the ground state of a multilevel quantum dot on the coupling to an external fermionic system and on the interactions in the dot. As the coupling to the external system increases, the rearrangement of the effective energy levels in the dot signals the transition from the Kondo regime to a mixed-valence (MV) regime. The MV regime in a two-level dot is characterized by an intrinsic mixing of the levels in the dot, resulting in nonperturbative subtunneling and supertunneling phenomena that strongly influence the Kondo effect

Levels of valence

Directory of Open Access Journals (Sweden)

Vera eShuman

2013-05-01

Full Text Available 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 (unpleasantness, goal obstructiveness/conduciveness, low or high power, self- (incongruence, 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.

Mixing positive and negative valence: Affective-semantic integration of bivalent words.

Science.gov (United States)

Kuhlmann, Michael; Hofmann, Markus J; Briesemeister, Benny B; Jacobs, Arthur M

2016-08-05

Single words have affective and aesthetic properties that influence their processing. Here we investigated the processing of a special case of word stimuli that are extremely difficult to evaluate, bivalent noun-noun-compounds (NNCs), i.e. novel words that mix a positive and negative noun, e.g. 'Bombensex' (bomb-sex). In a functional magnetic resonance imaging (fMRI) experiment we compared their processing with easier-to-evaluate non-bivalent NNCs in a valence decision task (VDT). Bivalent NNCs produced longer reaction times and elicited greater activation in the left inferior frontal gyrus (LIFG) than non-bivalent words, especially in contrast to words of negative valence. We attribute this effect to a LIFG-grounded process of semantic integration that requires greater effort for processing converse information, supporting the notion of a valence representation based on associations in semantic networks.

Valence-delocalization of the mixed-valence oxo-centered trinuclear iron propionates [FeIII2FeIIO(C2H5CO2)6(py)3[npy; n = 0, 1.5

International Nuclear Information System (INIS)

Nakamoto, Tadahiro; Katada, Motomi; Kawata, Satoshi; Kitagawa, Susumu; Sano, Hirotoshi; Konno, Michiko

1994-01-01

Mixed-valence trinuclear iron propionates [Fe III 2 Fe II O(C 2 H 5 CO 2 ) 6 (py) 3 [npy, where n = 0, 1.5, were synthesized and the structure of the pyridine-solvated complex was determined by single-crystal X-ray diffraction. Moessbauer spectra of the solvated propionate complex showed a temperature-dependent mixed-valence state related to phase transitions, reaching an almost delocalized valence state at room temperature. On the other hand, the non-solvated propionate showed a remarkable change of the spectral shape related to a phase transition, remaining in a localized valence state at higher temperatures up to room temperature. (orig.)

Spin dynamics and magnetic ordering in mixed valence systems

International Nuclear Information System (INIS)

Shapiro, S.M.; Moller, H.B.; Axe, J.D.; Birgeneau, R.J.; Bucher, E.

1977-01-01

Neutron scattering measurements are reported on the mixed valence compounds Ce/sub 1-x/Th/sub x/ and TmSe. The Chi''(Q,ω) as derived from the inelastic spectra of Ce 0 . 74 Th 0 . 26 shows a peak in the γ phase near 20.0 meV and shifts abruptly to greater than 70.0 meV at the transition to the α phase. The temperature independence of the susceptibility within the γ phase cannot be simply reconciled with the temperature dependence of the valence within the γ phase. TmSe is shown to order in a type I antiferromagnetic structure below T/sub N/ approx. 3.2 K. The magnetic phase diagram is understood as a successive domain reorientation and a metamagnetic phase transition for T 3+ orders in a type II structure but never achieves long range order

Levels of Valence

Science.gov (United States)

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

Neutron scattering studies of mixed-valence semiconductors

Energy Technology Data Exchange (ETDEWEB)

Mignot, J M [Laboratoire Leon Brillouin (LLB) - Centre d` Etudes de Saclay, 91 - Gif-sur-Yvette (France); Alekseev, P A [Kurchatov Institute, Moscow (Russian Federation)

1994-12-31

Neutron scattering experiments on the mixed-valence (MV) compounds SmB{sub 6} are reported. The inelastic magnetic response of SmB{sub 6} at T = 2 K, measured on a double-isotope single crystal,displays a strongly damped peak at 35 meV corresponding to the inter multiplet transition of Sm{sup 2+}. At lower energies ( h.{omega} {approx_equal} 14 meV), a narrow magnetic excitation is observed, with remarkable scattering-vector and temperature dependences of its intensity. This novel feature is discussed in terms of recent theoretical works describing the formation of an anisotropic local bound state in semiconducting MV materials. If the average samarium valence is decreased by substituting La for Sm, a peak is found to appear at high energies. The elastic magnetic form factor of SmB{sub 6} was determined using polarised neutrons and no significant difference is observed in its Q-dependence with respect to that of pure divalent samarium. This surprising behaviour is constant with previous measurements on the gold (high-pressure) phase of SmS. The above results are compared to those already reported for other MV materials. In particular existing information for TmSe is supplemented by recent inelastic scattering measurements carried out on a large stoichiometric single crystal. (author). 44 refs., 7 figs.

A novel extended architecture with 4 6·6 4 topology based on mixed-valence Wells-Dawson arsenotungstate and mixed-ligand Cu(I) units

Science.gov (United States)

Tong, Ruizhan; Ren, Xiaoyu; Li, Zuoxi; Liu, Bin; Hu, Huaiming; Xue, Ganglin; Fu, Feng; Wang, Jiwu

2010-09-01

A novel inorganic-organic hybrid compound based on mixed-valence Wells-Dawson arsenotungstate and mixed-ligand Cu(I) units, Cu 8I(imi) 4(bpy) 6(H 2O)[As 2VW 2VW 16VlO 62]·2H 2O ( 1) (bpy=4,4'-bipydine; imi=imidazole), has been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, luminescent spectrum and single crystal X-ray diffraction. Single-crystal X-ray diffraction revealed that four terminal and three bridging oxygen atoms of the Wells-Dawson cluster are coordinated to Cu(I) ions and form an unprecedented hepta-supporting polyoxometalate. The functionalized arsenotungstates are further connected by two kinds of tridentate linkers, Imi-Cu-(bpy)-Cu-(bpy)-Cu-(bpy)-Cu-Imi and Imi-Cu-(bpy)-Cu-(bpy)-Cu-H 2O, to construct a 3D framework with 4 6·6 4 topology. The hybrid material has an intense emission at about 397 nm.

Mixed-Initiative Clustering

Science.gov (United States)

Huang, Yifen

2010-01-01

Mixed-initiative clustering is a task where a user and a machine work collaboratively to analyze a large set of documents. We hypothesize that a user and a machine can both learn better clustering models through enriched communication and interactive learning from each other. The first contribution or this thesis is providing a framework of…

A study of the valence shell electronic states of s-triazine by photoabsorption spectroscopy and ab initio calculations

DEFF Research Database (Denmark)

Holland, D.M.P.; Shaw, D.A.; Stener, Mauro

2016-01-01

absorption bands due to excitation from the 1e00 or 6e0 orbitals. The interpretation of the experimental spectrum has been guided by transition energies and oscillator strengths, for Rydberg and valence states, calculated with the time-dependent version of density functional theory and with the coupled...... cluster linear response approach. The theoretical studies indicate that Rydberg/Rydberg and Rydberg/valence mixing is important....

Synthesis, Crystal Structure, and Electroconducting Properties of a 1D Mixed-Valence Cu(I–Cu(II Coordination Polymer with a Dicyclohexyl Dithiocarbamate Ligand

Directory of Open Access Journals (Sweden)

Kenji Nakatani

2015-04-01

Full Text Available A new mixed-valence Cu(I–Cu(II 1D coordination polymer, [CuI4CuIIBr4(Cy2dtc2]n, with an infinite chain structure is synthesized by the reaction of Cu(Cy2dtc2 (Cy2dtc− = dicyclohexyl dithiocarbamate, C13H22NS2 with CuBr·S(CH32. The as-synthesized polymer consists of mononuclear copper(II units of CuII(Cy2dtc2 and tetranuclear copper(I cluster units, CuI4Br4. In the cluster unit, all the CuI ions have distorted trigonal pyramidal coordination geometries, and the CuI–CuI or CuI–CuII distances between the nearest copper ions are shorter than the sum of van der Waals radii for Cu–Cu.

Cluster Correlation in Mixed Models

Science.gov (United States)

Gardini, A.; Bonometto, S. A.; Murante, G.; Yepes, G.

2000-10-01

We evaluate the dependence of the cluster correlation length, rc, on the mean intercluster separation, Dc, for three models with critical matter density, vanishing vacuum energy (Λ=0), and COBE normalization: a tilted cold dark matter (tCDM) model (n=0.8) and two blue mixed models with two light massive neutrinos, yielding Ωh=0.26 and 0.14 (MDM1 and MDM2, respectively). All models approach the observational value of σ8 (and hence the observed cluster abundance) and are consistent with the observed abundance of damped Lyα systems. Mixed models have a motivation in recent results of neutrino physics; they also agree with the observed value of the ratio σ8/σ25, yielding the spectral slope parameter Γ, and nicely fit Las Campanas Redshift Survey (LCRS) reconstructed spectra. We use parallel AP3M simulations, performed in a wide box (of side 360 h-1 Mpc) and with high mass and distance resolution, enabling us to build artificial samples of clusters, whose total number and mass range allow us to cover the same Dc interval inspected through Automatic Plate Measuring Facility (APM) and Abell cluster clustering data. We find that the tCDM model performs substantially better than n=1 critical density CDM models. Our main finding, however, is that mixed models provide a surprisingly good fit to cluster clustering data.

Iron valence in double-perovskite (Ba,Sr,Ca)2FeMoO6: isovalent substitution effect

International Nuclear Information System (INIS)

Yasukawa, Y.; Linden, J.; Chan, T.S.; Liu, R.S.; Yamauchi, H.; Karppinen, M.

2004-01-01

In the Fe-Mo based B-site ordered double-perovskite, A 2 FeMoO 6.0 , with iron in the mixed-valence II/III state, the valence value of Fe is not precisely fixed at 2.5 but may be fine-tuned by means of applying chemical pressure at the A-cation site. This is shown through a systematic 57 Fe Moessbauer spectroscopy study using a series of A 2 FeMoO 6.0 [A=(Ba,Sr) or (Sr,Ca)] samples with high degree of Fe/Mo order, the same stoichiometric oxygen content and also almost the same grain size. The isomer shift values and other hyperfine parameters obtained from the Moessbauer spectra confirm that Fe remains in the mixed-valence state within the whole range of A constituents. However, upon increasing the average cation size at the A site the precise valence of Fe is found to decrease such that within the A=(Ba,Sr) regime the valence of Fe is closer to II, while within the A=(Sr,Ca) regime it is closer to the actual mixed-valence II/III state. As the valence of Fe approaches II, the difference in charges between Fe and Mo increases, and parallel with this the degree of Fe/Mo order increases. Additionally, for the less-ordered samples an increased tendency of clustering of the antisite Fe atoms is deduced from the Moessbauer data

Spin and spinless conductivity in polypyrrole. Evidence for mixed-valence conduction

Energy Technology Data Exchange (ETDEWEB)

Zotti, G.; Schiavon, G. (Ist. di Polarografia ed Elettrochimica Preparativa, Padova (Italy))

In situ conductivity of polypyrrole (as tosylate) as a function of oxidative doping level attains a maximum at three-quarters the total oxidation charge and the relevant in situ ESR signal corresponds to an equal concentration of spin-carrying (polaron) and spinless (bipolaron) species. Results are explained on the basis of mixed-valence conduction. Bipolaron conduction, taking the place of polaron-bipolaron conductivity at higher oxidation levels, accounts for persisting conductivity in the high-oxidation state.

Universality class of non-Fermi liquid behaviour in mixed valence systems

International Nuclear Information System (INIS)

Zhang Guangming; Su Zhaobin; Lu Yu

1995-11-01

A generalized Anderson single-impurity model with off-site Coulomb interactions is derived from the extended three-band Hubbard model, originally proposed to describe the physics of the copper-oxides. Using the abelian bosonization technique and canonical transformations, an effective Hamiltonian is derived in the strong coupling limit, which is essentially analogous to the Toulouse limit of the ordinary Kondo problem. In this limit, the effective Hamiltonian can be exactly solved, with a mixed valence quantum critical point separating two different Fermi liquid phases, i.e. the Kondo phase and the empty orbital phase. In the mixed valence quantum critical regime, the local moment is only partially quenched and X-ray edge singularities are generated. Around the quantum critical point, a new type of non-Fermi liquid behaviour is predicted with an extra specific heat C imp ∼ T 1/4 and a singular spin-susceptibility χ imp ∼ T -3/4 . At the same time, the effective Hamiltonian under single occupancy is transformed into a resonant-level model, from which the correct Kondo physical properties (specific heat, spin susceptibility, and an enhanced Wilson ratio) are easily rederived. Finally, a brief discussion is given to relate these theoretical results to observations in U Pd x Cu 5-x (x=1, 1.5) alloys, which show single-impurity critical behaviour consistent with our predictions. (author). 30 refs

Universality class of non-Fermi-liquid behavior in mixed-valence systems

Science.gov (United States)

Zhang, Guang-Ming; Su, Zhao-Bin; Yu, Lu

1996-01-01

A generalized Anderson single-impurity model with off-site Coulomb interactions is derived from the extended three-band Hubbard model, originally proposed to describe the physics of the copper oxides. Using the Abelian bosonization technique and canonical transformations, an effective Hamiltonian is derived in the strong-coupling limit, which is essentially analogous to the Toulouse limit of the ordinary Kondo problem. In this limit, the effective Hamiltonian can be exactly solved, with a mixed-valence quantum critical point separating two different Fermi-liquid phases, i.e., the Kondo phase and the empty orbital phase. In the mixed-valence quantum critical regime, the local moment is only partially quenched and x-ray edge singularities are generated. Around the quantum critical point, a type of non-Fermi-liquid behavior is predicted with an extra specific heat Cimp~T1/4 and a singular spin susceptibility χimp~T-3/4. At the same time, the effective Hamiltonian under single occupancy is transformed into a resonant-level model, from which the correct Kondo physical properties (specific heat, spin susceptibility, and an enhanced Wilson ratio) are easily rederived. Finally, a brief discussion is given to relate these theoretical results to observations in UPdxCu5-x (x=1,1.5) alloys, which show single-impurity critical behavior consistent with our predictions.

Mechanism of pyridine-ligand exchanges at the different labile sites of 3d heterometallic and mixed valence mu3-oxo trinuclear clusters.

Science.gov (United States)

Novitchi, Ghenadie; Riblet, Fabrice; Scopelliti, Rosario; Helm, Lothar; Gulea, Aurelian; Merbach, André E

2008-11-17

The syntheses and single crystal X-ray structural analysis of five novel hetero- and homometallic mu 3-oxo trinuclear cluster with the formula [Fe (III) 2M (II)(mu 3-O)(mu-O 2CCH 3) 6(4-Rpy) 3]. x(4-Rpy). y(CH 3CN) where R = Ph for 1(Fe 2Mn), 2(Fe 2Fe), 3(Fe 2Co), 4(Fe 2Ni) and R = CF 3 for 5(Fe 2Co), are reported. The persistence of the structure for compounds 2- 5 in dichloromethane solution in the temperature range 190-320 K is demonstrated by (1)H and (19)F NMR spectroscopy. Even at the lowest temperature, the electron exchange in the homometallic mixed-valence compound 2(Fe 2Fe) is in the fast regime at the NMR time scale. Variable temperature and pressure NMR line broadening allowed quantifying the fast coordinated/free 4-Rpy exchanges at the two labile metal centers in these clusters: 2: Fe (III)( k (298)/10 (3) s (-1) = 16.6; Delta H (++) = 60.32 kJ mol (-1); Delta S (++) = + 34.8 J K (-1) mol (-1); Delta V (++) = + 12.5 cm (3) mol (-1)); 3: Fe (11.9; 58.92; +30.7; +10.6) and Co (2.8; 68.24; +49.8; +13.9); 4: Fe(12.2; 67.91; +61.0; -) and Ni (0.37; 78.62; +67.8; +12.3); 5: Fe (46; 58.21; +39.3; +14.2) and Co (4.7; 55.37; +11.2; +10.9). A limiting D mechanism is assigned to these exchange reactions. This assignment is based on a first-order rate law, the detection of intermediates, the positive and large entropies and volumes of activation. The order of reactivity k (Co) > k (Ni) is expected for a D mechanism at these metal centers: their low exchange rates are due to their strong binding with the 4-Rpy donor. Surrounded by oxygen donors the d (5) iron(III) usually reacts associatively; however, here due to low affinity of this ion for nitrogen the mechanism is D and the rate of exchange is very fast, even faster than on the divalent ions. There is no significant effect of the divalent ion in cluster 2, 3, and 5 on the exchange rates of 4-Phpy at the iron center, which seems to indicate that the specific electronic interactions between the three ions making

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

KAUST Repository

Minenkov, Yury

2017-03-07

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.

Theoretical and experimental study of high-magnetic-field XMCD spectra at the L2,3 absorption edges of mixed-valence rare-earth compounds

International Nuclear Information System (INIS)

Kotani, Akio; Matsuda, Yasuhiro H; Nojiri, Hiroyuki

2009-01-01

X-ray magnetic circular dichroism(XMCD) spectra at the L 2,3 edges of mixed-valence rare-earth compounds in high magnetic fields are studied both theoretically and experimentally. The theoretical study is based on a new framework proposed recently by Kotani. The Zeeman splitting of 4f states, the mixed-valence character of 4f states, and the 4f-5d exchange interaction are incorporated into a single impurity Anderson model. New XMCD experiments in high magnetic fields up to 40 T are carried out for the mixed-valence compounds EuNi 2 (Si 0.18 Ge 0.82 ) 2 and YbInCu 4 by using a miniature pulsed magnet, which was developed recently by Matsuda et al. The XMCD data are taken at 5 K by transmission measurements for incident X-rays with ± helicities at BL39XU in SPring-8. After giving a survey on recent developments in the theory of XMCD spectra for mixed-valence Ce and Yb compounds, we calculate the XMCD spectra of YbInCu 4 at the field-induced valence transition around 32 T by applying the recent theoretical framework and by newly introducing at 32 T a discontinuous change in the Yb 4f level and that in the hybridization strength between the Yb 4f and conduction electrons. The calculated results are compared with the experimental ones.

A valence-universal coupled-cluster single- and double-excitations method for atoms: Pt. 3

International Nuclear Information System (INIS)

Jankowski, K.; Malinowski, P.

1994-01-01

To better understand the problems met when solving the equations of VU-CC approaches in the presence of intruder states, we are concerned with the following aspects of the solvability problem for sets of non-linear equations: the existence and properties of multiple solutions and the attainability of these solutions by means of various numerical methods. Our study is concentrated on the equations obtained for Be within the framework of the recently formulated atomically oriented form of the valence-universal coupled-cluster theory accounting for one- and two-electron excitations (VU-CCSD/R) and based on the complete model space (2s 2 , 2p 2 ). Six pairs of multiple solutions representing four 1 S states are found and discussed. Three of these solutions provide amplitudes describing the 2p 2 1 S state for which the intruder state problem has been considered as extremely serious. Several known numerical methods have been applied to solve the same set of non-linear equations for the two-valence cluster amplitudes. It is shown that these methods perform quite differently in the presence of intruder states, which seems to indicate that the intruder state problem for VU-CC methods is partly caused by the commonly used methods of solving the non-linear equations. (author)

Happiness is pleasant, or is it? Implicit representations of affect valence are associated with contrahedonic motivation and mixed affect in daily life.

Science.gov (United States)

Riediger, Michaela; Wrzus, Cornelia; Wagner, Gert G

2014-10-01

People typically want to feel good. At times, however, they seek to maintain or enhance negative affect or to dampen positive affect. The prevalence of such contrahedonic motivation has been related to simultaneous experiences of positive and negative (i.e., mixed) affect. We investigated the role that implicit mental representations of affect valence may play in this regard in a study with N = 400 participants aged 11-88 years. Results demonstrated the age-fairness and reliability of the affect-valence Implicit Association Test, a newly developed implicit measure of interindividual differences in mental representations of affect valence. The older participants were, the more distinctively they implicitly associated happiness with pleasantness and/or unhappiness with unpleasantness. Participants furthermore carried mobile phones as assessment instruments with them for 3 weeks while pursuing their daily routines. The phones prompted participants on average 54 times to report their momentary affective experience and affect-regulation motivation. Contrahedonic motivation and mixed affect were most prevalent among adolescents and least prevalent among older adults, and thus showed a similar pattern of age differences as the affect-valence Implicit Association Test. Furthermore, the more distinctive participants' implicit associations of happiness with pleasantness, and/or unhappiness with unpleasantness, the less likely participants were to report contrahedonic motivation and mixed affect in their daily lives. These findings contribute to a refined understanding of the mixed-affect perspective on contrahedonic motivation by demonstrating the respective role of implicit affect-valence representations. PsycINFO Database Record (c) 2014 APA, all rights reserved.

Optical gain and gain suppression of quantum-well lasers with valence band mixing

International Nuclear Information System (INIS)

Ahn, D.; Chuang, S.L.

1990-01-01

The effects of valence band mixing on the nonlinear gains of quantum-well lasers are studied theoretically. The authors' analysis is based on the multiband effective-mass theory and the density matrix formalism with intraband relaxation taken into account. The gain and the gain-suppression coefficient of a quantum-well laser are calculated from the complex optical susceptibility obtained by the density matrix formulation with the theoretical dipole moments obtained from the multiband effective-mass theory. The calculated gain spectrum shows that there are remarkable differences (both in peak amplitude and spectral shape) between our model with valence band mixing and the conventional parabolic band model. The shape of the gain spectrum calculated by the authors' model becomes more symmetric due to intraband relaxation together with nonparabolic energy dispersions and is closer to the experimental observations when compared with the conventional method using the parabolic band model and the multiband effective-mass calculation without intraband relaxation. Both give quite asymmetric gain spectra. Optical intensity in the GaAs active region is estimated by solving rate equations for the stationary states with nonlinear gain suppression. The authors calculate the mode gain for the resonant mode including the gain suppression, which results in spectral hole burning of the gain spectrum

Non-Fermi Liquid Behavior in the Single-Impurity Mixed Valence Problem

Science.gov (United States)

Zhang, Guang-Ming; Su, Zhao-Bin; Yu, Lu

An effective Hamiltonian of the Anderson single-impurity model with finite-range Coulomb interactions is derived near a particular limit, which is analogous to the Toulouse limit of the ordinary Kondo problem, and the physical properties around the mixed valence quantum critical point are calculated. At this quantum critical point, the local moment is only partially quenched and X-ray edge singularities are exhibited. Around this point, a new type of non-Fermi liquid behavior is predicted with an extra specific heat Cimp ~ T1/4 + AT ln T and spin-susceptibility χimp ~T-3/4 + B ln T.

Persistent low-temperature spin dynamics in the mixed-valence iridate Ba3InIr2O9

Science.gov (United States)

Dey, Tusharkanti; Majumder, M.; Orain, J. C.; Senyshyn, A.; Prinz-Zwick, M.; Bachus, S.; Tokiwa, Y.; Bert, F.; Khuntia, P.; Büttgen, N.; Tsirlin, A. A.; Gegenwart, P.

2017-11-01

Using thermodynamic measurements, neutron diffraction, nuclear magnetic resonance, and muon spin relaxation, we establish putative quantum spin-liquid behavior in Ba3InIr2O9 , where unpaired electrons are localized on mixed-valence Ir2O9 dimers with Ir4.5 + ions. Despite the antiferromagnetic Curie-Weiss temperature on the order of 10 K, neither long-range magnetic order nor spin freezing are observed down to at least 20 mK, such that spins are short-range correlated and dynamic over nearly three decades in temperature. Quadratic power-law behavior of both the spin-lattice relaxation rate and specific heat indicates the gapless nature of the ground state. We envisage that this exotic behavior may be related to an unprecedented combination of the triangular and buckled honeycomb geometries of nearest-neighbor exchange couplings in the mixed-valence setting.

Magnetic properties of mixed valence La2/3Sr1/3Mn1−xTxO3 (T ...

Indian Academy of Sciences (India)

(T = Fe,Cr) manganites obtained by Pechini method. I BETANCOURT. ∗ ... structure. Keywords. Mixed valence manganites; magnetic manganites; magnetocaloric effect; Pechini method. 1. ..... IB thanks for financial support from research grant.

On the electrical conductivity for the mixed-valence model with d-f correlations

International Nuclear Information System (INIS)

Borgiel, W.; Matlak, M.

1984-08-01

The static electrical conductivity of mixed-valence systems is calculated in the model of Matlak and Nolting [Solid State Commun., 47, 11 (1983); Z. Phys., B55, 103 (1984)]. The method takes into account the atomic properties more exactly than those connected with bands, and hence emphasizes the ionic aspect of the problem in some way; indeed, the calculations overestimate the atomic properties. Some results are presented in a graph. It is found that the electrical conductivity depends strongly on temperature and the electron-hole attraction constant

Isotopic exchange in mixed valence compounds in the solid state

International Nuclear Information System (INIS)

Fernandez Valverde, S.M.

1986-01-01

This work aims at the determination of isotopic exchange kinetics and mechanism in two mixed valence compounds: Cs 10 (Sbsup(V)Cl 6 ) (Sbsup(III)Cl 6 ) 3 and Tl 3 sup(I)(Tlsup(III)Cl 6 ). The synthesis of the first compound is very difficult because in most of the cases mixtures of chloroantimoniates are obtained. Exchange in Tl 4 Cl 6 labelled on Tlsup(III) is studied in detail by radiochemical analysis and physical techniques: ionic conductivity and positon annihilation. Cation vacancies are easily created in the lattice with formation enthalpy of 0.35 eV and migration enthalpy of 0.52 eV. Isochronic and isothermal exchange curves are described by a kinetic based on species diffusion. Models are given. Exchange is increased by grinding probably because extrinseque defects are introduced [fr

An Affinity Propagation Clustering Algorithm for Mixed Numeric and Categorical Datasets

Directory of Open Access Journals (Sweden)

Kang Zhang

2014-01-01

Full Text Available Clustering has been widely used in different fields of science, technology, social science, and so forth. In real world, numeric as well as categorical features are usually used to describe the data objects. Accordingly, many clustering methods can process datasets that are either numeric or categorical. Recently, algorithms that can handle the mixed data clustering problems have been developed. Affinity propagation (AP algorithm is an exemplar-based clustering method which has demonstrated good performance on a wide variety of datasets. However, it has limitations on processing mixed datasets. In this paper, we propose a novel similarity measure for mixed type datasets and an adaptive AP clustering algorithm is proposed to cluster the mixed datasets. Several real world datasets are studied to evaluate the performance of the proposed algorithm. Comparisons with other clustering algorithms demonstrate that the proposed method works well not only on mixed datasets but also on pure numeric and categorical datasets.

Optical and electronic properties of polyvinyl alcohol doped with pairs of mixed valence metal ions

International Nuclear Information System (INIS)

Bulinski, Mircea; Kuncser, Victor; Plapcianu, Carmen; Krautwald, Stefan; Franke, Hilmar; Rotaru, P; Filoti, George

2004-01-01

The electronic mechanisms induced by the UV exposure of thin films of polyvinyl alcohol doped with pairs of mixed valence metal ions were studied in relation to their optical behaviour by Moessbauer spectroscopy and optical absorption. The results obtained definitely point to the role of each element from the pair in the electronic mechanism involved, with influence on the optical properties regarding applications in real-time holography and integrated optics

Microscopic solvation of a lithium atom in water-ammonia mixed clusters: solvent coordination and electron localization in presence of a counterion.

Science.gov (United States)

Pratihar, Subha; Chandra, Amalendu

2008-07-14

The microsolvation structures and energetics of water-ammonia mixed clusters containing a lithium atom, i.e., Li(H(2)O)(n)(NH(3)), n = 1-5, are investigated by means of ab initio theoretical calculations. Several structural aspects such as the solvent coordination to the metal ion and binding motifs of the free valence electron of the metal are investigated. We also study the energetics aspects such as the dependence of vertical ionization energies on the cluster size, and all these structural and energetics aspects are compared to the corresponding results of previously studied anionic water-ammonia clusters without a metal ion. It is found that the Li-O and Li-N interactions play a very important role in stabilizing the lithium-water-ammonia clusters, and the presence of these metal ion-solvent interactions also affect the characteristics of electron solvation in these clusters. This is seen from the spatial distribution of the singly occupied molecular orbital (SOMO) which holds the ejected valence electron of the Li atom. For very small clusters, SOMO electron density is found to exist mainly at the vicinity of the Li atom, whereas for larger clusters, it is distributed outside the first solvation shell. The free dangling hydrogens of water and ammonia molecules are involved in capturing the SOMO electron density. In some of the conformers, OH{e}HO and OH{e}HN types of interactions are found to be present. The presence of the metal ion at the center of the cluster ensures that the ejected electron is solvated at a surface state only, whereas both surface and interiorlike states were found for the free electron in the corresponding anionic clusters without a metal ion. The vertical ionization energies of the present clusters are found to be higher than the vertical detachment energies of the corresponding anionic clusters which signify a relatively stronger binding of the free electron in the presence of the positive metal counterion. The shifts in different

Treating sub-valence correlation effects in domain based pair natural orbital coupled cluster calculations: an out-of-the-box approach

KAUST Repository

Bistoni, Giovanni

2017-06-12

The validity of the main approximations used in canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) in standard chemical applications is discussed. In particular, we investigate the dependence of the results on the number of electrons included in the correlation treatment in frozen-core (FC) calculations and on the main threshold governing the accuracy of DLPNO all-electron (AE) calculations. Initially, scalar relativistic orbital energies for the ground state of the atoms from Li to Rn in the periodic table are calculated. An energy criterion is applied for determining the orbitals that can be excluded from the correlation treatment in FC coupled cluster calculations without significant loss of accuracy. The heterolytic dissociation energy (HDE) of a series of metal compounds (LiF, NaF, AlF3, CaF2, CuF, GaF3, YF3, AgF, InF3, HfF4 and AuF) is calculated at the canonical CCSD(T) level, and the dependence of the results on the number of correlated electrons is investigated. Although for many of the studied reactions sub-valence correlation effects contribute significantly to the HDE, the use of an energy criterion permits a conservative definition of the size of the core, allowing FC calculations to be performed in a black-box fashion while retaining chemical accuracy. A comparison of the CCSD and the DLPNO-CCSD methods in describing the core-core, core-valence and valence-valence components of the correlation energy is given. It is found that more conservative thresholds must be used for electron pairs containing at least one core electron in order to achieve high accuracy in AE DLPNO-CCSD calculations relative to FC calculations. With the new settings, the DLPNO-CCSD method reproduces canonical CCSD results in both AE and FC calculations with the same accuracy.

Treating sub-valence correlation effects in domain based pair natural orbital coupled cluster calculations: an out-of-the-box approach

KAUST Repository

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

2017-01-01

The validity of the main approximations used in canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) in standard chemical applications is discussed. In particular, we investigate the dependence of the results on the number of electrons included in the correlation treatment in frozen-core (FC) calculations and on the main threshold governing the accuracy of DLPNO all-electron (AE) calculations. Initially, scalar relativistic orbital energies for the ground state of the atoms from Li to Rn in the periodic table are calculated. An energy criterion is applied for determining the orbitals that can be excluded from the correlation treatment in FC coupled cluster calculations without significant loss of accuracy. The heterolytic dissociation energy (HDE) of a series of metal compounds (LiF, NaF, AlF3, CaF2, CuF, GaF3, YF3, AgF, InF3, HfF4 and AuF) is calculated at the canonical CCSD(T) level, and the dependence of the results on the number of correlated electrons is investigated. Although for many of the studied reactions sub-valence correlation effects contribute significantly to the HDE, the use of an energy criterion permits a conservative definition of the size of the core, allowing FC calculations to be performed in a black-box fashion while retaining chemical accuracy. A comparison of the CCSD and the DLPNO-CCSD methods in describing the core-core, core-valence and valence-valence components of the correlation energy is given. It is found that more conservative thresholds must be used for electron pairs containing at least one core electron in order to achieve high accuracy in AE DLPNO-CCSD calculations relative to FC calculations. With the new settings, the DLPNO-CCSD method reproduces canonical CCSD results in both AE and FC calculations with the same accuracy.

Mixed valence and metamagnetism in a metal flux grown compound Eu2Pt3Si5

International Nuclear Information System (INIS)

Sarkar, Sumanta; Subbarao, Udumula; Joseph, Boby; Peter, Sebastian C.

2015-01-01

A new compound Eu 2 Pt 3 Si 5 with plate shaped morphology has been grown from excess In flux. The compound crystallizes in the orthorhombic U 2 Co 3 Si 5 structure type, Ibam space group and the lattice parameters are a=10.007(2) Å, b=11.666(2) Å and c=6.0011(12) Å. The crystal structure of this compound can be conceived as inter-twinned chains of [Pt 2 Si 2 ] and [PtSi 3 ] tetrahedra connected along [100] direction to give rise to a complex three dimensional [Pt 3 Si 5 ] network. Temperature dependent magnetic susceptibility data suggests that Eu 2 Pt 3 Si 5 undergoes a strong antiferromagnetic ordering (T N =19 K) followed by a weak ferromagnetic transition (T C =5.5 K). The effective magnetic moment/Eu obtained from susceptibility data is 6.78 μ B accounts mixed valent Eu with almost 85% divalent Eu, which is supported by X-ray absorption near edge spectroscopy. The compound undergoes a metamagnetic transition under applied magnetic field through a probable spin flop mechanism. - Graphical abstract: Eu 2 Pt 3 Si 5 , a new member in the U 2 Co 3 Si 5 (Ibam) family undergoes metamagnetic transition at high magnetic field and Eu is in mixed valence state. - Highlights: • A new compound Eu 2 Pt 3 Si 5 has been synthesized using indium as an inactive metal flux. • The compound undergoes metamagnetic transition at higher field. • Eu in this compound resides in a mixed valence state

Structural and magnetic characterization of mixed valence Co(II, III)xZn1−xO epitaxial thin films

International Nuclear Information System (INIS)

Negi, D.S.; Loukya, B.; Dileep, K.; Sahu, R.; Shetty, S.; Kumar, N.; Ghatak, J.; Pachauri, N.; Gupta, A.; Datta, R.

2014-01-01

In this article, we report on the Co atom incorporation, secondary phase formation and composition-dependent magnetic and optical properties of mixed valence Co(II, III) x Zn 1−x O epitaxial thin films grown by pulsed laser deposition. The intended total Co concentration is varied between ∼6–60 at.% with relatively higher concentration of +3 over +2 charge state. Mixed valence Co(II, III) shows high solubility in ZnO (up to 38 at.%) and ferromagnetism is observed in samples with total Co incorporation of ∼29 and 38 at.%. Electron diffraction pattern and high resolution transmission electron microscopy images reveal single crystalline nature of the thin films with wurtzite structure. Co oxide interlayer, with both rock salt and spinel structure, are observed to be formed between the substrate and wurtzite film for total Co concentration at ∼17 at.% and above. Magnetization shows composition dependence with a saturation moment value of ∼93 emu cm −3 and a coercive field of ∼285 Oe observed for ∼38 at.% Co:ZnO films. Ferromagnetism was not observed for films with Co concentration 17 and 9 at.%. The Co oxide interlayer does not show any ferromagnetism. All the films are n-type with carrier concentration ∼10 19 cm −3 . The observed magnetism is probably resulting from direct antiferromagntic exchange interaction between Co 2+ and Co 3+ ions favored by heavy Co alloying giving rise to ferrimagnetism in the system. - Highlights: • Mixed valence Co doped ZnO ferromagnetic single crystal thin film. • Secondary phase formation in terms of CoO and Co3O4 and magnetism is observed only for high Co alloying. • Cathodoluminescence (CL) data showing increase in band gap with Co concentrations

5th International Conference on Valence Fluctuations

CERN Document Server

Malik, S

1987-01-01

During the Koln meeting (August 28-31, 1984), Irdia was chosen as the venue for the next International Conference on Valence Fluctuations. lhis was in recognition ard appreciation of the work done, both experimental ard theoretical, by the Irdian scientists in this area during the last decade. We decided to hold this Conference in the month of January, 1987 at Bangalore. lhe subject of Valence Fluctuations has kept itself alive ard active as it has provided many shocks ard suprises particularly among the Ce- ard U-based intermetallies. lhe richness of many interesting physical phenomena occurring in mixed valent materials, the flexibility of modifying their physical properties (by alloying, for example) ard the possibility of synthesizing a wide variety of new such materials seem to be the key factors in this regard. Barely six months before this Conference, an International Conference on Anomalous Rare Earths and Actinides (ICAREA) had been held at Grenoble (July, 1986) which also focussed on mixed valence a...

Ferromagnetic dinuclear mixed-valence Mn(II)/Mn(III) complexes: building blocks for the higher nuclearity complexes. structure, magnetic properties, and density functional theory calculations.

Science.gov (United States)

Hänninen, Mikko M; Välivaara, Juha; Mota, Antonio J; Colacio, Enrique; Lloret, Francesc; Sillanpää, Reijo

2013-02-18

A series of six mixed-valence Mn(II)/Mn(III) dinuclear complexes were synthesized and characterized by X-ray diffraction. The reactivity of the complexes was surveyed, and structures of three additional trinuclear mixed-valence Mn(III)/Mn(II)/Mn(III) species were resolved. The magnetic properties of the complexes were studied in detail both experimentally and theoretically. All dinuclear complexes show ferromagnetic intramolecular interactions, which were justified on the basis of the electronic structures of the Mn(II) and Mn(III) ions. The large Mn(II)-O-Mn(III) bond angle and small distortion of the Mn(II) cation from the ideal square pyramidal geometry were shown to enhance the ferromagnetic interactions since these geometrical conditions seem to favor the orthogonal arrangement of the magnetic orbitals.

Formation of nuclear molecules in cluster radioactivity. On interpretation of the cluster radioactivity mechanism

International Nuclear Information System (INIS)

Volkov, V.V.; Cherepanov, E.A.

2012-01-01

The basis for cluster radioactivity is the property of nuclei of light isotopes of elements heavier than lead to spontaneously form clusters - nuclei of light elements - from valence nucleons, which gives rise to asymmetric nuclear molecules. The cluster formation proceeds through successive excitation-free transfer of valence nucleons to the particle and to subsequent light nuclei. Nuclear molecule formation is accompanied by a considerable amount of released energy, which allows quantum-mechanical penetration of the cluster through the exit Coulomb barrier

Valence effects on adsorption: a preliminary assessment of the effects on valence state control on sorption measurements

International Nuclear Information System (INIS)

Meyer, R.E.; Arnold, W.D.; Case, F.; Shiao, S.Y.; Palmer, D.A.

1983-01-01

Electrochemical arguments are advanced to illustrate that what is usually measured in practice is a mixed potential determined by the kinetics of the electrode processes occurring at the indicator electrode. Valence states can be altered electrochemically or by use of added chemical reagents, including redox couples which can hold the potential to relatively specific potentials. The disadvantage of added chemical reagents is that they may alter the characteristics of the sorption reactions by interaction with the sorbent. Electrochemical methods are versatile and do not add reagents, but in some caes the nuclide can adsorb on the electrode itself. A description is given of the application of the electrochemical method of valence control to determination of sorption of Np(V) on alumina. Valence state control and analysis can be used to study possible redox reactions on materials which might be used as backfill materials. A description is given of survey experiments with a number of sulfides and iron-containing materials. Valence state analysis is used on the initial solutions and leachate from acid leaches of the sorbent after the sorption experiment to help determine whether valence state change is occurring. The preliminary results indicate that on the sulfides tested, sorption occurs both with and without valence state change

Valence instabilities as a source of actinide system inconsistencies

International Nuclear Information System (INIS)

Sandenaw, T.A.

1979-01-01

Light actinide elements alone, and in some of their alloys, may exist as a static or dynamic mixture of two configurations. Such a state can explain both a resistivity maximum and lack of magnetic order observed in so many actinide materials, and still be compatible with the existence of f-electrons in narrow bands. Impurity elements may stabilize slightly different intermediate valence states in U, Np, and Pu, thus contributing to inconsistencies in published results. The physical property behavior of mixed-valence, rare-earth compounds is very much like that observed in development of antiphase (martensitic) structures. Martensitic transformations in U, Np, and Pu, from high-temperature b. c. c. to alpha phase, may be a way of ordering an alloy-like metal of mixed or intermediate valence. The relative stability of each phase structure may depend upon its electron-valence ratio. A Hubbard model for electron correlations in a narrow energy band has been invoked in most recent theories for explaining light actinide behavior. Such a model may also be applicable to crystal symmetry changes in martensitic transformations in actinides

Clustering Mixed Data by Fast Search and Find of Density Peaks

Directory of Open Access Journals (Sweden)

Shihua Liu

2017-01-01

Full Text Available Aiming at the mixed data composed of numerical and categorical attributes, a new unified dissimilarity metric is proposed, and based on that a new clustering algorithm is also proposed. The experiment result shows that this new method of clustering mixed data by fast search and find of density peaks is feasible and effective on the UCI datasets.

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

Science.gov (United States)

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

Mössbauer spectroscopic and powder X-ray diffraction studies on incorporation of gaseous organic molecules into intermolecular nano-voids of mixed-valence trinuclear iron pentafluorobenzoate complex

International Nuclear Information System (INIS)

Sakai, Yoichi; Onaka, Satoru; Ogiso, Ryo; Takayama, Tsutomu; Takahashi, Masashi; Nakamoto, Tadahiro

2013-01-01

Incorporation of gaseous organic molecules into polycrystalline mixed-valence trinuclear iron (Fe 3+ ,Fe 3+ ,Fe 2+ ) pentafluorobenzoate complex Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 with intermolecular nano-voids was studied by 57 Fe-Mössbauer spectroscopic and powder XRD measurements. Organic-molecule incorporation was mainly chased by using iron-valence fluctuation observed in a Mössbauer spectrum, and also researched supportively by a powder XRD technique. (author)

Femtosecond dynamics of electron transfer in a neutral organic mixed-valence compound

International Nuclear Information System (INIS)

Maksimenka, Raman; Margraf, Markus; Koehler, Juliane; Heckmann, Alexander; Lambert, Christoph; Fischer, Ingo

2008-01-01

In this article we report a femtosecond time-resolved transient absorption study of a neutral organic mixed-valence (MV) compound with the aim to gain insight into its charge-transfer dynamics upon optical excitation. The back-electron transfer was investigated in five different solvents, toluene, dibutyl ether, methyl-tert-butyl ether (MTBE), benzonitrile and n-hexane. In the pump step, the molecule was excited at 760 nm and 850 nm into the intervalence charge-transfer band. The resulting transients can be described by two time constant. We assign one time constant to the rearrangement of solvent molecules in the charge-transfer state and the second time constant to back-electron transfer to the electronic ground state. Back-electron transfer rates range from 1.5 x 10 12 s -1 in benzonitrile through 8.3 x 10 11 s -1 in MTBE, around 1.6 x 10 11 s -1 in dibutylether and toluene and to 3.8 x 10 9 s -1 in n-hexane

Titanium oxide modification with oxides of mixed cobalt valence for photo catalysis

International Nuclear Information System (INIS)

Alanis O, R.; Jimenez B, J.

2010-01-01

In the present work, heterogenous photo catalysis, a technique often used for organic compound degradation toxic in water, was used. The photo catalyst most often used in this technique is TiO 2 , which due to its physical and chemical properties, can degrade a great number of organic compounds. In addition, in recent years it has been verified that the doping of semiconductors with metals or metallic oxides increases the photo catalytic activity of these semiconductors, which is why it was proposed for doping by the impregnating method using commercial TiO 2 synthesized by the Degussa company (TiO 2 Degussa P25) with and oxide of mixed cobalt valence (Co 3 O 4 ) synthesized using the sol-gel method. The synthesized photo catalyst TiO 2 /Co 3 O 4 was characterized by the techniques of X-ray diffraction, scanning electronic microscopy, Raman spectroscopy and finally, photo catalytic tests by means of the degradation of methylene blue. (Author)

The application of mixed recommendation algorithm with user clustering in the microblog advertisements promotion

Science.gov (United States)

Gong, Lina; Xu, Tao; Zhang, Wei; Li, Xuhong; Wang, Xia; Pan, Wenwen

2017-03-01

The traditional microblog recommendation algorithm has the problems of low efficiency and modest effect in the era of big data. In the aim of solving these issues, this paper proposed a mixed recommendation algorithm with user clustering. This paper first introduced the situation of microblog marketing industry. Then, this paper elaborates the user interest modeling process and detailed advertisement recommendation methods. Finally, this paper compared the mixed recommendation algorithm with the traditional classification algorithm and mixed recommendation algorithm without user clustering. The results show that the mixed recommendation algorithm with user clustering has good accuracy and recall rate in the microblog advertisements promotion.

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

Science.gov (United States)

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- .

Extension of K-Means Algorithm for clustering mixed data | Onuodu ...

African Journals Online (AJOL)

Also proposed is a new dissimilarity measure that uses relative cumulative frequency-based method in clustering objects with mixed values. The dissimilarity model developed could serve as a predictive tool for identifying attributes of objects in mixed datasets. It has been implemented using JAVA programming language ...

Nature of the magnetic ground state in the mixed valence compound CeRuSn: a single-crystal study

International Nuclear Information System (INIS)

Fikáček, J; Prokleška, J; Prchal, J; Custers, J; Sechovský, V

2013-01-01

We report on detailed low-temperature measurements of the magnetization, the specific heat and the electrical resistivity on high-quality CeRuSn single crystals. The compound orders antiferromagnetically at T N = 2.8 K with the Ce 3+ ions locked within the a–c plane of the monoclinic structure. Magnetization shows that below T N CeRuSn undergoes a metamagnetic transition when applying a magnetic field of 1.5 and 0.8 T along the a- and c-axis, respectively. This transition manifests in a tremendous negative jump of ∼25% in the magnetoresistance. The value of the saturated magnetization along the easy magnetization direction (c-axis) and the magnetic entropy above T N derived from specific heat data correspond to the scenario of only one third of the Ce ions in the compound being trivalent and carrying a stable Ce 3+ magnetic moment, whereas the other two thirds of the Ce ions are in a nonmagnetic tetravalent and/or mixed valence state. This is consistent with the low-temperature CeRuSn crystal structure i.e., a superstructure consisting of three unit cells of the CeCoAl type piled up along the c-axis, and in which the Ce 3+ ions are characterized by large distances from the Ru ligands while the Ce–Ru distances of the other Ce ions are much shorter causing a strong 4f-ligand hybridization and hence leading to tetravalent and/or mixed valence Ce ions. (paper)

Micro-Valences: Affective valence in neutral everyday objects

Directory of Open Access Journals (Sweden)

Sophie eLebrecht

2012-04-01

Full Text Available Affective valence influences both our cognition and our perception of the world. Indeed, the speed and quality with which we recognize objects in a visual scene can vary dramatically depending on its affective content. However, affective processing of visual objects has been typically studied using only stimuli with strong affective valences (e.g., guns or roses. Here we explore whether affective valence must be strong or obvious to exert an effect on our perception. We conclude that the majority of objects carry some affective valence (micro-valences and, thus, nominally neutral objects are not really neutral. Functionally, the perception of valence in everyday objects facilitates perceptually-driven choice behavior, decision-making, and affective responses.

Valence mixing in YbCuAl: a case study

International Nuclear Information System (INIS)

Mattens, W.

1980-01-01

Results are presented of a study of the valence state of Yb in the intermetallic compound YbCuAl. Both macroscopic physical properties (magnetic susceptibility, heat capacity, thermal expansion, electric resistivity) and microscopic physical properties (neutron inelastic scattering, nuclear magnetic resonance) are determined. The results are compared with a local Fermi liquid theory. (G.T.H.)

Titanium oxide modification with oxides of mixed cobalt valence for photo catalysis

Energy Technology Data Exchange (ETDEWEB)

Alanis O, R.; Jimenez B, J., E-mail: jaime.jimenez@inin.gob.m [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

2010-07-01

In the present work, heterogenous photo catalysis, a technique often used for organic compound degradation toxic in water, was used. The photo catalyst most often used in this technique is TiO{sub 2}, which due to its physical and chemical properties, can degrade a great number of organic compounds. In addition, in recent years it has been verified that the doping of semiconductors with metals or metallic oxides increases the photo catalytic activity of these semiconductors, which is why it was proposed for doping by the impregnating method using commercial TiO{sub 2} synthesized by the Degussa company (TiO{sub 2} Degussa P25) with and oxide of mixed cobalt valence (Co{sub 3}O{sub 4}) synthesized using the sol-gel method. The synthesized photo catalyst TiO{sub 2}/Co{sub 3}O{sub 4} was characterized by the techniques of X-ray diffraction, scanning electronic microscopy, Raman spectroscopy and finally, photo catalytic tests by means of the degradation of methylene blue. (Author)

A THIOLATO-BRIDGED OCTANUCLEAR COPPER(I,II MIXED- VALENCE COMPLEX WITH N,N,S-TRIDENTATE LIGAND

Directory of Open Access Journals (Sweden)

Takanori Kotera

2007-06-01

Full Text Available Thiolato-bridged complex [CuI4CuII4(peampt4Cl8]·2H2O (Hpeampt = 1-(2-pyridylethylamino methylpropane-2-thiol has been synthesized and characterized by the elemental analysis, IR and UV-vis spectroscopies and magnetic susceptibility measurement. The X-ray crystal structure analysis of this complex shows a localized mixed-valence octanuclear cage structure made up of four trigonal-bipyramidal CuIIN2SCl2, two trigonal CuIS2Cl, and two tetrahedral CuIS2Cl2 coordination sites. Temperature dependence of magnetic susceptibility (4.5— 300 K shows that a fairly strong antiferromagnetic interaction is operating between the four CuII ions.

Synthesis of an S T = 7 [Mn 3 ] Mixed-Valence Complex Based on 1,3-Propanediol Ligand Derivatives and Its One-Dimensional Assemblies

KAUST Repository

Huang, Jian; Wu, Gang; Bai, Jiaquan; Jiang, Yuan; Li, Guanghua; Qiu, Shilun; Clé rac, Rodolphe

2013-01-01

. In this work, a new ST = 7 trinuclear mixed-valence Mn complex, [MnIIIMnII 2(LA) 2(Br)4(CH3OH)6] ·Br· (CH3OH)1.5·(H2O)0.5 (1), is reported using a pyridinium-functionalized 1,3-propanediol ligand (H 2LABr = 1-(3-bromo-2,2-bis

Field-induced valence transition in rare-earth system

International Nuclear Information System (INIS)

Chattopadhaya, A.; Ghatak, S.K.

2000-01-01

The magnetic field-induced valence transition in rare-earth compound has been examined based on a pseudospin S=1 Ising model proposed earlier for valence transition. The model includes finite mixing between two pertinent ionic configurations (magnetic and non-magnetic) separated by an energy gap and with intersite interaction between rare-earth ions. Using the mean field approximation the magnetic behaviour and the critical field (H c ) for transition are obtained as a function of energy gap and temperature. The phase boundary defined in terms of reduced field H c /H co and reduced temperature T/T v (T v being valence transition temperature in absence of field) is nearly independent of energy gap. These results are in qualitative agreement with experimental observation in Yb- and Eu-compounds

The acoustic correlates of valence depend on emotion family.

Science.gov (United States)

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.

Core-electron binding energies from self-consistent field molecular orbital theory using a mixture of all-electron real atoms and valence-electron model atoms

International Nuclear Information System (INIS)

Quinn, C.M.; Schwartz, M.E.

1981-01-01

The chemistry of large systems such as clusters may be readily investigated by valence-electron theories based on model potentials, but such an approach does not allow for the examination of core-electron binding energies which are commonly measured experimentally for such systems. Here we merge our previously developed Gaussian based valence-electron model potential theory with all-electron ab initio theory to allow for the calculation of core orbital binding energies when desired. For the atoms whose cores are to be examined, we use the real nuclear changes, all of the electrons, and the appropriate many-electron basis sets. For the rest of the system we use reduced nuclear charges, the Gaussian based model potentials, only the valence electrons, and appropriate valence-electron basis sets. Detailed results for neutral Al 2 are presented for the cases of all-electron, mixed real--model, and model--model SCF--MO calculations. Several different all-electron and valence electron calculations have been done to test the use of the model potential per se, as well as the effect of basis set choice. The results are in all cases in excellent agreement with one another. Based on these studies, a set of ''double-zeta'' valence and all-electron basis functions have been used for further SCF--MO studies on Al 3 , Al 4 , AlNO, and OAl 3 . For a variety of difference combinations of real and model atoms we find excellent agreement for relative total energies, orbital energies (both core and valence), and Mulliken atomic populations. Finally, direct core-hole-state ionic calculations are reported in detail for Al 2 and AlNO, and noted for Al 3 and Al 4 . Results for corresponding frozen-orbital energy differences, relaxed SCF--MO energy differences, and relaxation energies are in all cases in excellent agreement (never differing by more than 0.07 eV, usually by somewhat less). The study clearly demonstrates the accuracy of the mixed real--model theory

Resonant electron attachment to mixed hydrogen/oxygen and deuterium/oxygen clusters

Science.gov (United States)

Renzler, Michael; Kranabetter, Lorenz; Barwa, Erik; Grubwieser, Lukas; Scheier, Paul; Ellis, Andrew M.

2017-11-01

Low energy electron attachment to mixed (H2)x/(O2)y clusters and their deuterated analogs has been investigated for the first time. These experiments were carried out using liquid helium nanodroplets to form the clusters, and the effect of the added electron was then monitored via mass spectrometry. There are some important differences between electron attachment to the pure clusters and to the mixed clusters. A particularly notable feature is the formation of HO2- and H2O- ions from an electron-induced chemical reaction between the two dopants. The chemistry leading to these anions appears to be driven by electron resonances associated with H2 rather than O2. The electron resonances for H2 can lead to dissociative electron attachment (DEA), just as for the free H2 molecule. However, there is evidence that the resonance in H2 can also lead to rapid electron transfer to O2, which then induces DEA of the O2. This kind of excitation transfer has not, as far as we are aware, been reported previously.

Transient dynamics of a quantum-dot: From Kondo regime to mixed valence and to empty orbital regimes

Science.gov (United States)

Cheng, YongXi; Li, ZhenHua; Wei, JianHua; Nie, YiHang; Yan, YiJing

2018-04-01

Based on the hierarchical equations of motion approach, we study the time-dependent transport properties of a strongly correlated quantum dot system in the Kondo regime (KR), mixed valence regime (MVR), and empty orbital regime (EOR). We find that the transient current in KR shows the strongest nonlinear response and the most distinct oscillation behaviors. Both behaviors become weaker in MVR and diminish in EOR. To understand the physical insight, we examine also the corresponding dot occupancies and the spectral functions, with their dependence on the Coulomb interaction, temperature, and applied step bias voltage. The above nonlinear and oscillation behaviors could be understood as the interplay between dynamical Kondo resonance and single electron resonant-tunneling.

Brillouin-Wigner theory of mixed-valence impurities in BCS superconductor: Tc/TcO and ΔC/ΔCO

International Nuclear Information System (INIS)

Li Jun; Gong Changde.

1986-08-01

The (lowest order) Brillouin-Wigner perturbational expansion theory is adopted to describe the mixed-valence impurities in the BCS superconductor. Two substantial quantities characterizing the superconducting state, i.e. the reduced transition temperature T c /T cO and the reduced specific heat jump ΔC/ΔC O are calculated numerically as a function of the impurity concentration x and the energy level difference E f between two 4f configurations. A comparison with the experimental data of the Th 1-x Ce x and Th 1-x U x alloy is also included with a more reasonable fitting than Kaiser's theory. (author)

Continuum limit of overlap valence quarks on a twisted mass sea

International Nuclear Information System (INIS)

Cichy, Krzysztof; Herdoiza, Gregorio; Univ. Autonoma de Madrid; Jansen, Karl

2010-12-01

We study a lattice QCD mixed action with overlap valence quarks on two flavours of Wilson maximally twisted mass sea quarks. Employing three different matching conditions to relate both actions to each other, we investigate the continuum limit by using three values of the lattice spacing ranging from a∼0.05 fm to 0.08 fm. A particular emphasis is put on the effect on physical observables of the topological zero modes appearing in the valence overlap operator. We estimate the region of parameter space where the contribution from these zero modes is sufficiently small such that their effects can be safely controlled and a restoration of unitarity of the mixed action in the continuum limit is reached. (orig.)

Micro-Valences: Affective valence in neutral everyday objects

OpenAIRE

Sophie eLebrecht; Moshe eBar; Lisa F Barrett; Michael J Tarr

2012-01-01

Affective valence influences both our cognition and our perception of the world. Indeed, the speed and quality with which we recognize objects in a visual scene can vary dramatically depending on its affective content. However, affective processing of visual objects has been typically studied using only stimuli with strong affective valences (e.g., guns or roses). Here we explore whether affective valence must be strong or obvious to exert an effect on our perception. We conclude that the maj...

Continuum limit of overlap valence quarks on a twisted mass sea

Energy Technology Data Exchange (ETDEWEB)

Cichy, Krzysztof [Adam Mickiewicz Univ., Poznan (Poland). Faculty of Physics; Herdoiza, Gregorio [DESY, Zeuthen (Germany). John von Neumann-Institut fuer Computing NIC; Univ. Autonoma de Madrid (Spain). Dept. de Fisica Teorica; Jansen, Karl [DESY, Zeuthen (Germany). John von Neumann-Institut fuer Computing NIC

2010-12-15

We study a lattice QCD mixed action with overlap valence quarks on two flavours of Wilson maximally twisted mass sea quarks. Employing three different matching conditions to relate both actions to each other, we investigate the continuum limit by using three values of the lattice spacing ranging from a{approx}0.05 fm to 0.08 fm. A particular emphasis is put on the effect on physical observables of the topological zero modes appearing in the valence overlap operator. We estimate the region of parameter space where the contribution from these zero modes is sufficiently small such that their effects can be safely controlled and a restoration of unitarity of the mixed action in the continuum limit is reached. (orig.)

Valence configurations in 214Rn

International Nuclear Information System (INIS)

Dracoulis, G.D.; Byrne, A.P.; Stuchbery, A.E.; Bark, R.A.; Poletti, A.R.

1987-01-01

Excited states of 214 Rn, up to spins of ≅ 24 ℎ have been studied using γ-ray and electron spectroscopy following the 208 Pb( 9 Be,3n) 214 Rn reaction. The level scheme (which differs substantially from earlier work) is compared with the results of a semi-empirical shell model calculation. The availability of high-spin orbitals for the four valence protons and two valence neutrons, and the effect of the attractive proton-neutron interaction, leads to the prediction of high-spin states at an unusually low excitation energy. Experimentally, the high level density leads to difficulties in the level scheme assignments at high spin. Nevertheless, configuration assignments, supported by transition strengths deduced from the measured lifetimes (in the nanosecond region) are suggested for the main yrast states. The decay properties also suggest that configuration mixing is important. The possibility of a gradual transition to octupole deformation, implied by the decay properties of the 11 - and 10 + yrast states is also discussed. (orig.)

Synthesis of a Neutral Mixed-Valence Diferrocenyl Carborane for Molecular Quantum-Dot Cellular Automata Applications.

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Valence universal multireference coupled cluster calculations of the properties of indium in its ground and excited states

International Nuclear Information System (INIS)

Das, Madhulita; Chaudhuri, Rajat K; Chattopadhyay, Sudip; Sinha Mahapatra, Uttam

2011-01-01

In view of its importance in high precision spectroscopy, the valence universal multireference coupled cluster (VU-MRCC) method with four-component relativistic spinors has been applied to compute ionization potential (IP) and excitation energies (EEs) of the indium atom (In I). The effect of electron correlations on the ground and excited state properties is investigated using different levels of CC approximations and basis sets. This study reveals that for a given basis, the linearized VU-MRCC method tends to underestimate the IP, EEs and other one-electron properties such as magnetic hyperfine constant (A) compared to the full blown VU-MRCC method. Our computed results have been compared with available theoretical and experimental data. The IP, EEs, A and oscillator strengths (f) determined at the VU-MRCC level are in excellent agreement with the experimental results. The properties reported here further demonstrate that a basis set with at least h-type of orbitals is ubiquitous to achieve converged results.

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

Science.gov (United States)

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.

Spin--orbit configuration-interaction study of valence and Rydberg states of LiBe

International Nuclear Information System (INIS)

Marino, M.M.; Ermler, W.C.; Kern, C.W.; Bondybey, V.E.

1992-01-01

Ab initio spin--orbit full configuration-interaction calculations in the context of relativistic effective core potentials are reported for the weakly bound metal dimer LiBe, a three-valence-electron system. The effects of basis set on the energies of valence and Rydberg states of the cluster are discussed, as are the effects of configuration space selection on the energy of the latter states. Results at the dissociative limit are compared to the experimental atomic spectra. Potential-energy curves and spectroscopic constants are presented for the ground state and fourteen excited states, which includes the Li and Be 2p valence states, the Li 3s, 3p, 3d, and 4s Rydberg states, as well as three low-lying states of the molecular cation

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.

Science.gov (United States)

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.

Mixing Matrix Estimation of Underdetermined Blind Source Separation Based on Data Field and Improved FCM Clustering

Directory of Open Access Journals (Sweden)

Qiang Guo

2018-01-01

Full Text Available In modern electronic warfare, multiple input multiple output (MIMO radar has become an important tool for electronic reconnaissance and intelligence transmission because of its anti-stealth, high resolution, low intercept and anti-destruction characteristics. As a common MIMO radar signal, discrete frequency coding waveform (DFCW has a serious overlap of both time and frequency, so it cannot be directly used in the current radar signal separation problems. The existing fuzzy clustering algorithms have problems in initial value selection, low convergence rate and local extreme values which will lead to the low accuracy of the mixing matrix estimation. Consequently, a novel mixing matrix estimation algorithm based on data field and improved fuzzy C-means (FCM clustering is proposed. First of all, the sparsity and linear clustering characteristics of the time–frequency domain MIMO radar signals are enhanced by using the single-source principal value of complex angular detection. Secondly, the data field uses the potential energy information to analyze the particle distribution, thus design a new clustering number selection scheme. Then the particle swarm optimization algorithm is introduced to improve the iterative clustering process of FCM, and finally get the estimated value of the mixing matrix. The simulation results show that the proposed algorithm improves both the estimation accuracy and the robustness of the mixing matrix.

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

Science.gov (United States)

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 (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.

Pulse and gamma radiolytic studies of Ag, Cd and mixed clusters in aqueous solutions of carboxymethyl cellulose and gelatin

International Nuclear Information System (INIS)

Kapoor, Sudhir; Gopinathan, C.

1996-01-01

Pulse and gamma radiolytic studies in aqueous solutions of Ag, Cd and mixed clusters were carried out in carboxymethylcellulose (CMC) or gelatin. The reaction rate of e aq - with Ag + is lower in the presence of CMC or gelatin and oligomeric clusters of silver, Cd and mixed clusters get stabilized in their presence. (author). 2 refs., 2 figs

Photoelectron spectroscopy and density functional theory studies of (FeS)mH- (m = 2-4) cluster anions: effects of the single hydrogen.

Science.gov (United States)

Yin, Shi; Bernstein, Elliot R

2017-12-20

Single hydrogen containing iron hydrosulfide cluster anions (FeS) m H - (m = 2-4) are studied by photoelectron spectroscopy (PES) at 3.492 eV (355 nm) and 4.661 eV (266 nm) photon energies, and by Density Functional Theory (DFT) calculations. The structural properties, relative energies of different spin states and isomers, and the first calculated vertical detachment energies (VDEs) of different spin states for these (FeS) m H - (m = 2-4) cluster anions are investigated at various reasonable theory levels. Two types of structural isomers are found for these (FeS) m H - (m = 2-4) clusters: (1) the single hydrogen atom bonds to a sulfur site (SH-type); and (2) the single hydrogen atom bonds to an iron site (FeH-type). Experimental and theoretical results suggest such available different SH- and FeH-type structural isomers should be considered when evaluating the properties and behavior of these single hydrogen containing iron sulfide clusters in real chemical and biological systems. Compared to their related, respective pure iron sulfur (FeS) m - clusters, the first VDE trend of the diverse type (FeS) m H 0,1 - (m = 1-4) clusters can be understood through (1) the different electron distribution properties of their highest singly occupied molecular orbital employing natural bond orbital analysis (NBO/HSOMO), and (2) the partial charge distribution on the NBO/HSOMO localized sites of each cluster anion. Generally, the properties of the NBO/HSOMOs play the principal role with regard to the physical and chemical properties of all the anions. The change of cluster VDE from low to high is associated with the change in nature of their NBO/HSOMO from a dipole bound and valence electron mixed character, to a valence p orbital on S, to a valence d orbital on Fe, and to a valence p orbital on Fe or an Fe-Fe delocalized valence bonding orbital. For clusters having the same properties for NBO/HSOMOs, the partial charge distributions at the NBO/HSOMO localized sites additionally

Valencies of the lanthanides

OpenAIRE

Johnson, David A.; Nelson, Peter G.

2018-01-01

The valencies of the lanthanides vary more than was once thought. In addition to valencies associated with a half-full shell, there are valencies associated with a quarter- and three-quarter-full shell. This can be explained on the basis of Slater’s theory of many-electron atoms. The same theory explains the variation in complexing constants in the trivalent state (the “tetrad effect”). Valency in metallic and organometallic compounds is also discussed.

Valence effects of sorption: laboratory control of valence state

International Nuclear Information System (INIS)

Meyer, R.E.; Arnold, W.D.; Case, F.I.

1984-01-01

Estimation of the rates of migration of nuclides from nuclear waste repositories required knowledge of the interaction of these nuclides with the components of the geological formations in the path of the migration. These interactions will be dependent upon the valence state and speciation of the nuclide. If the valence state is not known, then there can be little confidence in use of the data for safety analysis. An electrochemical method of valence state control was developed which makes use of a porous electrode in a flow system containing a column of the adsorbent. By use of this method and solvent extraction analyses of the valence states, a number of reactions of interest to HLW repositories were investigated. These include the reduction of Np(V) and Tc(VII) by crushed basalt and other minerals. For the reduction of Np(V) by basalt, the experiments indicate that sorption on basalt increases with pH and that most of the Np is reduced to Np(IV). The adsorbed Np(IV) is very difficult to remove from the basalt. For the experiments with Tc(VII), the results are considerably more complicated. The results of these experiments are used to assess some of the techniques and methods currently used in safety analyses of proposed HLW repositories. Perhaps the most important consideration is that predictive modeling of valence change reactions, such as the reduction of Np(V) and Tc(VII), must be used with considerable caution, and the occurrence of such reactions should be verified as best as possible with experiments using valence state control and analyses. 13 references, 3 figures, 1 table

[Mixed valent and heavy ferimons and related systems

International Nuclear Information System (INIS)

Schlottmann, P.

1991-01-01

The main objective of the project is to gain a better understanding of highly correlated fermion systems. High correlations appear in a variety of solid state phenomena: mixed-valence and heavy-fermions or Kondo systems, superfluid and normal He 3 , high-temperature superconductors, magnetism in low dimensions, quantum Hall effect, spin-fluctuations in transition metals, giant magnetic moments, tunneling of an atom interacting with a degenerate electron gas, quantum dissipative systems, organic superconductors, etc. The primary focus of the work is on valence mixing and heavy fermions, but elated highly correlated systems are also studied. In this paper a brief summary of the achievements grouped under four headings, namely (1) heavy fermions-mixed valence-Kondo, (2) magnetism in low dimensions, (3) narrow band phenomena/Hubbard model and (4) collaborations with experimentalists

MixSim : An R Package for Simulating Data to Study Performance of Clustering Algorithms

Directory of Open Access Journals (Sweden)

Volodymyr Melnykov

2012-11-01

Full Text Available The R package MixSim is a new tool that allows simulating mixtures of Gaussian distributions with different levels of overlap between mixture components. Pairwise overlap, defined as a sum of two misclassification probabilities, measures the degree of interaction between components and can be readily employed to control the clustering complexity of datasets simulated from mixtures. These datasets can then be used for systematic performance investigation of clustering and finite mixture modeling algorithms. Among other capabilities of MixSim, there are computing the exact overlap for Gaussian mixtures, simulating Gaussian and non-Gaussian data, simulating outliers and noise variables, calculating various measures of agreement between two partitionings, and constructing parallel distribution plots for the graphical display of finite mixture models. All features of the package are illustrated in great detail. The utility of the package is highlighted through a small comparison study of several popular clustering algorithms.

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

Science.gov (United States)

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.

The possibility of the mixed valence state in the uranium intermetallic compounds: UCoGa5, U2Ru2Sn and U2RuGa8

International Nuclear Information System (INIS)

Troc, Robert

2007-01-01

The mixed valence (MV) phenomenon has been observed so far in a large number of various compounds but containing only lanthanides. These properties are usually associated with the mixing of the localised f-state and the band states. The usual valence state for magnetic uranium intermetallics is the trivalent state 5f 3 or hybridised 5f 2 6d 1 , both are nearly degenerate in energy and can compete for a stability of the compound. In some cases a gain in an energy minimum may be achieved by very fast fluctuating between these two states with a time of 10 -14 s, which does not allow to yield the ordered state even if the exchange interactions (favourite the U-U distances) would be able for that. The latter cases seem to concern the described here intermetallics: one ternary compound based on Co, UCoGa 5 , and the two uranium ternary compounds based on Ru, namely U 2 Ru 2 Sn and U 2 RuGa 8 which all crystallize in a tetragonal unit cell. All these compounds show a maximum in their temperature dependences of the magnetic susceptibility measured along and perpendicular to the c-axis. Such a behaviour, which is reminiscent of a number of Ce (Sm, Eu) and Yb compounds for which χ(T) has in the past been considered by Sales and Wohlleben (SW) by applying their ICF model or by Lawrance et al. following their scaling procedure. It turned out that these phenomenological models can also be applied to the considered here two Ru-based uranium ternaries from which some reliable energy parameters could be found. In order to further support the mixing valence scenario for the first such cases in uranium compounds presented here, the transport and thermodynamic properties are also discussed. However, some of the most important results confirming the MV state, e.g., in U 2 RuGa 8 , has recently been achieved from the inelastic neutron scattering performed in the Rutherford Appleton Laboratory on the ISIS facility. From these measurements a characteristic gap of 60 meV has been

Investigation of thermal quenching and abnormal thermal quenching in mixed valence Eu co-doped LaAlO{sub 3} phosphor

Energy Technology Data Exchange (ETDEWEB)

Chen, Jingjing [Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384 (China); Zhao, Yang [China academy of civil aviation science and technology, Beijing 100028 (China); Mao, Zhiyong, E-mail: mzhy1984@163.com [Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384 (China); Wang, Dajian [Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384 (China); Bie, Lijian, E-mail: ljbie@tjut.edu.cn [Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384 (China)

2017-06-15

Temperature dependent luminescence of mixed valence Eu co-doped LaAlO{sub 3} phosphors are deeply investigated in this work. Different temperature properties of Eu{sup 2+} and Eu{sup 3+} luminescence are observed as the phosphor excited by different incident light. Eu{sup 3+} luminescence shows normal thermal quenching when excited at 320 nm and abnormal thermal quenching as the excitation light changed into 365 nm, while Eu{sup 2+} luminescence exhibits a normal thermal quenching independent on the incident excitation lights. The origin of these novel normal/abnormal thermal quenching phenomena are analyzed and discussed by the excitation-emission processes in terms of the configuration coordinate model. The presented important experimental and analysis results give insights into the temperature properties of phosphors.

cis-dioxovanadium(V) and mixed-valence divanadium(IV, V) complexes containing β-diketonate and heterocyclic nitrogen-base ligands

International Nuclear Information System (INIS)

Taguchi, Hiroshi; Isobe, Kiyoshi; Nakamura, Yukio; Kawaguchi, Shinichi

1978-01-01

Diamagnetic dioxovanadium(V) complexes, VO 2 (β-dik)(phen or bpy), were prepared by the direct reactions of VO(β-dik) 2 with 1,10-phenanthroline and 2,2'-bipyridine in dichloromethane under aerobic conditions as well as by two other methods. These compounds were concluded to have a cis configuration on the basis of the IR and Raman data. These complexes are solvolyzed to afford the di-μ-methoxo- or di-μ-hydroxo-divanadium(V) species, and are reduced by hydrogen bromide to the oxovanadium(IV) species in dichloromethane. In methanol instead of dichloromethane, VO(acac) 2 reacted with 2,2'-bipyridine to produce a novel mixed-valence divanadium(IV, V) complex, V 2 O 3 (acac) 3 (bpy), which was revealed by the magnetic, spectral, and polarographic data to be a trans adduct of VO(acac) 2 with VO 2 (acac)(bpy) via an oxide ligand. (auth.)

Valence and Magnetic Transitions in YbMn2Ge2-Applied Pressure

International Nuclear Information System (INIS)

Hofmann, M.; Link, P.; Campbell, S.J.; Goncharenko, I.

2005-01-01

Full text: Rare-earth intermetallic compounds containing ytterbium exhibit a wide range of interesting and unusual physical and magnetic properties. This occurs mainly as a result of their mixed valence states (II/III) or changes from one valence state to the other. We have recently determined the magnetic structures of tetragonal YbMn 2 Ge 2 (I4/mmm) by powder neutron diffraction experiments and demonstrated that YbMn 2 Ge 2 has a planar antiferromagnetic structure below T N1 ∼ 510 K with a canted antiferromagnetic structure below T N2 ∼ 185 K. As applied pressure favours changes in the valence character of intermediate valence systems and correspondingly influences the magnetic behaviour, we have investigated the effects of applied pressure on YbMn 2 Ge 2 . Analyses of our in situ neutron diffraction experiments (T=1.5-300 K; p=0-2.7 GPa), reveal a distinct change in magnetic structure and a sharp drop in the a-lattice parameter above ∼ 1.4 GPa with the changes associated with a valence transition. A full account of these effects will be discussed in relation to our current photoelectron spectroscopy measurements of YbMn 2 Ge 2 . (authors)

Breakdown of rotational symmetry at semiconductor interfaces; a microscopic description of valence subband mixing

International Nuclear Information System (INIS)

Cortez, S.; Krebs, O.; Voisin, P.

2000-01-01

The recently discovered in-plane optical anisotropy of [001]-grown quantum wells offers a new theoretical and experimental insight into the electronic properties of semiconductor interfaces. We first discuss the coupling of X and Y valence bands due to the breakdown of rotation inversion symmetry at a semiconductor hetero-interface, with special attention to its dependence on effective parameters such as valence band offset. The intracell localization of Bloch functions is explained from simple theoretical arguments and evaluated numerically from a pseudo-potential microscopic model. The role of envelope functions is considered, and we discuss the specific case of non-common atom interfaces. Experimental results and applications to interface characterization are presented. These calculations give a microscopic justification, and establish the limits of the heuristic 'H BF ' model. (author)

Temperature-induced valence transition in EuNi2(Si0.20Ge0.80)2 studied by hard X-ray photoemission spectroscopy

International Nuclear Information System (INIS)

Yamamoto, Kazuya; Kamakura, Nozomu; Taguchi, Munetaka; Chainani, Ashish; Takata, Yasutaka; Horiba, Koji; Shin, Shik; Ikenaga, Eiji; Mimura, Kojiro; Shiga, Masayuki; Wada, Hirofumi; Namatame, Hirofumi; Taniguchi, Masaki; Awaji, Mitsuhiro; Takeuchi, Akihisa; Nishino, Yoshinori; Miwa, Daigo; Tamasaku, Kenji; Ishikawa, Tetsuya; Kobayashi, Keisuke

2005-01-01

The temperature-induced mixed valence transition in EuNi 2 (Si 0.20 Ge 0.80 ) 2 has been investigated by hard X-ray (5940 eV) photoemission spectroscopy (HX-PES) for fractured surfaces, with a probing depth larger than 5 nm. The Eu 3d core-level states are studied below and above the critical valence transition temperature, T v = 80 K. The HX-PES spectra at 40 and 120 K show the mixed valence transition, with clear changes in the divalent and trivalent Eu 3d chemically shifted features. The Eu 3d HX-PES spectra indicate a mean valence of 2.70 ± 0.03 at 40 K which changes to 2.40 ± 0.03 at 120 K, in good accordance with the results of bulk Eu III -edge X-ray absorption spectroscopy measurements

Detecting treatment-subgroup interactions in clustered data with generalized linear mixed-effects model trees.

Science.gov (United States)

Fokkema, M; Smits, N; Zeileis, A; Hothorn, T; Kelderman, H

2017-10-25

Identification of subgroups of patients for whom treatment A is more effective than treatment B, and vice versa, is of key importance to the development of personalized medicine. Tree-based algorithms are helpful tools for the detection of such interactions, but none of the available algorithms allow for taking into account clustered or nested dataset structures, which are particularly common in psychological research. Therefore, we propose the generalized linear mixed-effects model tree (GLMM tree) algorithm, which allows for the detection of treatment-subgroup interactions, while accounting for the clustered structure of a dataset. The algorithm uses model-based recursive partitioning to detect treatment-subgroup interactions, and a GLMM to estimate the random-effects parameters. In a simulation study, GLMM trees show higher accuracy in recovering treatment-subgroup interactions, higher predictive accuracy, and lower type II error rates than linear-model-based recursive partitioning and mixed-effects regression trees. Also, GLMM trees show somewhat higher predictive accuracy than linear mixed-effects models with pre-specified interaction effects, on average. We illustrate the application of GLMM trees on an individual patient-level data meta-analysis on treatments for depression. We conclude that GLMM trees are a promising exploratory tool for the detection of treatment-subgroup interactions in clustered datasets.

Simulating Ru L3-edge X-ray absorption spectroscopy with time-dependent density functional theory: model complexes and electron localization in mixed-valence metal dimers.

Science.gov (United States)

Van Kuiken, Benjamin E; Valiev, Marat; Daifuku, Stephanie L; Bannan, Caitlin; Strader, Matthew L; Cho, Hana; Huse, Nils; Schoenlein, Robert W; Govind, Niranjan; Khalil, Munira

2013-05-30

Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of Ru(II) and Ru(III) complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6](4-) and Ru(II) 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)5M(II)-CN-Ru(III)(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.

Clustering Methods with Qualitative Data: a Mixed-Methods Approach for Prevention Research with Small Samples.

Science.gov (United States)

Henry, David; Dymnicki, Allison B; Mohatt, Nathaniel; Allen, James; Kelly, James G

2015-10-01

Qualitative methods potentially add depth to prevention research but can produce large amounts of complex data even with small samples. Studies conducted with culturally distinct samples often produce voluminous qualitative data but may lack sufficient sample sizes for sophisticated quantitative analysis. Currently lacking in mixed-methods research are methods allowing for more fully integrating qualitative and quantitative analysis techniques. Cluster analysis can be applied to coded qualitative data to clarify the findings of prevention studies by aiding efforts to reveal such things as the motives of participants for their actions and the reasons behind counterintuitive findings. By clustering groups of participants with similar profiles of codes in a quantitative analysis, cluster analysis can serve as a key component in mixed-methods research. This article reports two studies. In the first study, we conduct simulations to test the accuracy of cluster assignment using three different clustering methods with binary data as produced when coding qualitative interviews. Results indicated that hierarchical clustering, K-means clustering, and latent class analysis produced similar levels of accuracy with binary data and that the accuracy of these methods did not decrease with samples as small as 50. Whereas the first study explores the feasibility of using common clustering methods with binary data, the second study provides a "real-world" example using data from a qualitative study of community leadership connected with a drug abuse prevention project. We discuss the implications of this approach for conducting prevention research, especially with small samples and culturally distinct communities.

Clustering Methods with Qualitative Data: A Mixed Methods Approach for Prevention Research with Small Samples

Science.gov (United States)

Henry, David; Dymnicki, Allison B.; Mohatt, Nathaniel; Allen, James; Kelly, James G.

2016-01-01

Qualitative methods potentially add depth to prevention research, but can produce large amounts of complex data even with small samples. Studies conducted with culturally distinct samples often produce voluminous qualitative data, but may lack sufficient sample sizes for sophisticated quantitative analysis. Currently lacking in mixed methods research are methods allowing for more fully integrating qualitative and quantitative analysis techniques. Cluster analysis can be applied to coded qualitative data to clarify the findings of prevention studies by aiding efforts to reveal such things as the motives of participants for their actions and the reasons behind counterintuitive findings. By clustering groups of participants with similar profiles of codes in a quantitative analysis, cluster analysis can serve as a key component in mixed methods research. This article reports two studies. In the first study, we conduct simulations to test the accuracy of cluster assignment using three different clustering methods with binary data as produced when coding qualitative interviews. Results indicated that hierarchical clustering, K-Means clustering, and latent class analysis produced similar levels of accuracy with binary data, and that the accuracy of these methods did not decrease with samples as small as 50. Whereas the first study explores the feasibility of using common clustering methods with binary data, the second study provides a “real-world” example using data from a qualitative study of community leadership connected with a drug abuse prevention project. We discuss the implications of this approach for conducting prevention research, especially with small samples and culturally distinct communities. PMID:25946969

Capabilities of R Package mixAK for Clustering Based on Multivariate Continuous and Discrete Longitudinal Data

Directory of Open Access Journals (Sweden)

Arnošt Komárek

2014-09-01

Full Text Available R package mixAK originally implemented routines primarily for Bayesian estimation of finite normal mixture models for possibly interval-censored data. The functionality of the package was considerably enhanced by implementing methods for Bayesian estimation of mixtures of multivariate generalized linear mixed models proposed in Komrek and Komrkov (2013. Among other things, this allows for a cluster analysis (classification based on multivariate continuous and discrete longitudinal data that arise whenever multiple outcomes of a different nature are recorded in a longitudinal study. This package also allows for a data-driven selection of a number of clusters as methods for selecting a number of mixture components were implemented. A model and clustering methodology for multivariate continuous and discrete longitudinal data is overviewed. Further, a step-by-step cluster analysis based jointly on three longitudinal variables of different types (continuous, count, dichotomous is given, which provides a user manual for using the package for similar problems.

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.

Science.gov (United States)

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.

Cu(I)/Cu(II) mixed-valence surface complexes of S-[(2-hydroxyamino)-2-oxoethyl]-N,N-dibutyldithiocarbamate: Hydrophobic mechanism to malachite flotation.

Science.gov (United States)

Liu, Sheng; Zhong, Hong; Liu, Guangyi; Xu, Zhenghe

2018-02-15

Hydroxamate and sulfhydryl surfactants are effective collectors for flotation of copper minerals. The combination application of hydroxamate and sulfhydryl collectors has been proved to be an effective approach for improving the flotation recovery of non-sulfide copper minerals. A surfactant owing both hydroxamate and dithiocarbamate groups might exhibit strong affinity to non-sulfide copper minerals through double sites adsorption, rendering an enhanced hydrophobization to non-sulfide copper minerals flotation. The flotation performance of S-[(2-hydroxyamino)-2-oxoethyl]- N,N-dibutyldithiocarbamate (HABTC) to malachite, calcite and quartz were first evaluated through systematic micro-flotation experiments. HABTC's hydrophobic mechanism to malachite was further investigated and analyzed by zeta potential, Fourier transform infrared spectroscopy (FTIR), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The micro-flotation results demonstrated HABTC was an excellent collector for malachite flotation and exhibited favorable selectivity for flotation separation of malachite from quartz or calcite under pH 8.5-10.3. Zeta potential and FTIR implied that HABTC might bond with the surface copper atoms of malachite, with releasing the H + ions of its hydroxamate group into pulp. ToF-SIMS provided clear evidences that the Cu-hydroxamate and Cu-dithiocarbamate groups were formed on malachite surfaces after HABTC adsorption. XPS revealed that Cu(I)/Cu(II) mixed-valence surface complexes of HABTC anchored on malachite through formation of Cu(I)S and Cu(II)O bonds, accompanying with reduction of partial surface Cu(II) to Cu(I). The Cu(I)/Cu(II) mixed-valence double chelating character and "chair"-shape N,N-dibutyldithiocarbamate hydrophobic group, resulting in an enhanced affinity and hydrophobization of HABTC to malachite flotation. Copyright © 2017 Elsevier Inc. All rights reserved.

Theory of Valence Transitions in Ytterbium and Europium Intermetallics

International Nuclear Information System (INIS)

Zlatic, V.; Freericks, J.K.

2001-01-01

The exact solution of the multi-component Falicov-Kimball model in infinite-dimensions is presented and used to discuss a new fixed point of valence fluctuating intermetallics with Yb and Eu ions. In these compounds, temperature, external magnetic field, pressure, or chemical pressure induce a transition between a metallic state with the f-ions in a mixed-valent (non-magnetic) configuration and a semi-metallic state with the f-ions in an integral-valence (paramagnetic) configuration. The zero-field transition occurs at the temperature T V , while the zero-temperature transition sets in at the critical field H c . We present the thermodynamic and dynamic properties of the model for an arbitrary concentration of d- and f -electrons. For large U, we find a MI transition, triggered by the temperature or field- induced change in the f-occupancy. (author)

Generalized oscillator strengths for some higher valence-shell excitations of krypton atom

Institute of Scientific and Technical Information of China (English)

2007-01-01

The valence-shell excitations of krypton atom have been investigated by fast electron impact with an angle-resolved electron-energy-loss spectrometer. The generalized oscillator strengths for some higher mixed valence-shell excitations in 4d, 4f, 5p, 5d, 6s, 6p, 7s ← 4p of krypton atom have been determined. Their profiles are discussed, and the generalized oscillator strengths for the electric monopole and quadrupole excitations in 5p ← 4p are compared with the calculations of Amusia et al. (Phys. Rev. A 67 022703 (2003)). The differences between the experimental results and theoretical calculations show that more studies are needed.

Calculation of fluctuations and photoemission properties in a tetrahedral-cluster model for an intermediate-valence system

International Nuclear Information System (INIS)

Reich, A.; Falicov, L.M.

1986-01-01

An exact solution of a four-site tetrahedral-crystal model, the smallest face-centered-cubic crystal, is presented in the case of an intermediate-valence system. The model consists of the following: (a) one extended orbital and one localized orbital per atom, (b) an interatomic transfer term between extended orbitals, (c) an interatomic hybridization between the localized and extended orbitals, (d) strong intra-atomic Coulomb repulsion between opposite-spin localized states, and (e) intermediate-strength intra-atomic Coulomb repulsion between the localized and extended states. These competing effects are examined as they manifest themselves in the intermediate-valence, photoemission, inverse-photoemission, and thermodynamic properties

Constraints from stellar models on mixing as a viable explanation of abundance anomalies in globular clusters

International Nuclear Information System (INIS)

Vandenberg, D.A.; Smith, G.H.

1988-01-01

Published observational data on changes in the surface abundances of evolving stars in globular clusters are compiled and compared with the predictions of theoretical evolutionary sequences (for stars of mass 0.8 solar mass and metallicity Z = 0.0001 or mass 0.9 solar mass and Z = 0.006) and of models incorporating enhanced envelope-interior mixing at various evolutionary phases. The results are presented in graphs and characterized in detail. It is found that mixing models of CN bimodality in globular-cluster stars can encounter difficulties when abundance anomalies appear early in the evolution of the star. 63 references

A grand unified model for liganded gold clusters

Science.gov (United States)

Xu, Wen Wu; Zhu, Beien; Zeng, Xiao Cheng; Gao, Yi

2016-12-01

A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three `flavours' (namely, bottom, middle and top) to represent three possible valence states. The `composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design.

Uptake of methanol on mixed HNO3/H2O clusters: An absolute pickup cross section

Science.gov (United States)

Pysanenko, A.; Lengyel, J.; Fárník, M.

2018-04-01

The uptake of atmospheric oxidized organics on acid clusters is relevant for atmospheric new particle formation. We investigate the pickup of methanol (CH3OH) on mixed nitric acid-water clusters (HNO3)M(H2O)N by a combination of mass spectrometry and cluster velocity measurements in a molecular beam. The mass spectra of the mixed clusters exhibit (HNO3)m(H2O)nH+ series with m = 0-3 and n = 0-12. In addition, CH3OH.(HNO3)m(H2O)nH+ series with very similar patterns appear in the spectra after the methanol pickup. The velocity measurements prove that the undoped (HNO3)m(H2O)nH+ mass peaks in the pickup spectra originate from the neutral (HNO3)M(H2O)N clusters which have not picked up any CH3OH molecule, i.e., methanol has not evaporated upon the ionization. Thus the fraction of the doped clusters can be determined and the mean pickup cross section can be estimated, yielding σs ¯ ≈ 20 Å2. This is compared to the lower estimate of the mean geometrical cross section σg ¯ ≈ 60 Å2 obtained from the theoretical cluster geometries. Thus the "size" of the cluster corresponding to the methanol pickup is at least 3-times smaller than its geometrical size. We have introduced a method which can yield the absolute pickup cross sections relevant to the generation and growth of atmospheric aerosols, as illustrated in the example of methanol and nitric acid clusters.

Magnetic excitations in intermediate valence semiconductors with singlet ground state

International Nuclear Information System (INIS)

Kikoin, K.A.; Mishchenko, A.S.

1994-01-01

The explanation of the origin inelastic peaks in magnetic neutron scattering spectra of the mixed-valent semiconductor SmB 6 is proposed. It is shown that the excitonic theory of intermediate valence state not only gives the value of the peak frequency but also explains the unusual angular dependence of intensity of inelastic magnetic scattering and describes the dispersion of magnetic excitations in good agreement with experiment

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

Science.gov (United States)

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

Coupled cluster valence bond theory for open-shell systems with application to very long range strong correlation in a polycarbene dimer.

Science.gov (United States)

Small, David W; Head-Gordon, Martin

2017-07-14

The Coupled Cluster Valence Bond (CCVB) method, previously presented for closed-shell (CS) systems, is extended to open-shell (OS) systems. The theoretical development is based on embedding the basic OS CCVB wavefunction in a fictitious singlet super-system. This approach reveals that the OS CCVB amplitude equations are quite similar to those of CS CCVB, and thus that OS CCVB requires the same level of computational effort as CS CCVB, which is an inexpensive method. We present qualitatively correct CCVB potential energy curves for all low-lying spin states of P 2 and Mn 2 + . CCVB is successfully applied to the low-lying spin states of some model linear polycarbenes, systems that appear to be a hindrance to standard density functionals. We examine an octa-carbene dimer in a side-by-side orientation, which, in the monomer dissociation limit, exhibits maximal strong correlation over the length of the polycarbene.

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

Science.gov (United States)

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

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

Science.gov (United States)

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%.

Near-Edge X-ray Absorption Fine Structure within Multilevel Coupled Cluster Theory.

Science.gov (United States)

Myhre, Rolf H; Coriani, Sonia; Koch, Henrik

2016-06-14

Core excited states are challenging to calculate, mainly because they are embedded in a manifold of high-energy valence-excited states. However, their locality makes their determination ideal for local correlation methods. In this paper, we demonstrate the performance of multilevel coupled cluster theory in computing core spectra both within the core-valence separated and the asymmetric Lanczos implementations of coupled cluster linear response theory. We also propose a visualization tool to analyze the excitations using the difference between the ground-state and excited-state electron densities.

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

Energy Technology Data Exchange (ETDEWEB)

Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, Nils; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira

2013-05-30

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

Event-related brain potential correlates of words' emotional valence irrespective of arousal and type of task.

Science.gov (United States)

Espuny, Javier; Jiménez-Ortega, Laura; Casado, Pilar; Fondevila, Sabela; Muñoz, Francisco; Hernández-Gutiérrez, David; Martín-Loeches, Manuel

2018-03-23

Many Event-Related brain Potential (ERP) experiments have explored how the two main dimensions of emotion, arousal and valence, affect linguistic processing. However, the heterogeneity of experimental paradigms and materials has led to mixed results. In the present study, we aim to clarify words' emotional valence effects on ERP when arousal is controlled, and determine whether these effects may vary as a function of the type of task performed. For these purposes, we designed an ERP experiment with the valence of words manipulated, and arousal equated across valences. The participants performed two types of task: in one, they had to read aloud each word, written in black on a white background; in the other, they had to name the color of the ink in which each word was written. The results showed the main effects of valence irrespective of task, and no interaction between valence and task. The most marked effects of valence were in response to negative words, which elicited an Early Posterior Negativity (EPN) and a Late Positive Complex (LPC). Our results suggest that, when arousal is controlled, the cognitive information in negative words triggers a 'negativity bias', these being the only words able to elicit emotion-related ERP modulations. Moreover, these modulations are largely unaffected by the types of task explored here. Copyright © 2018 Elsevier B.V. All rights reserved.

Continuum-limit scaling of overlap fermions as valence quarks

International Nuclear Information System (INIS)

Cichy, Krzysztof; Herdoiza, Gregorio; Jansen, Karl

2009-10-01

We present the results of a mixed action approach, employing dynamical twisted mass fermions in the sea sector and overlap valence fermions, with the aim of testing the continuum limit scaling behaviour of physical quantities, taking the pion decay constant as an example. To render the computations practical, we impose for this purpose a fixed finite volume with lattice size L∼1.3 fm. We also briefly review the techniques we have used to deal with overlap fermions. (orig.)

The valence state of Yb metal under high pressure determined by XANES measurement up to 34.6 GPa

International Nuclear Information System (INIS)

Fuse, Akinori; Nakamoto, Go; Kurisu, Makio; Ishimatsu, Naoki; Tanida, Hajime

2004-01-01

The purpose of this study was to accurately determine the valency of Yb at high pressure and room temperature and to clarify the relation between the valence state and the crystal structure of Yb metal. L III -edge X-ray absorption near-edge structure (XANES) spectra were measured to determine the valence state of Yb metal in the pressure range from 0 to 34.6 GPa at room temperature, using a diamond anvil cell (DAC) and synchrotron radiation at SPring-8. In the fcc phase, Yb metal exhibits mixed valence (the mean valence ν-bar >2.1). At the fcc-to-bcc phase transition, a 0.1 jump is found in ν-bar. In the bcc phase, ν-bar(P) is an increasing function of pressure with downward curvature, reaching only 2.55 at 26 GPa. The ν-bar is only 2.65 in the hcp phase at 34.6 GPa. A tendency for saturation in ν-bar(P) to values smaller than 3.0 is found

Polymer complexes.. XXXX. Supramolecular assembly on coordination models of mixed-valence-ligand poly[1-acrylamido-2-(2-pyridyl)ethane] complexes

Science.gov (United States)

El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.

2003-02-01

The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [( 11)+( 12)] in the paper and in mononuclear polymer complexes ( 1)-( 5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX 2 and KPtCl 4 in the presence of N-heterocyclic base consisting of polymer complexes ( 9)+( 10), and in monouclear compounds ( 6)-( 8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds ( 13)+( 14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.

Manganese L-edge X-ray absorption spectroscopy of manganese catalase from Lactobacillus plantarum and mixed valence manganese complexes

Energy Technology Data Exchange (ETDEWEB)

Grush, M.M.; Chen, J.; George, S.J. [Univ. of California, Davis, CA (United States)] [and others

1996-01-10

The first Mn L-edge absorption spectra of a Mn metalloprotein are presented in this paper. Both reduced and superoxidized Mn catalase have been examined by fluorescence-detected soft X-ray absorption spectroscopy, and their Mn L-edge spectra are dramatically different. The spectrum of reduced Mn(II)Mn(II) catalase has been interpreted by ligand field atomic multiplet calculations and by comparison to model compound spectra. The analysis finds a 10 Dq value of nearly 1.1 eV, consistent with coordination by predominately nitrogen and oxygen donor ligands. For interpretation of mixed valence Mn spectra, an empirical simulation procedure based on the addition of homovalent model compound spectra has been developed and was tested on a variety of Mn complexes and superoxidized Mn catalase. This routine was also used to determine the oxidation state composition of the Mn in [Ba{sub 8}Na{sub 2}ClMn{sub 16}(OH){sub 8}(CO{sub 3}){sub 4}L{sub 8}] .53 H{sub 2}O (L=1,3-diamino-2-hydroxypropane-N,N,N`N`-tetraacetic acid). 27 refs., 6 figs.

Sample size adjustments for varying cluster sizes in cluster randomized trials with binary outcomes analyzed with second-order PQL mixed logistic regression.

Science.gov (United States)

Candel, Math J J M; Van Breukelen, Gerard J P

2010-06-30

Adjustments of sample size formulas are given for varying cluster sizes in cluster randomized trials with a binary outcome when testing the treatment effect with mixed effects logistic regression using second-order penalized quasi-likelihood estimation (PQL). Starting from first-order marginal quasi-likelihood (MQL) estimation of the treatment effect, the asymptotic relative efficiency of unequal versus equal cluster sizes is derived. A Monte Carlo simulation study shows this asymptotic relative efficiency to be rather accurate for realistic sample sizes, when employing second-order PQL. An approximate, simpler formula is presented to estimate the efficiency loss due to varying cluster sizes when planning a trial. In many cases sampling 14 per cent more clusters is sufficient to repair the efficiency loss due to varying cluster sizes. Since current closed-form formulas for sample size calculation are based on first-order MQL, planning a trial also requires a conversion factor to obtain the variance of the second-order PQL estimator. In a second Monte Carlo study, this conversion factor turned out to be 1.25 at most. (c) 2010 John Wiley & Sons, Ltd.

Electronic structure of the BiSI cluster

Energy Technology Data Exchange (ETDEWEB)

Audzijonis, A. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Gaigalas, G. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Institute of Theoretical Physics and Astronomy, Vilnius University, A. Gostauto 12, LT-01108 Vilnius (Lithuania); Zigas, L. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania)]. E-mail: kkol@vpu.lt; Pauliukas, A. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Zaltauskas, R. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Cerskus, A. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Narusis, J. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Institute of Theoretical Physics and Astronomy, Vilnius University, A. Gostauto 12, LT-01108 Vilnius (Lithuania); Kvedaravicius, A. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania)

2007-03-15

The energy levels of valence bands (VB) and core levels (CL) of the BiSI crystals have been investigated theoretically. The molecular model of this crystal was used for calculation of VB and CL by the unrestricted Hartree-Fock method using GAMESS program, with Hw and MINI basis set. The molecular cluster consisting of 20 molecules of BiSI was used for calculations of averaged total density of states including atom vibrations. The spectra of averaged total density of states from VB of BiSI cluster has been compared with experimental X-ray photoelectron spectra (XPS) of VB of SbSI crystal. The results clarify that the atomic vibrations is one of possible reasons for the smoother appearance of the experimental XPS. The investigation of vibrational spectrum reveals new experimental information about the reflection spectrum of BiSI crystals. The cluster model calculations have shown that the splitting of the CL in the BiSI may be caused by the photoelectron emission from the atoms at the surface that is in different valence states. The cluster model calculation showed that splitting energy of CL depends on difference of ionic charges of the same atoms at the edges of BiSI cluster.

Electronic structure of the BiSI cluster

International Nuclear Information System (INIS)

Audzijonis, A.; Gaigalas, G.; Zigas, L.; Pauliukas, A.; Zaltauskas, R.; Cerskus, A.; Narusis, J.; Kvedaravicius, A.

2007-01-01

The energy levels of valence bands (VB) and core levels (CL) of the BiSI crystals have been investigated theoretically. The molecular model of this crystal was used for calculation of VB and CL by the unrestricted Hartree-Fock method using GAMESS program, with Hw and MINI basis set. The molecular cluster consisting of 20 molecules of BiSI was used for calculations of averaged total density of states including atom vibrations. The spectra of averaged total density of states from VB of BiSI cluster has been compared with experimental X-ray photoelectron spectra (XPS) of VB of SbSI crystal. The results clarify that the atomic vibrations is one of possible reasons for the smoother appearance of the experimental XPS. The investigation of vibrational spectrum reveals new experimental information about the reflection spectrum of BiSI crystals. The cluster model calculations have shown that the splitting of the CL in the BiSI may be caused by the photoelectron emission from the atoms at the surface that is in different valence states. The cluster model calculation showed that splitting energy of CL depends on difference of ionic charges of the same atoms at the edges of BiSI cluster

Improved Density Functional Tight Binding Potentials for Metalloid Aluminum Clusters

Science.gov (United States)

2016-06-01

unlimited IMPROVED DENSITY-FUNCTIONAL TIGHT BINDING POTENTIALS FOR METALLOID ALUMINUM CLUSTERS by Joon H. Kim June 2016 Thesis Advisor...DATES COVERED Master’s thesis 4. TITLE AND SUBTITLE IMPROVED DENSITY-FUNCTIONAL TIGHT BINDING POTENTIALS FOR METALLOID ALUMINUM CLUSTERS 5. FUNDING...repulsive potentials for use in density-functional tight binding (DFTB) simulations of low-valence aluminum metalloid clusters . These systems are under

Scaling properties for the first RE-like mixed valence examples in uranium compounds: U2Ru2Sn and U2RuGa8

International Nuclear Information System (INIS)

Troc, Robert

2006-01-01

The present study was motivated by the scaling characterization of the first example of mixed valence (MV) RE-like behaviour found recently among intermetallic ternary uranium compounds. The χ(T) function for both title compounds has been fitted to the interconfigurational fluctuation (ICF) model of Sales and Wohlleben in order to determine the characteristic fluctuation temperatures T sf and interconfigurational excitation energies E ex . A good scaling, with similar values of T sf like from those derived from the ICF model, has been achieved for both these ternaries by plotting Tχ(T)/C against the reduced T/T sf . Moreover, this scaling follows almost exactly those found earlier in a number of MV- RE compounds

Molecular cluster theory of chemical bonding in actinide oxide

International Nuclear Information System (INIS)

Ellis, D.E.; Gubanov, V.A.; Rosen, A.

1978-01-01

The electronic structure of actinide monoxides AcO and dioxides AcO 2 , where Ac = Th, U, Np, Pu, Am, Cm and Bk has been studied by molecular cluster methods based on the first-principles one-electron local density theory. Molecular orbitals for nearest neighbor clusters AcO 10- 6 and AcO 12- 8 representative of monoxide and dioxide lattices were obtained using non-relativistic spin-restricted and spin-polarized Hartree-Fock-Slater models for the entire series. Fully relativistic Dirac-Slater calculations were performed for ThO, UO and NpO in order to explore magnitude of spin-orbit splittings and level shifts in valence structure. Self-consistent iterations were carried out for NpO, in which the NpO 6 cluster was embedded in the molecular field of the solid. Finally, a ''moment polarized'' model which combines both spin-polarization and relativistic effects in a consistent fashion was applied to the NpO system. Covalent mixing of oxygen 2p and Ac 5f orbitals was found to increase rapidly across the actinide series; metal s,p,d covalency was found to be nearly constant. Mulliken atomic population analysis of cluster eigenvectors shows that free-ion crystal field models are unreliable, except for the light actinides. X-ray photoelectron line shapes have been calculated and are found to compare rather well with experimental data on the dioxides

Negative pressure driven valence instability of Eu in cubic Eu0.4La0.6Pd3

International Nuclear Information System (INIS)

Pandey, Abhishek; Mazumdar, Chandan; Ranganathan, R

2009-01-01

We report the change in the valency of Eu-ions in the binary intermetallic cubic compound EuPd 3 induced by La doping at rare-earth sites. Doping of La generates negative chemical pressure in the lattice, resulting in a significant increase of the lattice parameter without altering the simple-cubic structure of the compound. Results of dc-magnetic measurements suggest that this increase in the lattice parameter is associated with the valence transition of Eu-ions from Eu 3+ to a mixed-valent state. As Eu 2+ -ions possess a large magnetic moment, this valence transition significantly modifies the magnetic behavior of the compound. In contrast to introducing boron at the vacant body center site of the unit cell to change the valency of Eu-ions, as in the case of EuPd 3 B, our results suggest it can also be altered by doping a rare-earth ion of larger size at the lattice site of Eu in EuPd 3 .

If You Don't Have Valence, Ask Your Neighbor: Evaluation of Neutral Words as a Function of Affective Semantic Associates.

Science.gov (United States)

Kuhlmann, Michael; Hofmann, Markus J; Jacobs, Arthur M

2017-01-01

How do humans perform difficult forced-choice evaluations, e.g., of words that have been previously rated as being neutral? Here we tested the hypothesis that in this case, the valence of semantic associates is of significant influence. From corpus based co-occurrence statistics as a measure of association strength we computed individual neighborhoods for single neutral words comprised of the 10 words with the largest association strength. We then selected neutral words according to the valence of the associated words included in the neighborhoods, which were either mostly positive, mostly negative, mostly neutral or mixed positive and negative, and tested them using a valence decision task (VDT). The data showed that the valence of semantic neighbors can predict valence judgments to neutral words. However, all but the positive neighborhood items revealed a high tendency to elicit negative responses. For the positive and negative neighborhood categories responses congruent with the neighborhood's valence were faster than incongruent responses. We interpret this effect as a semantic network process that supports the evaluation of neutral words by assessing the valence of the associative semantic neighborhood. In this perspective, valence is considered a semantic super-feature, at least partially represented in associative activation patterns of semantic networks.

Lithium Storage in Microstructures of Amorphous Mixed-Valence Vanadium Oxide as Anode Materials.

Science.gov (United States)

Zhao, Di; Zheng, Lirong; Xiao, Ying; Wang, Xia; Cao, Minhua

2015-07-08

Constructing three-dimensional (3 D) nanostructures with excellent structural stability is an important approach for realizing high-rate capability and a high capacity of the electrode materials in lithium-ion batteries (LIBs). Herein, we report the synthesis of hydrangea-like amorphous mixed-valence VOx microspheres (a-VOx MSs) through a facile solvothermal method followed by controlled calcination. The resultant hydrangea-like a-VOx MSs are composed of intercrossed nanosheets and, thus, construct a 3 D network structure. Upon evaluation as an anode material for LIBs, the a-VOx MSs show excellent lithium-storage performance in terms of high capacity, good rate capability, and long-term stability upon extended cycling. Specifically, they exhibit very stable cycling behavior with a highly reversible capacity of 1050 mA h g(-1) at a rate of 0.1 A g(-1) after 140 cycles. They also show excellent rate capability, with a capacity of 390 mA h g(-1) at a rate as high as 10 A g(-1) . Detailed investigations on the morphological and structural changes of the a-VOx MSs upon cycling demonstrated that the a-VOx MSs went through modification of the local VO coordinations accompanied with the formation of a higher oxidation state of V, but still with an amorphous state throughout the whole discharge/charge process. Moreover, the a-VOx MSs can buffer huge volumetric changes during the insertion/extraction process, and at the same time they remain intact even after 200 cycles of the charge/discharge process. Thus, these microspheres may be a promising anode material for LIBs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Valence skipping driven superconductivity and charge Kondo effect

International Nuclear Information System (INIS)

Yanagisawa, Takashi; Hase, Izumi

2013-01-01

Highlights: •Valence skipping in metallic compounds can give rise to an unconventional superconductivity. •Several elements in the periodic table show valence skipping (or valence missing), for example, Bi forms the compounds in valence states +3 and +5. •The doping of valence skipping elements will induce superconductivity and this will lead to a possibility of high temperature superconductivity. •We consider the Wolf model with negative-U impurities, and show a phase diagram including superconducting phase. •There is a high temperature region near the boundary. -- Abstract: Valence skipping in metallic compounds can give rise to an unconventional superconductivity. Several elements in the periodic table show valence skipping (or valence missing), for example, Bi forms the compounds in valence states +3 and +5. The doping of valence skipping elements will induce superconductivity and this will lead to a possibility of high temperature superconductivity. We consider the Wolf model with negative-U impurities, and show a phase diagram including superconducting phase. The superconducting state is changed into a metallic state with a local singlet as the attractive interaction |U| increases. There is a high temperature region near the boundary

Simultaneous conditioning of valence and arousal.

Science.gov (United States)

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.

Synthesis and characterization of a multifunctional inorganic-organic hybrid mixed-valence copper(I/II) coordination polymer: {[CuCN][Cu(isonic)2]}n

Science.gov (United States)

Liu, Dong-Sheng; Chen, Wen-Tong; Ye, Guang-Ming; Zhang, Jing; Sui, Yan

2017-12-01

A new multifunctional mixed-valence copper(I/II) coordination polymer, {[CuCN][Cu(isonic)2]}n(1) (Hisonic = isonicotinic acid), was synthesized by treating isonicotinic acid and 5-amino-tetrazolate (Hatz = 5-amino-tetrazolate) with copper(II) salts under hydrothermal conditions, and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction, respectively. The X-ray diffraction analysis reveals that compound exhibit noncentrosymmetric polar packing arrangement. It is three-dimensional (3D) framework with (3,5)-connected 'seh-3' topological network constructed from metal organic framework {[Cu(isonic)2]}n and the inorganic linear chain{Cu(CN)}n subunits. A remarkable feature of 1 is the rhombic open channels that are occupied by a linear chain of {Cu(CN)}n. Impressively compound 1 displays not only a second harmonic generation (SHG) response, but also a ferroelectric behavior and magnetic properties.

Applicability of a valence fluctuation model to the observed physical property response of actinide materials

International Nuclear Information System (INIS)

Sandenaw, T.A.

1978-01-01

It is shown that the physical property behavior of the light actinide elements, U, Np, and Pu, and certain of their alloys, is like that of known mixed-valence, R.E. metallic compounds. It is inferred that interconfiguration fluctuation (ICF) theory should also be applicable to actinide materials

Ground-state structures of Hafnium clusters

Energy Technology Data Exchange (ETDEWEB)

Ng, Wei Chun; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technoloty, Multimedia University, Melaca Campus, 75450 Melaka (Malaysia)

2015-04-24

Hafnium (Hf) is a very large tetra-valence d-block element which is able to form relatively long covalent bond. Researchers are interested to search for substitution to silicon in the semi-conductor industry. We attempt to obtain the ground-state structures of small Hf clusters at both empirical and density-functional theory (DFT) levels. For calculations at the empirical level, charge-optimized many-body functional potential (COMB) is used. The lowest-energy structures are obtained via a novel global-minimum search algorithm known as parallel tempering Monte-Carlo Basin-Hopping and Genetic Algorithm (PTMBHGA). The virtue of using COMB potential for Hf cluster calculation lies in the fact that by including the charge optimization at the valence shells, we can encourage the formation of proper bond hybridization, and thus getting the correct bond order. The obtained structures are further optimized using DFT to ensure a close proximity to the ground-state.

PREFACE: Nuclear Cluster Conference; Cluster'07

Science.gov (United States)

Freer, Martin

2008-05-01

The Cluster Conference is a long-running conference series dating back to the 1960's, the first being initiated by Wildermuth in Bochum, Germany, in 1969. The most recent meeting was held in Nara, Japan, in 2003, and in 2007 the 9th Cluster Conference was held in Stratford-upon-Avon, UK. As the name suggests the town of Stratford lies upon the River Avon, and shortly before the conference, due to unprecedented rainfall in the area (approximately 10 cm within half a day), lay in the River Avon! Stratford is the birthplace of the `Bard of Avon' William Shakespeare, and this formed an intriguing conference backdrop. The meeting was attended by some 90 delegates and the programme contained 65 70 oral presentations, and was opened by a historical perspective presented by Professor Brink (Oxford) and closed by Professor Horiuchi (RCNP) with an overview of the conference and future perspectives. In between, the conference covered aspects of clustering in exotic nuclei (both neutron and proton-rich), molecular structures in which valence neutrons are exchanged between cluster cores, condensates in nuclei, neutron-clusters, superheavy nuclei, clusters in nuclear astrophysical processes and exotic cluster decays such as 2p and ternary cluster decay. The field of nuclear clustering has become strongly influenced by the physics of radioactive beam facilities (reflected in the programme), and by the excitement that clustering may have an important impact on the structure of nuclei at the neutron drip-line. It was clear that since Nara the field had progressed substantially and that new themes had emerged and others had crystallized. Two particular topics resonated strongly condensates and nuclear molecules. These topics are thus likely to be central in the next cluster conference which will be held in 2011 in the Hungarian city of Debrechen. Martin Freer Participants and Cluster'07

Photoemission on gold-55-clusters derived from gold-phosphine AuP(C6H5)3Cl

International Nuclear Information System (INIS)

Quinten, M.; Sander, I.; Steiner, P.; Kreibig, U.; Fauth, K.; Schmid, G.

1991-01-01

We measured XPS and UPS spectra of gold clusters with 55 atoms, embedded in an electrically isolating phosphine matrix, and of gold-phosphine, from which the clusters were chemically derived. Compared to the spectra of bulk gold the valence band spectrum and the core level spectra of the clusters showed shifts of the peaks and the fermi level to higher binding energies. The shift of the peaks could qualitatively be interpreted by a final state effect. We succeeded in a separation of bulk and surface contributions to the core level spectra and in a reasonable quantitative analysis of the valence band spectrum of the clusters. The Au 4f core level spectrum of gold-phosphine showed two peaks at 1.5 eV higher binding energies than the corresponding peaks of the clusters. (orig.)

Mixing and matching siderophore clusters: structure and biosynthesis of serratiochelins from Serratia sp. V4.

Science.gov (United States)

Seyedsayamdost, Mohammad R; Cleto, Sara; Carr, Gavin; Vlamakis, Hera; João Vieira, Maria; Kolter, Roberto; Clardy, Jon

2012-08-22

Interrogation of the evolutionary history underlying the remarkable structures and biological activities of natural products has been complicated by not knowing the functions they have evolved to fulfill. Siderophores-soluble, low molecular weight compounds-have an easily understood and measured function: acquiring iron from the environment. Bacteria engage in a fierce competition to acquire iron, which rewards the production of siderophores that bind iron tightly and cannot be used or pirated by competitors. The structures and biosyntheses of "odd" siderophores can reveal the evolutionary strategy that led to their creation. We report a new Serratia strain that produces serratiochelin and an analog of serratiochelin. A genetic approach located the serratiochelin gene cluster, and targeted mutations in several genes implicated in serratiochelin biosynthesis were generated. Bioinformatic analyses and mutagenesis results demonstrate that genes from two well-known siderophore clusters, the Escherichia coli enterobactin cluster and the Vibrio cholera vibriobactin cluster, were shuffled to produce a new siderophore biosynthetic pathway. These results highlight how modular siderophore gene clusters can be mixed and matched during evolution to generate structural diversity in siderophores.

Gender moderates valence effects on the late positive potential to emotional distracters

OpenAIRE

Syrjänen, Elmeri

2013-01-01

Attention is captured more strongly by emotional pictures than by neutral pictures. This allocation of attention to emotional pictures is commonly indexed by the late positive potential (LPP), an event-related potential (ERP) that is larger for negative and positive pictures than for neutral pictures. However, findings are mixed in regards to valence effects, that is, whether the LPP is larger for negative pictures than for positive pictures (negativity bias) or vice versa (positivity bias). ...

Human Amygdala Represents the Complete Spectrum of Subjective Valence

Science.gov (United States)

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

Reactions probing effects of quark clusters in nuclei

International Nuclear Information System (INIS)

Lassila, K.E.; Sukhatme, U.P.

1988-01-01

We study signatures of quark clusters in reactions which probe quarks in nuclei. We examine the EMC effect and use physical arguments to establish features of valence and ocean parton distributions in multiquark clusters. We predict from these distributions ratios of structure functions and cross sections measured with neutrino, antineutrinos and proton beams. It appears that a unique determination of the source of the EMC effect will be possible. 6 refs., 4 figs

Emotional valence and the free-energy principle.

Science.gov (United States)

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.

Emotional valence and the free-energy principle.

Directory of Open Access Journals (Sweden)

Mateus Joffily

Full Text Available 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.

Ab initio valence calculations in chemistry

CERN Document Server

Cook, D B

1974-01-01

Ab Initio Valence Calculations in Chemistry describes the theory and practice of ab initio valence calculations in chemistry and applies the ideas to a specific example, linear BeH2. Topics covered include the Schrödinger equation and the orbital approximation to atomic orbitals; molecular orbital and valence bond methods; practical molecular wave functions; and molecular integrals. Open shell systems, molecular symmetry, and localized descriptions of electronic structure are also discussed. This book is comprised of 13 chapters and begins by introducing the reader to the use of the Schrödinge

Ferromagnetic bond of Li{sub 10} cluster: An alternative approach in terms of effective ferromagnetic sites

Energy Technology Data Exchange (ETDEWEB)

Donoso, Roberto; Fuentealba, Patricio, E-mail: pfuentea@hotmail.es, E-mail: cardena@macul.ciencias.uchile.cl; Cárdenas, Carlos, E-mail: pfuentea@hotmail.es, E-mail: cardena@macul.ciencias.uchile.cl [Departamento de Física, Facultad de Ciencias, Universidad de Chile, Casilla 653, Santiago (Chile); Centro para el Desarrollo de la Nanociencia y la Nanotecnología (CEDENNA), Avda. Ecuador 3493, Santiago 9170124 (Chile); Rössler, Jaime [Departamento de Física, Facultad de Ciencias, Universidad de Chile, Casilla 653, Santiago (Chile); Llano-Gil, Sandra [Faculty of Engineering, Food Engineering Program, Corporación Universitaria Lasallista, Caldas, Antioquia (Colombia)

2016-09-07

In this work, a model to explain the unusual stability of atomic lithium clusters in their highest spin multiplicity is presented and used to describe the ferromagnetic bonding of high-spin Li{sub 10} and Li{sub 8} clusters. The model associates the (lack of-)fitness of Heisenberg Hamiltonian with the degree of (de-)localization of the valence electrons in the cluster. It is shown that a regular Heisenberg Hamiltonian with four coupling constants cannot fully explain the energy of the different spin states. However, a more simple model in which electrons are located not at the position of the nuclei but at the position of the attractors of the electron localization function succeeds in explaining the energy spectrum and, at the same time, explains the ferromagnetic bond found by Shaik using arguments of valence bond theory. In this way, two different points of view, one more often used in physics, the Heisenberg model, and the other in chemistry, valence bond, come to the same answer to explain those atypical bonds.

Light quark correlators in a mixed-action setup

Energy Technology Data Exchange (ETDEWEB)

Bernardoni, Fabio [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Garron, Nicolas [Edinburgh Univ. (United Kingdom). SUPA, School of Physics; Hernandez, Pilar [CSIC-Univ. de Valencia (Spain). Inst. de Fisica Corpuscular; Necco, Silvia [European Organization for Nuclear Research (CERN), Geneva (Switzerland); Pena, Carlos [Univ. Autonoma de Madrid (Spain). Dept. de Fisica Teorica y Inst. de Fisica Teorica UAM/CSIC

2011-11-15

We report our progress in simulating Neuberger valence fermions on N{sub f}=2 Wilson O(a)-improved sea quarks. We compute correlators with valence quark masses both in the p- and in the e-regime, and we match the results with the predictions of the Chiral Effective Theory in the mixed regime. This allows us to extract the Low Energy Couplings (LECs) of the N{sub f}=2 theory and to test the validity of the approach. (orig.)

Overlap valence quarks on an twisted mass sea

Energy Technology Data Exchange (ETDEWEB)

Cichy, K. [Adam Mickiewicz Univ., Poznan (Poland). Faculty of Physics; Drach, V.; Garcia-Ramos, E.; Herdoiza, G.; Jansen, K. [DESY, Zeuthen (Germany). John von Neumann-Institut fuer Computing NIC

2010-12-15

We present the results of an investigation of a mixed action approach of overlap valence and maximally twisted mass sea quarks. Employing a particular matching condition on the pion mass, we analyze the continuum limit scaling of the pion decay constant and the role of chiral zero modes of the overlap operator in this process. We employ gauge field configurations generated by the European Twisted Mass Collaboration with linear lattice size L ranging from 1.3 to 1.9 fm. The continuum limit is taken at a fixed value of L=1.3 fm, employing three values of the lattice spacing and two values of the pion mass constructed from sea quarks only. (orig.)

Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Slenkamp, Karla M.; Lynch, Michael S.; Van Kuiken, Benjamin E.; Brookes, Jennifer F.; Bannan, Caitlin C.; Daifuku, Stephanie L.; Khalil, Munira, E-mail: mkhalil@chem.washington.edu [Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195 (United States)

2014-02-28

Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (ν{sub CN}) vibrations found in [(NH{sub 3}){sub 5}Ru{sup III}NCFe{sup II}(CN){sub 5}]{sup −} (FeRu) dissolved in D{sub 2}O and formamide and [(NC){sub 5}Fe{sup II}CNPt{sup IV}(NH{sub 3}){sub 4}NCFe{sup II}(CN){sub 5}]{sup 4−} (FePtFe) dissolved in D{sub 2}O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the ν{sub CN} modes in the electronic ground state. The FTIR spectra of the ν{sub CN} modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic ν{sub CN} modes. The vibrational mode anharmonicities of the individual ν{sub CN} modes range from 14 to 28 cm{sup −1}. The mixed-mode anharmonicities range from 2 to 14 cm{sup −1}. In general, the bridging ν{sub CN} mode is most weakly coupled to the radial ν{sub CN} mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four ν{sub CN} modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D{sub 2}O. The ν{sub CN} modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm{sup −1}. This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the ν{sub CN} modes in cyanide-bridged transition metal mixed valence complexes.

Valency and molecular structure

CERN Document Server

Cartmell, E

1977-01-01

Valency and Molecular Structure, Fourth Edition provides a comprehensive historical background and experimental foundations of theories and methods relating to valency and molecular structures. In this edition, the chapter on Bohr theory has been removed while some sections, such as structures of crystalline solids, have been expanded. Details of structures have also been revised and extended using the best available values for bond lengths and bond angles. Recent developments are mostly noted in the chapter on complex compounds, while a new chapter has been added to serve as an introduction t

[Emotional valence of words in schizophrenia].

Science.gov (United States)

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

Localized description of valence fluctuations

International Nuclear Information System (INIS)

Alascio, B.; Allub, R.; Aligia, A.

1979-07-01

The authors set up a model for intermediate valence equivalent to the ''atomic'' limit of the Anderson Hamiltonian. Detailed analysis of this model shows that most of the essential characteristics of valence fluctuators are already present in this crudely simplified Hamiltonian. The spin-spin and the 4f charge-charge correlation functions are studied and it is shown that it is possible to define a spin fluctuation frequency ωsub(s.f.) and a charge fluctuation frequency ωsub(ch.f.).ωsub(s.f.) and ωsub(ch.f.) can differ considerably for some values of the parameters of the model. The magnetic susceptibility and the specific heat are calculated as functions of temperature and it is shown how the results simulate the behaviour found in valence fluctuators. (author)

The structure and energetic of AlAsn (n = 1-15) clusters: A first-principles study

International Nuclear Information System (INIS)

Guo Ling

2010-01-01

Geometric structures of AlAs n (n = 1-15) clusters are reported. The binding energy, dissociation energy, stability of these clusters are studied with the three-parameter hybrid generalized gradient approximation (GGA) due to Becke-Lee-Yang-Parr (B3LYP). Ionization potentials, electron affinities, hardness, and static polarizabilities are calculated for the ground-state structures within the same method. The growth pattern for AlAs n (n = 6-15) clusters is Al-substituted pure As n+1 clusters and it keeps the similar frameworks of the most stable As n+1 clusters (for example AlAs 6 , AlAs 7 , AlAs 9 , AlAs 14 and AlAs 15 clusters) or capping the different sides of the low-lying geometry of As n clusters (for example AlAs 8 , AlAs 10 , AlAs 11 , and AlAs 12 clusters). The Al atom prefer to occupy a peripheral position for n n (n = 1-5, 13) clusters. The odd-even oscillations from AlAs n (n = 5-15) in the dissociation energy, the second-order energy differences, the HOMO-LUMO gaps, the electron affinity, and the hardness are more pronounced. The stability analysis based on the energies clearly shows the AlAs n clusters from n = 5 with an even number of valence electrons are more stable than clusters with odd number of valence electrons.

Evidence of dithionite contribution to the low-frequency resonance Raman spectrum of reduced and mixed-valence cytochrome c oxidase.

Science.gov (United States)

Centeno, J A

1992-02-01

The resonance Raman spectra of deoxygenated solutions of mixed-valence cyanide-bound and fully reduced cytochrome oxidase derivatives that have been reduced in the presence of aqueous or solid sodium dithionite exhibit two new low-frequency lines centered at 474 and 590 cm-1. These lines were not observed when the reductant system was changed to a solution containing ascorbate and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD). Under enzyme turnover conditions, the addition of dithionite to the reoxidized protein (the 428-nm or "oxygenated" form) increases the intensity of these lines, while reoxidation and rereduction of the enzyme in the presence of ascorbate/TMPD resulted in the absence of both lines. Our data suggest that both lines must have contributions from species formed from aqueous dithionite, presumably the SO2 species, since these two lines are also observed in the Raman spectrum of a solution of aqueous dithionite, but not in the spectrum of an ascorbate/TMPD solution. Since heme metal-ligand stretch vibrations are expected to appear in the low-frequency region from 215 to 670 cm-1, our results indicate that special care should be exercised during the interpretation of the cytochrome a3 resonance Raman spectrum.

Isotopic clusters

International Nuclear Information System (INIS)

Geraedts, J.M.P.

1983-01-01

Spectra of isotopically mixed clusters (dimers of SF 6 ) are calculated as well as transition frequencies. The result leads to speculations about the suitability of the laser-cluster fragmentation process for isotope separation. (Auth.)

Positive valence music restores executive control over sustained attention.

Science.gov (United States)

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.

Negative pressure driven valence instability of Eu in cubic Eu{sub 0.4}La{sub 0.6}Pd{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Pandey, Abhishek [S N Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata-700098 (India); Mazumdar, Chandan; Ranganathan, R [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata-700064 (India)], E-mail: abhishek.phy@gmail.com, E-mail: chandan.mazumar@saha.ac.in

2009-05-27

We report the change in the valency of Eu-ions in the binary intermetallic cubic compound EuPd{sub 3} induced by La doping at rare-earth sites. Doping of La generates negative chemical pressure in the lattice, resulting in a significant increase of the lattice parameter without altering the simple-cubic structure of the compound. Results of dc-magnetic measurements suggest that this increase in the lattice parameter is associated with the valence transition of Eu-ions from Eu{sup 3+} to a mixed-valent state. As Eu{sup 2+}-ions possess a large magnetic moment, this valence transition significantly modifies the magnetic behavior of the compound. In contrast to introducing boron at the vacant body center site of the unit cell to change the valency of Eu-ions, as in the case of EuPd{sub 3}B, our results suggest it can also be altered by doping a rare-earth ion of larger size at the lattice site of Eu in EuPd{sub 3}.

Investigation of the 9B nucleus and its cluster-nucleon correlations

Science.gov (United States)

Zhao, Qing; Ren, Zhongzhou; Lyu, Mengjiao; Horiuchi, Hisashi; Funaki, Yasuro; Röpke, Gerd; Schuck, Peter; Tohsaki, Akihiro; Xu, Chang; Yamada, Taiichi; Zhou, Bo

2018-05-01

In order to study the correlations between clusters and nucleons in light nuclei, we formulate a new superposed Tohsaki-Horiuchi-Schuck-Röpke (THSR) wave function which describes both spatially large spreading and cluster-correlated dynamics of valence nucleons. Using this new THSR wave function, the binding energy of 9B is significantly improved in comparison with our previous studies. We calculate the excited states of 9B and obtain an energy spectrum of 9B which is consistent with the experimental results. This includes the prediction of the first 1 /2+ excited state of 9B which is not yet fixed experimentally. We study the proton dynamics in 9B and find that the cluster-proton correlation plays an essential role for the proton dynamics in the ground state of 9B. Furthermore, we discuss the density distribution of the valence proton with special attention to its tail structure. Finally, the resonance nature of excited states of 9B is illustrated comparing root-mean-square radii between the ground and excited states.

Architectural Representation of Valence in the Limbic System

Science.gov (United States)

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

Local valence balance in the structure of a high-temperature superconductor

International Nuclear Information System (INIS)

Nalbandyan, V.B.

1990-01-01

Hitherto superconductivity of complex oxides has been observed only if the metal is present in a mixed (nonintegral) degree of oxidation. It is of interest to verify the statement that in YBa 2 Cu 3 O x there is no copper in a degree of oxidation above 2+; instead of this, part of the oxygen is in the degree of oxidation 1-. Thus, the calculations of the valence forces tell against the presence of copper in a mixed degree of oxidation between 2+ and 3+ in high-temperature superconductors of the stoichiometric composition RBa 2 Cu 3 O 7 . In two-dimensional layers, copper is in the degree of oxidation 2+ (or even lower), while the electron holes are concentrated in one-dimensional chains - either in the form Cu(3+) or in the form O(1-)

RESONANT MAGNETIC-X-RAY SCATTERING FROM MIXED-VALENCE TMSE

NARCIS (Netherlands)

MCWHAN, DB; ISAACS, ED; CARRA, P; SHAPIRO, SM; THOLE, BT; HOSHINO, S

1993-01-01

The mixed-valent compound TmSe has been studied in its antiferromagnetic state (T

On triangle meshes with valence dominant vertices

KAUST Repository

Morvan, Jean-Marie

2018-02-16

We study triangulations $\\\\cal T$ defined on a closed disc $X$ satisfying the following condition: In the interior of $X$, the valence of all vertices of $\\\\cal T$ except one of them (the irregular vertex) is $6$. By using a flat singular Riemannian metric adapted to $\\\\cal T$, we prove a uniqueness theorem when the valence of the irregular vertex is not a multiple of $6$. Moreover, for a given integer $k >1$, we exhibit non isomorphic triangulations on $X$ with the same boundary, and with a unique irregular vertex whose valence is $6k$.

On triangle meshes with valence dominant vertices

KAUST Repository

Morvan, Jean-Marie

2018-01-01

We study triangulations $\\cal T$ defined on a closed disc $X$ satisfying the following condition: In the interior of $X$, the valence of all vertices of $\\cal T$ except one of them (the irregular vertex) is $6$. By using a flat singular Riemannian metric adapted to $\\cal T$, we prove a uniqueness theorem when the valence of the irregular vertex is not a multiple of $6$. Moreover, for a given integer $k >1$, we exhibit non isomorphic triangulations on $X$ with the same boundary, and with a unique irregular vertex whose valence is $6k$.

Electronic structures and water reactivity of mixed metal sulfide cluster anions

Energy Technology Data Exchange (ETDEWEB)

Saha, Arjun; Raghavachari, Krishnan [Department of Chemistry, Indiana University, Bloomington, Indiana 47405 (United States)

2014-08-21

The electronic structures and chemical reactivity of the mixed metal sulfide cluster anion (MoWS{sub 4}{sup −}) have been investigated with density functional theory. Our study reveals the presence of two almost isoenergetic structural isomers, both containing two bridging sulfur atoms in a quartet state. However, the arrangement of the terminal sulfur atoms is different in the two isomers. In one isomer, the two metals are in the same oxidation state (each attached to one terminal S). In the second isomer, the two metals are in different oxidation states (with W in the higher oxidation state attached to both terminal S). The reactivity of water with the two lowest energy isomers has also been studied, with an emphasis on pathways leading to H{sub 2} release. The reactive behavior of the two isomers is different though the overall barriers in both systems are small. The origin of the differences are analyzed and discussed. The reaction pathways and barriers are compared with the corresponding behavior of monometallic sulfides (Mo{sub 2}S{sub 4}{sup −} and W{sub 2}S{sub 4}{sup −}) as well as mixed metal oxides (MoWO{sub 4}{sup −})

Social learning modulates the lateralization of emotional valence.

Science.gov (United States)

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.

Impaired mixed emotion processing in the right ventrolateral prefrontal cortex in schizophrenia: an fMRI study.

Science.gov (United States)

Szabó, Ádám György; Farkas, Kinga; Marosi, Csilla; Kozák, Lajos R; Rudas, Gábor; Réthelyi, János; Csukly, Gábor

2017-12-08

Schizophrenia has a negative effect on the activity of the temporal and prefrontal cortices in the processing of emotional facial expressions. However no previous research focused on the evaluation of mixed emotions in schizophrenia, albeit they are frequently expressed in everyday situations and negative emotions are frequently expressed by mixed facial expressions. Altogether 37 subjects, 19 patients with schizophrenia and 18 healthy control subjects were enrolled in the study. The two study groups did not differ in age and education. The stimulus set consisted of 10 fearful (100%), 10 happy (100%), 10 mixed fear (70% fear and 30% happy) and 10 mixed happy facial expressions. During the fMRI acquisition pictures were presented in a randomized order and subjects had to categorize expressions by button press. A decreased activation was found in the patient group during fear, mixed fear and mixed happy processing in the right ventrolateral prefrontal cortex (VLPFC) and the right anterior insula (RAI) at voxel and cluster level after familywise error correction. No difference was found between study groups in activations to happy facial condition. Patients with schizophrenia did not show a differential activation between mixed happy and happy facial expression similar to controls in the right dorsolateral prefrontal cortex (DLPFC). Patients with schizophrenia showed decreased functioning in right prefrontal regions responsible for salience signaling and valence evaluation during emotion recognition. Our results indicate that fear and mixed happy/fear processing are impaired in schizophrenia, while happy facial expression processing is relatively intact.

Valence nucleons in self-consistent fields

International Nuclear Information System (INIS)

Di Toro, M.; Lomnitz-Adler, J.

1978-01-01

An iterative approach to determine directly the best Hartree-Fock one-body density rho is extended by expressing rho in terms of a core and a valence part and allowing for general crossings of occupied and unoccupied levels in the valence part. Results are shown for 152 Sm and a microscopic analysis of the core structure of deformed light nuclei is carried out. (author)

Standard formation enthalpies of mononuclear and cluster oxoanions of boron, silicon and phosphorus

International Nuclear Information System (INIS)

Glybin, V.P.; Svirko, L.K.

2000-01-01

Standard formation enthalpies of boron, silicon and phosphorus are calculated. For calculations thermochemical method in conjunction with potential energy model of oxoanions in approximation of valence-force field of molecules and crystals are used. In the model of valence-force field ion-covalent crystals are considered as population of clusters of molecular type the number of which is equal to number of translation-nonequivalent atoms in the lattice dipped in nonhomogeneous electrostatic field of long-range interactions. For gaseous oxoanions field created by end oxygen atoms or other ones on which negative charge of anions is localized serves as equivalent of nonhomogeneous electrostatic field. In such approach potential energy of oxoanion is equal to sum of energy of electrostatic repulsion of negatively charged atoms and energy of valent element-oxygen bonds in neutral cluster [ru

Heparan sulfate chain valency controls syndecan-4 function in cell adhesion

DEFF Research Database (Denmark)

Gopal, Sandeep; Bober, Adam; Whiteford, James R

2010-01-01

, clustering of one-chain syndecan-4 forms with antibodies overcame the block, indicating that valency of interactions with ligands is a key component of syndecan-4 function. Measurements of focal contact/adhesion size and focal adhesion kinase phosphorylation correlated with syndecan-4 status and alpha...... of the core protein cytoplasmic domain, though not interactions with PDZ proteins. A second key requirement is multiple heparan sulfate chains. Mutant syndecan-4 with no chains, or only one chain, failed to restore the wild type phenotype, while those expressing two or three were competent. However......-smooth muscle actin organization, being reduced where syndecan-4 function was compromised by a lack of multiple heparan sulfate chains....

Theory of dressed bosons and nuclear matter distributions

International Nuclear Information System (INIS)

Tomaselli, M.; Liu, L.C.; Tanihata, I.

2002-09-01

The structure of nuclei with large neutron or proton-neutron excess, i.e., with large isospin components, is investigated in the Boson Dynamic Correlation Model where the valence particle pairs are dressed by their interactions with the microscopic clusters of the core. The mixed-mode states of the model are the eigenstates of a set of nonlinear equations. We solve these equations in terms of the cluster factorizations that are introduced to compute the n-boson matrix elements. Our calculation of the energy levels of 18 O reveals a strong mixing between the valence and core clusters which leads to a large reduction of the spectroscopic factors as calculated in Shell-Model approximations. The coupling of valence- to core-clusters gives a new insight into the halo formation in neutron-rich nuclei, namely, the halo is also a consequence of the excitation of the core protons. The calculated matter distributions of 6 He and 6 Li exhibit strong similarities, which indicate that halo formation in nuclei with proton-neutron excess must be postulated. The matter distributions of these two isotopes reproduce well the differential cross sections obtained in the proton elastic scattering experiments performed at GSI in inverse kinematics at an energy of 0.7 GeV/u. (orig.)

M-edge x-ray absorption spectroscopy: A new tool for dilute mixed-valent materials

International Nuclear Information System (INIS)

Kaindl, G.; Brewer, W.D.; Kalkowski, G.; Holtzberg, F.

1983-01-01

The valence of Tm compounds is derived from M/sub V/ x-ray absorption spectra recorded by total electron yield under ultra-high-vacuum conditions. For mixed-valent systems the spectra are superpositions of Tm 3+ (three lines) and Tm 2+ (one line) components, providing accurate mean valence values even in highly dilute systems, such as Tm/sub x/Y/sub 1-x/Se, which agree well with those from lattice constant systematics. A surface valence change on TmS(100) is identified as an initial-state effect

Clustering of attitudes towards obesity: a mixed methods study of Australian parents and children.

Science.gov (United States)

Olds, Tim; Thomas, Samantha; Lewis, Sophie; Petkov, John

2013-10-12

Current population-based anti-obesity campaigns often target individuals based on either weight or socio-demographic characteristics, and give a 'mass' message about personal responsibility. There is a recognition that attempts to influence attitudes and opinions may be more effective if they resonate with the beliefs that different groups have about the causes of, and solutions for, obesity. Limited research has explored how attitudinal factors may inform the development of both upstream and downstream social marketing initiatives. Computer-assisted face-to-face interviews were conducted with 159 parents and 184 of their children (aged 9-18 years old) in two Australian states. A mixed methods approach was used to assess attitudes towards obesity, and elucidate why different groups held various attitudes towards obesity. Participants were quantitatively assessed on eight dimensions relating to the severity and extent, causes and responsibility, possible remedies, and messaging strategies. Cluster analysis was used to determine attitudinal clusters. Participants were also able to qualify each answer. Qualitative responses were analysed both within and across attitudinal clusters using a constant comparative method. Three clusters were identified. Concerned Internalisers (27% of the sample) judged that obesity was a serious health problem, that Australia had among the highest levels of obesity in the world and that prevalence was rapidly increasing. They situated the causes and remedies for the obesity crisis in individual choices. Concerned Externalisers (38% of the sample) held similar views about the severity and extent of the obesity crisis. However, they saw responsibility and remedies as a societal rather than an individual issue. The final cluster, the Moderates, which contained significantly more children and males, believed that obesity was not such an important public health issue, and judged the extent of obesity to be less extreme than the other clusters

Fe II/Fe III mixed-valence state induced by Li-insertion into the metal-organic-framework Mil53(Fe): A DFT+U study

Science.gov (United States)

Combelles, C.; Ben Yahia, M.; Pedesseau, L.; Doublet, M.-L.

The iron-based metal-organic-framework MIL53(Fe) has recently been tested as a cathode materials for Li-Ion batteries, leading to promising cycling life and rate capability. Despite a poor capacity of 70 mAh g -1 associated with the exchange of almost 0.5Li/Fe, this result is the first evidence of a reversible lithium insertion never observed in a MOF system. In the present study, the MIL53(Fe) redox mechanism is investigated through first-principles DFT+U calculations. The results show that MIL53(Fe) is a weak antiferromagnetic charge transfer insulator at T = 0 K, with iron ions in the high-spin S = 5/2 state. Its reactivity vs elemental lithium is then investigated as a function of lithium composition and distribution over the most probable Li-sites of the MOF structure. The redox mechanism is fully interpreted as a two-step insertion/conversion mechanism, associated with the stabilization of the Fe 3+/Fe 2+ mixed-valence state prior to the complete decomposition of the inorganic-organic interactions within the porous MOF architecture.

Valence and charge-transfer optical properties for some SinCm (m, n ≤ 12) clusters: Comparing TD-DFT, complete-basis-limit EOMCC, and benchmarks from spectroscopy

Science.gov (United States)

Lutz, Jesse J.; Duan, Xiaofeng F.; Ranasinghe, Duminda S.; Jin, Yifan; Margraf, Johannes T.; Perera, Ajith; Burggraf, Larry W.; Bartlett, Rodney J.

2018-05-01

Accurate optical characterization of the closo-Si12C12 molecule is important to guide experimental efforts toward the synthesis of nano-wires, cyclic nano-arrays, and related array structures, which are anticipated to be robust and efficient exciton materials for opto-electronic devices. Working toward calibrated methods for the description of closo-Si12C12 oligomers, various electronic structure approaches are evaluated for their ability to reproduce measured optical transitions of the SiC2, Si2Cn (n = 1-3), and Si3Cn (n = 1, 2) clusters reported earlier by Steglich and Maier [Astrophys. J. 801, 119 (2015)]. Complete-basis-limit equation-of-motion coupled-cluster (EOMCC) results are presented and a comparison is made between perturbative and renormalized non-iterative triples corrections. The effect of adding a renormalized correction for quadruples is also tested. Benchmark test sets derived from both measurement and high-level EOMCC calculations are then used to evaluate the performance of a variety of density functionals within the time-dependent density functional theory (TD-DFT) framework. The best-performing functionals are subsequently applied to predict valence TD-DFT excitation energies for the lowest-energy isomers of SinC and Sin-1C7-n (n = 4-6). TD-DFT approaches are then applied to the SinCn (n = 4-12) clusters and unique spectroscopic signatures of closo-Si12C12 are discussed. Finally, various long-range corrected density functionals, including those from the CAM-QTP family, are applied to a charge-transfer excitation in a cyclic (Si4C4)4 oligomer. Approaches for gauging the extent of charge-transfer character are also tested and EOMCC results are used to benchmark functionals and make recommendations.

Observations on small anionic clusters in an electrostatic ion beam trap

International Nuclear Information System (INIS)

Eritt, Markus

2008-01-01

The term atomic cluster relates to compounds of at least two or three atoms. Thereby the physical properties are size dependent and the property transitions between single atoms and bulk material are not always smooth. Ion traps allow it to observe internal cluster properties independent from the influence of external forces. In this work the electron induced decay of singly negatively charged atomic clusters was observed. The dissociation cross section of the clusters is dominated by detachment of the only weakly bound outer electrons. For simple atoms at low electron energies a simple scaling law can be obtained that includes only the binding energies of the valence electrons. Nevertheless for larger sizes theoretical calculations predict so called ''giant resonances'' as dominant decay process in metal clusters. Due to mass limitations in storage rings exist so far only cross section measurements for simple anions and small negative molecules. In this work the electron detachment cross sections of small negatively charged carbon (C n - n=2-12), aluminium (Al n - n=2-7) and silver clusters (Ag n - n=1-11) were measured in an electrostatic ion beam trap. The classical scaling law, including only the binding energies of the valence electrons, turned out to be not sufficient, especially for larger clusters. In order to improve the correlation between measured and predicted values it was proposed to involve the influence of the cluster volume and the specific polarisability induced by long range coulomb interaction. For silver clusters the best agreement was obtained using a combination of the projected area reduced by the polarisability. The existence of ''giant resonances'' could not be confirmed. According to theory for clusters with a broad internal energy distribution, a power-law decay close to 1/time is expected. For some clusters the lifetime behaviour would be strongly quenched by photon emission. The thermionic evaporative decay of anionic aluminium and

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

DEFF Research Database (Denmark)

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

2017-01-01

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...... valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitals 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....

Valence behavior of Eu-ions in intermetallic compound Ce{sub 0.5}Eu{sub 0.5}Pd{sub 3}B{sub 0.5}

Energy Technology Data Exchange (ETDEWEB)

Pandey, Abhishek, E-mail: apandey@ameslab.gov [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India); S.N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Mazumdar, Chandan, E-mail: chandan.mazumdar@saha.ac.in [S.N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Ranganathan, R. [S.N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Raghavendra Reddy, V.; Gupta, Ajay [UGC-DAE Consortium for Scientific Research, University Campus, Khandawa Road, Indore (India)

2011-12-15

We have studied the valence behavior of rare-earth ions, in particular Eu-ions, in a cubic intermetallic compound Ce{sub 0.5}Eu{sub 0.5}Pd{sub 3}B{sub 0.5} which is a homogeneous solid solution of two mixed-valent compounds CePd{sub 3} and EuPd{sub 3}B. Results of {sup 151}Eu Moessbauer spectroscopic measurements show that two different valence states, i.e., divalent- and trivalent-like states of Eu-ions exist in the compound. The possible reason for the observed heterogeneous valency vis-a-vis the variation in the chemical environment and the number of nearest-neighbor B atoms surrounding the Eu-ions has been discussed. Our results demonstrate that B incorporation in such Eu-based cubic intermetallic compounds leads to a situation where heterogeneous-valence state of Eu-ions is an energetically favorable ground state. - Highlights: > Intermetallic compound Ce{sub 0.5}Eu{sub 0.5}Pd{sub 3}B{sub 0.5} crystallizes in a single phase. > Eu-ions in Ce{sub 0.5}Eu{sub 0.5}Pd{sub 3}B{sub 0.5} are charge-ordered compared to +2.3 valency in Ce{sub 0.5}Eu{sub 0.5}Pd{sub 3}. > B incorporation makes charge-ordered state of Eu-ions energetically more favorable. > Nearest-neighbor chemical environment affects the Eu valency.

Chemical and valence reconstruction at the surface of SmB6 revealed by means of resonant soft x-ray reflectometry

Science.gov (United States)

Zabolotnyy, V. B.; Fürsich, K.; Green, R. J.; Lutz, P.; Treiber, K.; Min, Chul-Hee; Dukhnenko, A. V.; Shitsevalova, N. Y.; Filipov, V. B.; Kang, B. Y.; Cho, B. K.; Sutarto, R.; He, Feizhou; Reinert, F.; Inosov, D. S.; Hinkov, V.

2018-05-01

Samarium hexaboride (SmB6), a Kondo insulator with mixed valence, has recently attracted much attention as a possible host for correlated topological surface states. Here, we use a combination of x-ray absorption and reflectometry techniques, backed up with a theoretical model for the resonant M4 ,5 absorption edge of Sm and photoemission data, to establish laterally averaged chemical and valence depth profiles at the surface of SmB6. We show that upon cleaving, the highly polar (001) surface of SmB6 undergoes substantial chemical and valence reconstruction, resulting in boron termination and a Sm3 + dominated subsurface region. Whereas at room temperature, the reconstruction occurs on a timescale of less than 2 h, it takes about 24 h below 50 K. The boron termination is eventually established, irrespective of the initial termination. Our findings reconcile earlier depth resolved photoemission and scanning tunneling spectroscopy studies performed at different temperatures and are important for better control of surface states in this system.

Importance-truncated shell model for multi-shell valence spaces

Energy Technology Data Exchange (ETDEWEB)

Stumpf, Christina; Vobig, Klaus; Roth, Robert [Institut fuer Kernphysik, TU Darmstadt (Germany)

2016-07-01

The valence-space shell model is one of the work horses in nuclear structure theory. In traditional applications, shell-model calculations are carried out using effective interactions constructed in a phenomenological framework for rather small valence spaces, typically spanned by one major shell. We improve on this traditional approach addressing two main aspects. First, we use new effective interactions derived in an ab initio approach and, thus, establish a connection to the underlying nuclear interaction providing access to single- and multi-shell valence spaces. Second, we extend the shell model to larger valence spaces by applying an importance-truncation scheme based on a perturbative importance measure. In this way, we reduce the model space to the relevant basis states for the description of a few target eigenstates and solve the eigenvalue problem in this physics-driven truncated model space. In particular multi-shell valence spaces are not tractable otherwise. We combine the importance-truncated shell model with refined extrapolation schemes to approximately recover the exact result. We present first results obtained in the importance-truncated shell model with the newly derived ab initio effective interactions for multi-shell valence spaces, e.g., the sdpf shell.

Eliciting mixed emotions: A meta-analysis comparing models, types and measures.

Directory of Open Access Journals (Sweden)

Raul eBerrios

2015-04-01

Full Text Available The idea that people can experience two oppositely valenced emotions has been controversial ever since early attempts to investigate the construct of mixed emotions. This meta-analysis examined the robustness with which mixed emotions have been elicited experimentally. A systematic literature search identified 63 experimental studies that instigated the experience of mixed emotions. Studies were distinguished according to the structure of the underlying affect model – dimensional or discrete – as well as according to the type of mixed emotions studied (e.g., happy-sad, fearful-happy, positive-negative. The meta-analysis using a random-effects model revealed a moderate to high effect size for the elicitation of mixed emotions (dIG+ = .77, which remained consistent regardless of the structure of the affect model, and across different types of mixed emotions. Several methodological and design moderators were tested. Studies using the minimum index (i.e., the minimum value between a pair of opposite valenced affects resulted in smaller effect sizes, whereas subjective measures of mixed emotions increased the effect sizes. The presence of more women in the samples was also associated with larger effect sizes. The current study indicates that mixed emotions are a robust, measurable and non-artifactual experience. The results are discussed in terms of the implications for an affect system that has greater versatility and flexibility than previously thought.

Eliciting mixed emotions: a meta-analysis comparing models, types, and measures

Science.gov (United States)

Berrios, Raul; Totterdell, Peter; Kellett, Stephen

2015-01-01

The idea that people can experience two oppositely valenced emotions has been controversial ever since early attempts to investigate the construct of mixed emotions. This meta-analysis examined the robustness with which mixed emotions have been elicited experimentally. A systematic literature search identified 63 experimental studies that instigated the experience of mixed emotions. Studies were distinguished according to the structure of the underlying affect model—dimensional or discrete—as well as according to the type of mixed emotions studied (e.g., happy-sad, fearful-happy, positive-negative). The meta-analysis using a random-effects model revealed a moderate to high effect size for the elicitation of mixed emotions (dIG+ = 0.77), which remained consistent regardless of the structure of the affect model, and across different types of mixed emotions. Several methodological and design moderators were tested. Studies using the minimum index (i.e., the minimum value between a pair of opposite valenced affects) resulted in smaller effect sizes, whereas subjective measures of mixed emotions increased the effect sizes. The presence of more women in the samples was also associated with larger effect sizes. The current study indicates that mixed emotions are a robust, measurable and non-artifactual experience. The results are discussed in terms of the implications for an affect system that has greater versatility and flexibility than previously thought. PMID:25926805

Unscrambling the Omlette: a New Bubble and Crystal Clustering Mechanism in Chaotically Mixed Magma Flows

Science.gov (United States)

Robertson, J.; Metcalfe, G.; Wang, S.; Barnes, S. J.

2014-12-01

The concentration of bubbles, crystals or droplets into small volumes of magma is a key trigger for many interesting magmatic processes. For example, gas slugs driving Strombolian eruptions form from the coalesence of exsolved bubbles within a volcanic conduit, while Ni-Cu-PGE magmatic sulfide deposits require a concentration of dense sulfide droplets from a large volume of magma to form a massive ore body. However the physical mechanism for this clustering remains unresolved - especially since small particles in active magma flows are expected to mostly track flow streamlines rather than clustering. We have uncovered a previously unreported clustering mechanism which is applicable to magmatic flows. This mechanism involves the interaction of particles with two kinds of chaotic flow structure: (a) high-strain regions within the well-mixed chaotic zones of the flow, and (b) unmixed islands of stability within the chaotic flow, known as Kolmogorov-Arnold-Moser (KAM) regions. The first figure shows the difference between chaotic and KAM regions in a chaotic laminar pipe flow. Trapping occurs when particles are scattered from high-strain regions in the chaotic zones and become trapped in the KAM regions, leading to a rapid concentration of particles relative to their original distribution (shown in the second series of figures). Using a combination of these analogue experiments and theoretical analysis we outline the conditions under which this clustering process can occur. We examine the onset of secondary density-related instabilities and the effects of increased particle-particle interaction within the clustered particles, and highlight the impact of particle clustering on the dynamics of magma ascent and emplacement.

Ion collision-induced chemistry in pure and mixed loosely bound clusters of coronene and C60 molecules.

Science.gov (United States)

Domaracka, Alicja; Delaunay, Rudy; Mika, Arkadiusz; Gatchell, Michael; Zettergren, Henning; Cederquist, Henrik; Rousseau, Patrick; Huber, Bernd A

2018-05-23

Ionization, fragmentation and molecular growth have been studied in collisions of 22.5 keV He2+- or 3 keV Ar+-projectiles with pure loosely bound clusters of coronene (C24H12) molecules or with loosely bound mixed C60-C24H12 clusters by using mass spectrometry. The heavier and slower Ar+ projectiles induce prompt knockout-fragmentation - C- and/or H-losses - from individual molecules and highly efficient secondary molecular growth reactions before the clusters disintegrate on picosecond timescales. The lighter and faster He2+ projectiles have a higher charge and the main reactions are then ionization by ions that are not penetrating the clusters. This leads mostly to cluster fragmentation without molecular growth. However, here penetrating collisions may also lead to molecular growth but to a much smaller extent than with 3 keV Ar+. Here we present fragmentation and molecular growth mass distributions with 1 mass unit resolution, which reveals that the same numbers of C- and H-atoms often participate in the formation and breaking of covalent bonds inside the clusters. We find that masses close to those with integer numbers of intact coronene molecules, or with integer numbers of both intact coronene and C60 molecules, are formed where often one or several H-atoms are missing or have been added on. We also find that super-hydrogenated coronene is formed inside the clusters.

Valence-Dependent Belief Updating: Computational Validation

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Bojana Kuzmanovic

2017-06-01

Full Text Available 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

Emotion and language: Valence and arousal affect word recognition

Science.gov (United States)

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

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

Science.gov (United States)

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.

Intensification of Development of Mixed Transportation of Freight in Ukraine through Formation of the Network of Transportation and Logistic Centres and Transportation and Logistic Clusters

Directory of Open Access Journals (Sweden)

Karpenko Oksana O.

2013-11-01

Full Text Available Development of mixed transportation is a prospective direction of development of the transportation system of Ukraine. The article analyses the modern state of development of mixed transportation of freight in Ukraine. The most popular types of combined transportation (refers to multi-modal are container and contrailer trains, which are formed both in Ukraine (Viking and Yaroslav and in other countries, first of all, Belarus (Zubr. One of the reasons of underdevelopment of mixed transportation of freight in Ukraine is absence of a developed network of transportation and logistic centres. The article offers to form a network of transportation and logistic centres in Ukraine as a way of intensification of development of mixed transportations of freight, since they facilitate co-ordination of use of various types of transport and support integrated management of material flows. Transportation and logistic centres should become a start-up complex, around which transportation and logistic clusters would be gradually formed. Transportation and logistic clusters is a new efficient form of network organisation and management of transportation and logistic services and they also ensure growth of efficiency of use of the regional transportation and logistic potential of Ukraine. The article shows prospective supporting transportation and logistic centres and centres of formation of transportation and logistic clusters in the territory of Ukraine. Formation of efficient transportation and logistic system of Ukraine on the basis of a network of transportation and logistic clusters would facilitate entering of Ukraine into the world transportation environment and would allow acceleration of introduction of efficient logistic schemes of freight delivery, in particular, mixed transportation of freight.

Modeling of mixing processes: Fluids, particulates, and powders

Energy Technology Data Exchange (ETDEWEB)

Ottino, J.M.; Hansen, S. [Northwestern Univ., Evanston, IL (United States)

1995-12-31

Work under this grant involves two main areas: (1) Mixing of Viscous Liquids, this first area comprising aggregation, fragmentation and dispersion, and (2) Mixing of Powders. In order to produce a coherent self-contained picture, we report primarily on results obtained under (1), and within this area, mostly on computational studies of particle aggregation in regular and chaotic flows. Numerical simulations show that the average cluster size of compact clusters grows algebraically, while the average cluster size of fractal clusters grows exponentially; companion mathematical arguments are used to describe the initial growth of average cluster size and polydispersity. It is found that when the system is well mixed and the capture radius independent of mass, the polydispersity is constant for long-times and the cluster size distribution is self-similar. Furthermore, our simulations indicate that the fractal nature of the clusters is dependent upon the mixing.

Pulse-coupled mixed-mode oscillators: Cluster states and extreme noise sensitivity

Science.gov (United States)

Karamchandani, Avinash J.; Graham, James N.; Riecke, Hermann

2018-04-01

Motivated by rhythms in the olfactory system of the brain, we investigate the synchronization of all-to-all pulse-coupled neuronal oscillators exhibiting various types of mixed-mode oscillations (MMOs) composed of sub-threshold oscillations (STOs) and action potentials ("spikes"). We focus particularly on the impact of the delay in the interaction. In the weak-coupling regime, we reduce the system to a Kuramoto-type equation with non-sinusoidal phase coupling and the associated Fokker-Planck equation. Its linear stability analysis identifies the appearance of various cluster states. Their type depends sensitively on the delay and the width of the pulses. Interestingly, long delays do not imply slow population rhythms, and the number of emerging clusters only loosely depends on the number of STOs. Direct simulations of the oscillator equations reveal that for quantitative agreement of the weak-coupling theory the coupling strength and the noise have to be extremely small. Even moderate noise leads to significant skipping of STO cycles, which can enhance the diffusion coefficient in the Fokker-Planck equation by two orders of magnitude. Introducing an effective diffusion coefficient extends the range of agreement significantly. Numerical simulations of the Fokker-Planck equation reveal bistability and solutions with oscillatory order parameters that result from nonlinear mode interactions. These are confirmed in simulations of the full spiking model.

Reactions of mixed silver-gold cluster cations AgmAun+ (m+n=4,5,6) with CO: Radiative association kinetics and density functional theory computations

International Nuclear Information System (INIS)

Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M.

2006-01-01

Near thermal energy reactive collisions of small mixed metal cluster cations Ag m Au n + (m+n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu 3 + and Ag 2 Au 2 + are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu 2 CO + . In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77 to 1.09 eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a ''head-on'' fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag 2 Au 2 + suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed

Reactions of mixed silver-gold cluster cations AgmAun+ (m+n=4,5,6) with CO: Radiative association kinetics and density functional theory computations

Science.gov (United States)

Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M.

2006-09-01

Near thermal energy reactive collisions of small mixed metal cluster cations AgmAun+ (m +n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu3+ and Ag2Au2+ are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu2CO+. In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77to1.09eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a "head-on" fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag2Au2+ suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed.

16O + 16O + valence neutrons in molecular orbitals structures of positive- and negative-parity superdeformed bands in 34S

International Nuclear Information System (INIS)

Taniguchi, Yasutaka

2015-01-01

The structures of superdeformed (SD) states in 34 S have been investigated using the antisymmetrized molecular dynamics and generator coordinate method (GCM). The GCM basis wave functions are calculated via energy variation with a constraint on the quadrupole deformation parameter β. By applying the GCM after parity and angular momentum projections, the coexistence of two positive- and one negative-parity SD bands are predicted, and low-lying states and other deformed bands are obtained. The SD bands have structures of 16 O + 16 O + two valence neutrons in molecular orbitals around the two 16 O cores in a cluster picture. The configurations of the two valence neutrons are δ 2 and π 2 for the positive-parity SD bands and π 1 δ 1 for the negative-parity SD band. (author)

16O + 16O + valence neutrons in molecular orbitals structures of positive- and negative-parity superdeformed bands in 34S

International Nuclear Information System (INIS)

Taniguchi, Yasutaka

2014-01-01

The structures of superdeformed (SD) states in 34 S are investigated using the antisymmetrized molecular dynamics and generator coordinate method (GCM). The GCM basis wave functions are calculated via energy variation with a constraint on the quadrupole deformation parameter β. By applying the GCM after parity and angular momentum projections, the coexistence of two positive- and one negative-parity SD bands are predicted, and low-lying states and other deformed bands are obtained. The SD bands have structures of 16 O + 16 O + two valence neutrons in molecular orbitals around the two 16 O cores in a cluster picture. The configurations of the two valence neutrons are δ 2 and π 2 for the positive-parity SD bands and π 1 δ 1 for the negative-parity SD band

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

Science.gov (United States)

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.

Directory of Open Access Journals (Sweden)

Peter Graf

Full Text Available 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.

The A-dependence of deep inelastic lepton-nuclear scattering from 6-quark clustering

International Nuclear Information System (INIS)

Chemtob, M.; Peschanszi, R.

1984-03-01

The correction to the nucleon valence quark structure functions implied by 6-quark clustering in nuclei are found to be in remarkable agreement with recent data from S.L.A.C. on the A-dependence of electron-nucleus deep inelastic scattering

Core level photoelectron spectroscopy probed heterogeneous xenon/neon clusters

International Nuclear Information System (INIS)

Pokapanich, Wandared; Björneholm, Olle; Öhrwall, Gunnar; Tchaplyguine, Maxim

2017-01-01

Binary rare gas clusters; xenon and neon which have a significant contrariety between sizes, produced by a co-expansion set up and have been studied using synchrotron radiation based x-ray photoelectron spectroscopy. Concentration ratios of the heterogeneous clusters; 1%, 3%, 5% and 10% were controlled. The core level spectra were used to determine structure of the mixed cluster and analyzed by considering screening mechanisms. Furthermore, electron binding energy shift calculations demonstrated cluster aggregation models which may occur in such process. The results showed that in the case of low mixing ratios of 3% and 5% of xenon in neon, the geometric structures exhibit xenon in the center and xenon/neon interfaced in the outer shells. However, neon cluster vanished when the concentration of xenon was increased to 10%. - Highlights: • Co-expansion setup is suitable for producing binary Xe/Ne clusters. • Appropriate temperature, pressure, and mixing ratios should be strictly controlled. • Low mixing ratio, Xe formed in the core and Xe/Ne interfacing in the outer shell. • High mixing ratio, only pure Xe clusters were detected.

Structure, magnetism, and theoretical study of a mixed-valence Co(II)3Co(III)4 heptanuclear wheel: lack of SMM behavior despite negative magnetic anisotropy.

Science.gov (United States)

Chibotaru, Liviu F; Ungur, Liviu; Aronica, Christophe; Elmoll, Hani; Pilet, Guillaume; Luneau, Dominique

2008-09-17

A mixed-valence Co(II)/Co(III) heptanuclear wheel [Co(II)3Co(III)4(L)6(MeO)6] (LH2 = 1,1,1-trifluoro-7-hydroxy-4-methyl-5-aza-hept-3-en-2-one) has been synthesized and its crystal structure determined using single-crystal X-ray diffraction. The valence state of each cobalt ion was established by bond valence sum calculations. Studies of the temperature dependence of the magnetic susceptibility and the field dependence of the magnetization evidence ferromagnetic interactions within the compound. In order to understand the magnetic properties of this Co7 wheel, we performed ab initio calculations for each cobalt fragment at the CASSCF/CASPT2 level, including spin-orbit coupling effects within the SO-RASSI approach. The four Co(III) ions were found to be diamagnetic and to give a significant temperature-independent paramagnetic contribution to the susceptibility. The spin-orbit coupling on the three Co(II) sites leads to separations of approximately 200 cm(-1) between the ground and excited Kramers doublets, placing the Co7 wheel into a weak-exchange limit in which the lowest electronic states are adequately described by the anisotropic exchange interaction between the lowest Kramers doublets on Co(II) sites. Simulation of the exchange interaction was done within the Lines model, keeping the fully ab initio treatment of magnetic anisotropy effects on individual cobalt fragments using a recently developed methodology. A good description of the susceptibility and magnetization was obtained for nearest-neighbor (J1) and next-nearest-neighbor (J2) exchange parameters (1.5 and 5.5 cm(-1), respectively). The strong ferromagnetic interaction between distant cobalt ions arises as a result of low electron-promotion energies in the exchange bridges containing Co(III) ions. The calculations showed a large value of the magnetization along the main magnetic axis (10.1 mu(B)), which is a combined effect of the ferromagnetic exchange interaction and negative magnetic anisotropy on

Energy band dispersion in photoemission spectra of argon clusters

International Nuclear Information System (INIS)

Foerstel, Marko; Mucke, Melanie; Arion, Tiberiu; Lischke, Toralf; Barth, Silko; Ulrich, Volker; Ohrwall, Gunnar; Bjoerneholm, Olle; Hergenhahn, Uwe; Bradshaw, Alex M.

2011-01-01

Using photoemission we have investigated free argon clusters from a supersonic nozzle expansion in the photon energy range from threshold up to 28 eV. Measurements were performed both at high resolution with a hemispherical electrostatic energy analyser and at lower resolution with a magnetic bottle device. The latter experiments were performed for various mean cluster sizes. In addition to the ∼1.5 eV broad 3p-derived valence band seen in previous work, there is a sharper feature at ∼15 eV binding energy. Surprisingly for non-oriented clusters, this peak shifts smoothly in binding energy over the narrow photon energy range 15.5-17.7 eV, indicating energy band dispersion. The onset of this bulk band-like behaviour could be determined from the cluster size dependence.

Decoding emotional valence from electroencephalographic rhythmic activity.

Science.gov (United States)

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.

Virtual Distance and Soundstage, and their Impacts on Experienced Emotional Valence

DEFF Research Database (Denmark)

Christensen, Justin

2015-01-01

stimuli should cause stronger valenced responses in the nearfield than at a distance. Thus, music experienced as being negatively valenced at a distance should be more negatively valenced in nearfield, and music that is experienced as having a positive valence at a distance should be more positively......Research from animal ethology and affective neuroscience suggest that a listener’s perceived distance from a signal source can alter their experienced emotional valence of the music. Furthermore, appraisal theories of emotion suggest that emotionally valenced responses will diverge according...... to the type of emotion presented. For these exploratory investigations, subjects listen to selected musical excerpts on speakers in combination with a tactile transducer attached to their chair. The listening sessions are recorded on EEG supported by subject feedback responses. My hypothesis is that musical...

Space-Valence Priming with Subliminal and Supraliminal Words

Directory of Open Access Journals (Sweden)

Ulrich eAnsorge

2013-02-01

Full Text Available 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.

Valence, arousal and cognitive control: A voluntary task switching study

Directory of Open Access Journals (Sweden)

Jelle eDemanet

2011-11-01

Full Text Available The present study focused on the interplay between arousal, valence and cognitive control. To this end, we investigated how arousal and valence associated with affective stimuli influenced cognitive flexibility when switching between tasks voluntarily. Three hypotheses were tested. First, a valence hypothesis that states that the positive valence of affective stimuli will facilitate both global and task-switching performance because of increased cognitive flexibility. Second, an arousal hypothesis that states that arousal, and not valence, will specifically impair task-switching performance by strengthening the previously executed task-set. Third, an attention hypothesis that states that both cognitive and emotional control ask for limited attentional resources, and predicts that arousal will impair both global and task-switching performance. The results showed that arousal affected task-switching but not global performance, possibly by phasic modulations of the noradrenergic system that reinforces the previously executed task. In addition, positive valence only affected global performance but not task-switching performance, possibly by phasic modulations of dopamine that stimulates the general ability to perform in a multitasking environment.

Hole energy and momentum distributions in valence bands

International Nuclear Information System (INIS)

Laan, G. van der.

1982-01-01

In order to understand the electrical and magnetic properties of solids, the knowledge of the density of states and the dispersion relation of the valence bands is indispensable. This thesis offers some alternative methods to obtain information about the nature of the valence band. Part A deals with the energy distribution of the photoelectrons. A simple model, which explains the core hole satellite structure in compounds with large correlation effects between the valence band holes and the created photo-hole, is outlined. CuCl, CuX 2 (X = F Cl and Br) are studied, by photoemission and Auger electron spectroscopies in determining the valence band properties. Part B deals with the simultaneous measurement of the energy and the wave vector of the emitted electrons. A practical example is given for the determination of the dispersion relation in copper. The measurements of a surface resonance band and the distribution of the secondary electrons are also reported. (Auth.)

Effect of valence on the electromigration in silver

International Nuclear Information System (INIS)

Nguyen Van Doan

1970-01-01

It is shown that the apparent effective valence Z B ** of a solute deduced from experiments differs from the true effective valence Z B * defined in the atomic models by a corrective term due to the 'vacancy flow effect'. The experimental results suggest that this corrective term is very important and that it is negative for transition elements; this hypothesis is confirmed for the case of iron in a copper matrix. For the elements to the right of silver in the periodic table, where the correction can be neglected, the effective valence of the solute varies linearly with z (z + 1), z being the difference between the valency of the solute and the solvent; in contrast, the further the solute is from the solvent in the periodic table the more nearly the electronic structure of the ion at the saddle point resembles that of the ion at the equilibrium position. (author) [fr

Looking for a gift of Nature: Hadron loops and hybrid mixing

International Nuclear Information System (INIS)

Close, Frank; Thomas, Christopher

2009-01-01

We investigate how coupling of valence q qbar to meson pairs can modify the properties of conventional q qbar and hybrid mesons. In a symmetry limit the mixing between hybrids and conventional q qbar with the same J PC is shown to vanish. Flavor mixing between heavy and light q qbar due to meson loops is shown to be dual to the

Prediction of valence and arousal from music features

NARCIS (Netherlands)

Den Brinker, A.C.; Van Dinther, C.H.B.A.; Skowronek, J.

2011-01-01

Mood is an important attribute of music and knowledge on mood can beused as a basic ingredient in music recommender and retrieval systems. Moods are assumed to be dominantly determined by two dimensions:valence and arousal. An experiment was conducted to attain data forsong-based ratings of valence

Electronic states in clusters of H forms of zeolites with variation of the Si/Al ratio

International Nuclear Information System (INIS)

Gun'ko, V.M.

1987-01-01

Fragments of H forms of zeolites of the faujasite type including up to 12 silicon- and aluminum-oxygen tetrahedrons and having different Si/Al ratios have been calculated in the cluster approximation by the MINDO/3 and CNDO/2 methods. The dependence of the integral and orbital densities of electronic states in the clusters on the aluminum content has been investigated. It has been shown that the profiles of the s- and p-orbital density of states of Al remain practically unchanged as the Si/Al ratio is lowered and that the maxima of the orbital density of states of Si broaden, and new maxima appear at the bottom and top of the valence band. When the acidity of the structural OH groups is lowered, the maxima of the orbital density of states of the H atoms are displaced appreciably only in the deep valence band, while in the upper valence band the positions of the peaks of the s-orbital density of states of the H atoms remain constant. Satisfactory agreement of the calculated orbital densities of states of Si, Al, and O with the corresponding x-ray photoelectron spectra has been obtained. In the deep valence band the data from the MINDO/3 method are better than those from the CNDO/2 method and reproduce the positions of the maxima in the x-ray photoelectron spectra

Valence photoelectron spectrum of KBr: Effects of electron correlation

International Nuclear Information System (INIS)

Calo, A.; Huttula, M.; Patanen, M.; Aksela, H.; Aksela, S.

2008-01-01

The valence photoelectron spectrum has been measured for molecular KBr. Experimental energies of the main and satellite structures have been compared with the results of ab initio calculations based on molecular orbital theory including configuration and multiconfiguration interaction approaches. Comparison between the experimental KBr spectrum and previously reported Kr valence photoelectron spectrum has also been performed in order to find out if electron correlation is of the same importance in the valence ionized state of KBr as in the corresponding state of Kr

Electron scattering in large water clusters from photoelectron imaging with high harmonic radiation.

Science.gov (United States)

Gartmann, Thomas E; Hartweg, Sebastian; Ban, Loren; Chasovskikh, Egor; Yoder, Bruce L; Signorell, Ruth

2018-06-06

Low-energy electron scattering in water clusters (H2O)n with average cluster sizes of n < 700 is investigated by angle-resolved photoelectron spectroscopy using high harmonic radiation at photon energies of 14.0, 20.3, and 26.5 eV for ionization from the three outermost valence orbitals. The measurements probe the evolution of the photoelectron anisotropy parameter β as a function of cluster size. A remarkably steep decrease of β with increasing cluster size is observed, which for the largest clusters reaches liquid bulk values. Detailed electron scattering calculations reveal that neither gas nor condensed phase scattering can explain the cluster data. Qualitative agreement between experiment and simulations is obtained with scattering calculations that treat cluster scattering as an intermediate case between gas and condensed phase scattering.

Valence QCD: Connecting QCD to the quark model

International Nuclear Information System (INIS)

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

1999-01-01

A valence QCD theory is developed to study the valence quark properties of hadrons. To keep only the valence degrees of freedom, the pair creation through the Z graphs is deleted in the connected insertions, whereas the sea quarks are eliminated in the disconnected insertions. This is achieved with a new 'valence QCD' Lagrangian where the action in the time direction is modified so that the particle and antiparticle decouple. It is shown in this valence version of QCD that the ratios of isovector to isoscalar matrix elements (e.g., F A /D A and F S /D S ratios) in the nucleon reproduce the SU(6) quark model predictions in a lattice QCD calculation. We also consider how the hadron masses are affected on the lattice and discover new insights into the origin of dynamical mass generation. It is found that, within statistical errors, the nucleon and the Δ become degenerate for the quark masses we have studied (ranging from 1 to 4 times the strange mass). The π and ρ become nearly degenerate in this range. It is shown that valence QCD has the C, P, T symmetries. The lattice version is reflection positive. It also has the vector and axial symmetries. The latter leads to a modified partially conserved axial Ward identity. As a result, the theory has a U(2N F ) symmetry in the particle-antiparticle space. Through lattice simulation, it appears that this is dynamically broken down to U q (N F )xU bar q (N F ). Furthermore, the lattice simulation reveals spin degeneracy in the hadron masses and various matrix elements. This leads to an approximate U q (2N F )xU bar q (2N F ) symmetry which is the basis for the valence quark model. In addition, we find that the masses of N, Δ,ρ,π,a 1 , and a 0 all drop precipitously compared to their counterparts in the quenched QCD calculation. This is interpreted as due to the disappearance of the 'constituent' quark mass which is dynamically generated through tadpole diagrams. The origin of the hyperfine splitting in the baryon is

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

Science.gov (United States)

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.

Electronic structure of metal clusters

International Nuclear Information System (INIS)

Wertheim, G.K.

1989-01-01

Photoemission spectra of valence electrons in metal clusters, together with threshold ionization potential measurements, provide a coherent picture of the development of the electronic structure from the isolated atom to the large metallic cluster. An insulator-metal transition occurs at an intermediate cluster size, which serves to define the boundary between small and large clusters. Although the outer electrons may be delocalized over the entire cluster, a small cluster remains insulating until the density of states near the Fermi level exceeds 1/kT. In large clusters, with increasing cluster size, the band structure approaches that of the bulk metal. However, the bands remain significantly narrowed even in a 1000-atom cluster, giving an indication of the importance of long-range order. The core-electron binding-energy shifts of supported metal clusters depend on changes in the band structure in the initial state, as well as on various final-state effects, including changes in core hole screening and the coulomb energy of the final-state charge. For cluster supported on amorphous carbon, this macroscopic coulomb shift is often dominant, as evidenced by the parallel shifts of the core-electron binding energy and the Fermi edge. Auger data confirm that final-state effects dominate in cluster of Sn and some other metals. Surface atom core-level shifts provide a valuable guide to the contributions of initial-state changes in band structure to cluster core-electron binding energy shifts, especially for Au and Pt. The available data indicate that the shift observed in supported, metallic clusters arise largely from the charge left on the cluster by photoemission. As the metal-insulator transition is approached from above, metallic screening is suppressed and the shift is determined by the local environment. (orig.)

Observations on small anionic clusters in an electrostatic ion beam trap

Energy Technology Data Exchange (ETDEWEB)

Eritt, Markus

2008-10-02

The term atomic cluster relates to compounds of at least two or three atoms. Thereby the physical properties are size dependent and the property transitions between single atoms and bulk material are not always smooth. Ion traps allow it to observe internal cluster properties independent from the influence of external forces. In this work the electron induced decay of singly negatively charged atomic clusters was observed. The dissociation cross section of the clusters is dominated by detachment of the only weakly bound outer electrons. For simple atoms at low electron energies a simple scaling law can be obtained that includes only the binding energies of the valence electrons. Nevertheless for larger sizes theoretical calculations predict so called ''giant resonances'' as dominant decay process in metal clusters. Due to mass limitations in storage rings exist so far only cross section measurements for simple anions and small negative molecules. In this work the electron detachment cross sections of small negatively charged carbon (C{sub n}{sup -} n=2-12), aluminium (Al{sub n}{sup -} n=2-7) and silver clusters (Ag{sub n}{sup -} n=1-11) were measured in an electrostatic ion beam trap. The classical scaling law, including only the binding energies of the valence electrons, turned out to be not sufficient, especially for larger clusters. In order to improve the correlation between measured and predicted values it was proposed to involve the influence of the cluster volume and the specific polarisability induced by long range coulomb interaction. For silver clusters the best agreement was obtained using a combination of the projected area reduced by the polarisability. The existence of ''giant resonances'' could not be confirmed. According to theory for clusters with a broad internal energy distribution, a power-law decay close to 1/time is expected. For some clusters the lifetime behaviour would be strongly quenched by photon

Reducing the negative valence of stressful memories through emotionally valenced, modality-specific tasks

NARCIS (Netherlands)

Tadmor, Avia; McNally, Richard J; Engelhard, Iris M

2016-01-01

BACKGROUND AND OBJECTIVES: People who perform a cognitively demanding secondary task while recalling a distressing memory often experience the memory as less emotional, vivid, or accurate during subsequent recollections. In this experiment, we tested whether the emotional valence (positive versus

Quantum kinetic theory of metal clusters in an intense electromagnetic field

Directory of Open Access Journals (Sweden)

M.Bonitz

2004-01-01

Full Text Available A quantum kinetic theory for weakly inhomogeneous charged particle systems is derived within the framework of nonequilibrium Green's functions. The results are of relevance for valence electrons of metal clusters as well as for confined Coulomb systems, such as electrons in quantum dots or ultracold ions in traps and similar systems. To be specific, here we concentrate on the application to metal clusters, but the results are straightforwardly generalized. Therefore, we first give an introduction to the physics of correlated valence electrons of metal clusters in strong electromagnetic fields. After a brief overview on the jellium model and the standard density functional approach to the ground state properties, we focus on the extension of the theory to nonequilibrium. To this end a general gauge-invariant kinetic theory is developed. The results include the equations of motion of the two-time correlation functions, the equation for the Wigner function and an analysis of the spectral function. Here, the concept of an effective quantum potential is introduced which retains the convenient local form of the propagators. This allows us to derive explicit results for the spectral function of electrons in a combined strong electromagnetic field and a weakly inhomogeneous confinement potential.

Valence, magnetism and conduction in the intermediate valence compounds: the case SmB6

International Nuclear Information System (INIS)

Derr, J.

2006-09-01

In some rare earth based compounds, the 4f level is situated so close to the Fermi level that the valence of the compound can become intermediate between two integer values. The so called 'intermediate valence' compound of Samarium hexaboride (SmB 6 ) is one typical example of the exciting physics which can result from this quantum equilibrium between two valence configurations. The first configuration (Sm 2+ ) corresponds to an insulating and non magnetic state whereas the second one (Sm 3+ ) would theoretically give a magnetic and metallic ground state. This dissertation deals with the influence of pressure on this equilibrium. Specific heat measurements under pressure evidenced a new long range magnetic ordering for pressures higher than p c ∼ 10 GPa. On another hand, transport measurements measured for the first time in good conditions of hydrostatics found a reliable and reproducible critical pressure for the insulator to metal transition equal to p c . The phase diagram of SmB 6 is now well known and the observation for the first time of a magnetic anomaly in the high pressure resistivity curves certifies that the onset of the magnetic phase really coincide with the closure of the gap. This change at the critical pressure p c is discussed in a general frame taking into account the Kondo lattice temperature as a key parameter for the renormalization of the wavefunction from one integer configuration to the other whereas the valence itself is still intermediate. This general idea seems to be valid also for other systems studied in this dissertation like SmS or TmSe and could even be valid for more general cases (Ytterbium, Cerium). In the same time, resistivity measurements under uniaxial stress were undertaken. The result is a strong anisotropy effect observed on the pressure dependence of the residual resistivity in the compound SmB 6 . The comparison with the transport under hydrostatic conditions enables us to consider a new idea for the nature of the gap

An experimental and theoretical study of the valence shell photoelectron spectra of 2-chloropyridine and 3-chloropyridine

Science.gov (United States)

Holland, D. M. P.; Powis, I.; Trofimov, A. B.; Menzies, R. C.; Potts, A. W.; Karlsson, L.; Badsyuk, I. L.; Moskovskaya, T. E.; Gromov, E. V.; Schirmer, J.

2017-10-01

The valence shell photoelectron spectra of 2-chloropyridine and 3-chloropyridine have been studied both experimentally and theoretically. Synchrotron radiation has been employed to record angle resolved photoelectron spectra in the photon energy range 20-100 eV, and these have enabled anisotropy parameters and branching ratios to be derived. The experimental results have been compared with theoretical predictions obtained using the continuum multiple scattering Xα approach. This comparison shows that the anisotropy parameter associated with the nominally chlorine lone-pair orbital lying in the molecular plane is strongly affected by the atomic Cooper minimum. In contrast, the photoionization dynamics of the second lone-pair orbital, orientated perpendicular to the molecular plane, seem relatively unaffected by this atomic phenomenon. The outer valence ionization has been studied theoretically using the third-order algebraic-diagrammatic construction (ADC(3)) approximation scheme for the one-particle Green's function, the outer valence Green's function method, and the equation-of-motion (EOM) coupled cluster (CC) theory at the level of the EOM-IP-CCSD and EOM-EE-CC3 models. The convergence of the results to the complete basis set limit has been investigated. The ADC(3) method has been employed to compute the complete valence shell ionization spectra of 2-chloropyridine and 3-chloropyridine. The relaxation mechanism for ionization of the nitrogen σ-type lone-pair orbital (σN LP) has been found to be different to that for the corresponding chlorine lone-pair (σCl LP). For the σN LP orbital, π-π* excitations play the main role in the screening of the lone-pair hole. In contrast, excitations localized at the chlorine site involving the chlorine πCl LP lone-pair and the Cl 4p Rydberg orbital are the most important for the σCl LP orbital. The calculated photoelectron spectra have allowed assignments to be proposed for most of the structure observed in the

Explaining the effect of event valence on unrealistic optimism.

Science.gov (United States)

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.

EXAFS analysis of the L3 edge of Ce in CeO2: effects of multielectron excitations and final-state mixed valence

International Nuclear Information System (INIS)

Fonda, E.; Andreatta, D.; Colavita, P.E.; Vlaic, G.

1999-01-01

Cerium oxide (IV) (CeO 2 ) is extensively employed in heterogeneous catalysis, particularly as a promoter of noble metal action in three-way catalysts. For this reason there is a great scientific and economical interest in the development of any possible chemical or structural analysis technique that could provide information on these systems. EXAFS spectroscopy has revealed itself as a powerful technique for structural characterization of such catalysts. Unfortunately, good quality K-edge spectra of cerium are not yet easily obtainable because of the high photon energy required (>40 keV). On the other hand, at lower energies it is easy to collect very good spectra of the L 3 edge (5.5 keV), but L 3 -edge spectra of cerium (IV) are characterized by the presence of two undesired additional phenomena that interfere with EXAFS analysis: final-state mixed-valence behaviour and intense multi-electron excitations. Here, a comparative analysis of the K, L 3 , L 2 and L 1 edges of Ce in CeO 2 has been made and a procedure for obtaining structural parameters from L 3 -edge EXAFS, even in the presence of these features, has been developed. This procedure could allow further studies of catalytic compounds containing tetravalent cerium surrounded by oxygen ligands. (au)

Concordance of X-ray cluster data with big bang nucleosynthesis in mixed dark matter models

International Nuclear Information System (INIS)

Strickland, R.W.; Schramm, D.N.

1997-01-01

If the hot, X-ray-emitting gas in rich clusters forms a fair sample of the universe as in cold dark matter (CDM) models and the universe is at the critical density Ω T =1, then the data appear to imply a baryon fraction Ω b,X (Ω b,X ≡Ω b derived from X-ray cluster data), larger than that predicted by big bang nucleosynthesis (BBN). While other systematic effects such as clumping can lower Ω b,X , in this paper we use an elementary analysis to show that a simple admixture of hot dark matter (HDM; low-mass neutrinos) with CDM to yield mixed dark matter shifts Ω b,X down so that significant overlap with Ω b from BBN can occur for H 0 approx-lt 73kms -1 Mpc -1 , even without invoking the possible aforementioned effects. The overlap interval is slightly larger for lower mass neutrinos since fewer of them cluster on the scale of the hot X-ray gas. We illustrate this result quantitatively in terms of a simple isothermal model. More realistic velocity dispersion profiles, with less centrally peaked density profiles, imply that fewer neutrinos are trapped and thus further increase the interval of overlap. copyright 1997 The American Astronomical Society

Valence bond model potential energy surface for H4

International Nuclear Information System (INIS)

Silver, D.M.; Brown, N.J.

1980-01-01

Potential energy surfaces for the H 4 system are derived using the valence bond procedure. An ab initio evaluation of the valence bond energy expression is described and some of its numerical properties are given. Next, four semiempirical evaluations of the valence bond energy are defined and parametrized to yield reasonable agreement with various ab initio calculations of H 4 energies. Characteristics of these four H 4 surfaces are described by means of tabulated energy minima and equipotential contour maps for selected geometrical arrangements of the four nuclei

In-medium pion valence distributions in a light-front model

Energy Technology Data Exchange (ETDEWEB)

Melo, J.P.B.C. de, E-mail: joao.mello@cruzeirodosul.edu.br [Laboratório de Física Teórica e Computacional – LFTC, Universidade Cruzeiro do Sul, 01506-000 São Paulo (Brazil); Tsushima, K. [Laboratório de Física Teórica e Computacional – LFTC, Universidade Cruzeiro do Sul, 01506-000 São Paulo (Brazil); Ahmed, I. [Laboratório de Física Teórica e Computacional – LFTC, Universidade Cruzeiro do Sul, 01506-000 São Paulo (Brazil); National Center for Physics, Quaidi-i-Azam University Campus, Islamabad 45320 (Pakistan)

2017-03-10

Pion valence distributions in nuclear medium and vacuum are studied in a light-front constituent quark model. The in-medium input for studying the pion properties is calculated by the quark-meson coupling model. We find that the in-medium pion valence distribution, as well as the in-medium pion valence wave function, are substantially modified at normal nuclear matter density, due to the reduction in the pion decay constant.

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

Science.gov (United States)

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…

Full dimensional (15-dimensional) quantum-dynamical simulation of the protonated water-dimer III: Mixed Jacobi-valence parametrization and benchmark results for the zero point energy, vibrationally excited states, and infrared spectrum.

Science.gov (United States)

Vendrell, Oriol; Brill, Michael; Gatti, Fabien; Lauvergnat, David; Meyer, Hans-Dieter

2009-06-21

Quantum dynamical calculations are reported for the zero point energy, several low-lying vibrational states, and the infrared spectrum of the H(5)O(2)(+) cation. The calculations are performed by the multiconfiguration time-dependent Hartree (MCTDH) method. A new vector parametrization based on a mixed Jacobi-valence description of the system is presented. With this parametrization the potential energy surface coupling is reduced with respect to a full Jacobi description, providing a better convergence of the n-mode representation of the potential. However, new coupling terms appear in the kinetic energy operator. These terms are derived and discussed. A mode-combination scheme based on six combined coordinates is used, and the representation of the 15-dimensional potential in terms of a six-combined mode cluster expansion including up to some 7-dimensional grids is discussed. A statistical analysis of the accuracy of the n-mode representation of the potential at all orders is performed. Benchmark, fully converged results are reported for the zero point energy, which lie within the statistical uncertainty of the reference diffusion Monte Carlo result for this system. Some low-lying vibrationally excited eigenstates are computed by block improved relaxation, illustrating the applicability of the approach to large systems. Benchmark calculations of the linear infrared spectrum are provided, and convergence with increasing size of the time-dependent basis and as a function of the order of the n-mode representation is studied. The calculations presented here make use of recent developments in the parallel version of the MCTDH code, which are briefly discussed. We also show that the infrared spectrum can be computed, to a very good approximation, within D(2d) symmetry, instead of the G(16) symmetry used before, in which the complete rotation of one water molecule with respect to the other is allowed, thus simplifying the dynamical problem.

Observation of site-specific decay processes in Ar-Kr mixed clusters following K-shell excitation of Kr

International Nuclear Information System (INIS)

Nagaya, K.; Murakami, H.; Iwayama, H.; Yao, M.

2008-01-01

Multiple ion coincidence momentum imaging measurements have been performed for an Ar-Kr mixed rare-gas cluster with an average cluster size = 100 in the 1s threshold region of Kr. The signals resulting due to the photoabsorption by Kr have been extracted on the basis of the difference in the spectra between 14.08 and 14.50 keV, i.e., on both sides of the 1s threshold for Kr. The time-of-flight spectra for the clusters reveal that multiply charged cluster ions produced as a result of inner-core excitation emit many singly charged ions such as Kr + , Ar + , ArKr + , and Ar 2 + . The abundance of daughter ions suggests the transfer of positive charges from the X-ray absorbing atom to the surrounding atoms before the Coulomb explosion is suggested from. The momentum of daughter ions is deduced from the time-of-flight and position data, and the momentum distribution shows the characteristic size dependence of the ions on the number of coincidence signals N coin , i.e., the average momentum of the Ar + ions increases with N coin , while that of the Kr + ions decreases. The N coin dependence of momentum is interpreted according to the site-dependent decay processes

Bond-Valence Constraints on Liquid Water Structure

International Nuclear Information System (INIS)

Bickmore, Barry R.; Rosso, Kevin M.; Brown, I. David; Kerisit, Sebastien N.

2009-01-01

The recent controversy about the structure of liquid water pits a new model involving water molecules in relatively stable rings-and-chains structures against the standard model that posits water molecules in distorted tetrahedral coordination. Molecular dynamics (MD) simulations 'both classical and ab initio' almost uniformly support the standard model, but since none of them can yet reproduce all the anomalous properties of water, they leave room for doubt. We argue that it is possible to evaluate these simulations by testing them against their adherence to the bond-valence model, a well known, and quantitatively accurate, empirical summary of the behavior of atoms in the bonded networks of inorganic solids. Here we use the results of ab initio molecular dynamics simulations of ice, water, and several solvated aqueous species to show that the valence sum rule (the first axiom of the bond-valence model,) is followed in both solid and liquid bond networks. We then test MD simulations of water, employing several popular potential models, against this criterion and the experimental O-O radial distribution function. It appears that most of those tested cannot satisfy both criteria well, except TIP4P and TIP5P. If the valence sum rule really can be applied to simulated liquid structures, then it follows that the bonding behaviors of atoms in liquids are in some ways identical to those in solids. We support this interpretation by showing that the simulations produce O-H-O geometries completely consistent with the range of geometries available in solids, and the distributions of instantaneous valence sums reaching the atoms in both the ice and liquid water simulations are essentially identical. Taken together, this is powerful evidence in favor of the standard distorted tetrahedral model of liquid water structure

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

Science.gov (United States)

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.

Stabilities of protonated water-ammonia clusters

Science.gov (United States)

Sundén, A. E. K.; Støchkel, K.; Hvelplund, P.; Brøndsted Nielsen, S.; Dynefors, B.; Hansen, K.

2018-05-01

Branching ratios of water and ammonia evaporation have been measured for spontaneous evaporation from protonated mixed clusters H+(H2O)n(NH3)m in the size range 0 ≤ n ≤ 11 and 0 ≤ m ≤ 7. Mixed clusters evaporate water except for clusters containing six or more ammonia molecules, indicating the formation of a stable core of one ammonium ion surrounded by four ammonia molecules and a second shell consisting predominantly of water. We relate evaporative branching ratios to free energy differences between the products of competing channels and determine the free energy differences for clusters with up to seven ammonia molecules. Clusters containing up to five ammonia molecules show a very strong scaling of these free energy differences.

Plutonium valence state distributions

International Nuclear Information System (INIS)

Silver, G.L.

1974-01-01

A calculational method for ascertaining equilibrium valence state distributions of plutonium in acid solutions as a function of the plutonium oxidation number and the solution acidity is illustrated with an example. The method may be more practical for manual use than methods based upon polynomial equations. (T.G.)

CzEngVallex: a Bilingual Czech-English Valency Lexicon

Directory of Open Access Journals (Sweden)

Urešová Zdeňka

2016-04-01

Full Text Available This paper introduces a new bilingual Czech-English verbal valency lexicon (called CzEng-Vallex representing a relatively large empirical database. It includes 20,835 aligned valency frame pairs (i.e., verb senses which are translations of each other and their aligned arguments. This new lexicon uses data from the Prague Czech-English Dependency Treebank and also takes advantage of the existing valency lexicons for both languages: the PDT-Vallex for Czech and the EngVallex for English. The CzEngVallex is available for browsing as well as for download in the LINDAT/CLARIN repository.

THE VALENCE OF CORPUSCULAR PROTEINS.

Science.gov (United States)

Gorin, M H; Mover, L S

1942-07-20

BY THE USE OF TWO EXTREME MODELS: a hydrated sphere and an unhydrated rod the valence (net charge) of corpuscular proteins can be successfully calculated from electric mobility data by the Debye-Hückel theory (modified to include the effect of the ions in the ion atmosphere) in conjunction with the electrophoretic theory of Henry. As pointed out by Abramson, this permits a comparison with values for the valence from titration data. Electrometric titration measurements of serum albumin B (Kekwick) have been determined at several ionic strengths. These results, together with the available data in the literature for serum albumin B, egg albumin, and beta-lactoglobulin have been used to compare values for the valence calculated from measurements of titration, electrophoresis, and membrane potentials. The results indicate that the usual interpretation of titration curves is open to serious question. By extrapolation of the titration data to zero ionic strength and protein concentration, there results an "intrinsic" net charge curve describing the binding of H(+) (OH(-)) ion alone. This curve agrees closely, in each case, with values of the valence calculated from mobility data (which in turn are in close accord with those estimated from membrane potential measurements). The experimental titration curves in the presence of appreciable quantities of ions and protein deviate widely from the ideal curve. It is suggested that, under these conditions, binding of undissociated acid (base) leads to erroneous values for the net charge. This binding would not affect the electrophoretic mobility. Values of the net charge obtained by the two extreme models from electrophoretic data are in agreement within 15 to 20 per cent. The agreement between the cylindrical model and the titration data is somewhat better in each case than with the sphere; i.e., this comparison enables a choice to be made between asymmetry and hydration in the interpretation of results from sedimentation and

Core polarisation and configuration mixing in 58Ni studied by high resolution electron scattering

International Nuclear Information System (INIS)

Blok, H.

1986-01-01

The nucleus 58 Ni is studied by inelastic electron-scattering. This nucleus has two valence neutrons outside a closed 58 Ni core which implies that no valence protons contribute to the transitions and thus, besides configuration mixing of the valence neutrons, proton-core polarization can be studied in detail. From inelastic electron-scattering data one obtains the charge- and current-transition densities by determining the Fourier-Bessel transform of the cross sections measured over a wide range of linear momenta transferred to the nucleus. The results of an analysis of the excitation of two 0 ++ states at low-momentum transfer are presented. These transitions are particularly interesting for studying core-polarization contributions. (Auth.)

Doubly end-on azido bridged mixed-valence cobalt trinuclear complex: Spectral study, VTM, inhibitory effect and antimycobacterial activity on human carcinoma and tuberculosis cells

Science.gov (United States)

Datta, Amitabha; Das, Kuheli; Sen, Chandana; Karan, Nirmal Kumar; Huang, Jui-Hsien; Lin, Chia-Her; Garribba, Eugenio; Sinha, Chittaranjan; Askun, Tulin; Celikboyun, Pinar; Mane, Sandeep B.

2015-09-01

Doubly end-on azido-bridged mixed-valence trinuclear cobalt complex, [Co3(L)2(N3)6(CH3OH)2] (1) is afforded by employing a potential monoanionic tetradentate-N2O2 Schiff base precursor (2-[{[2-(dimethylamino)ethyl]imino}methyl]-6-methoxyphenol; HL). Single crystal X-ray structure reveals that in 1, the adjacent CoII and CoIII ions are linked by double end-on azido bridges and thus the full molecule is generated by the site symmetry of a crystallographic twofold rotation axis. Complex 1 is subjected on different spectral analysis such as IR, UV-vis, emission and EPR spectroscopy. On variable temperature magnetic study, we observe that during cooling, the χMT values decrease smoothly until 15 K and then reaches to the value 1.56 cm3 K mol-1 at 2 K. Complex 1 inhibits the cell growth on human lung carcinoma (A549 cells), human colorectal (COLO 205 and HT-29 cells), and human heptacellular (PLC5 cells) carcinoma cells. Complex 1 exhibits anti-mycobacterial activity and considerable efficacy on Mycobacterium tuberculosis H37Rv ATCC 27294 and H37Ra ATCC 25177 strains.

Valence fluctuations between two magnetic configurations

International Nuclear Information System (INIS)

Mazzaferro, J.O.

1982-01-01

The subject of this work is the study of a microscopic model which describes TmSe through its most important feature, i.e.: the valence fluctuations between two magnetic configurations. Chapter I is a general review of the most important physical properties of rare-earth systems with intermediate valence (I.V.) and a general description of experimental results and theoretical models on Tm compounds. In Chapter II the Hamiltonian model is discussed and the loss of rotational invariance is also analyzed. Chapter III is devoted to the study of non-stoichiometric Tsub(x)Se compounds. It is shown that these compounds can be considered as a mixture of TmSe (I.V. system) and Tm 3+ 0.87Se. Chapter IV is devoted to the calculation of spin-and charge susceptibilities. The results obtained permit to explain the essential features of the neutron scattering spectrum in TmSe. In Chapter V, an exactly solvable periodic Hamiltonian is presented. From the experimental results, some fundamental features are deduced to describe TmSe as an intermediate valence system whose two accessible ionic configurations are magnetic (degenerated fundamental state). (M.E.L) [es

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

Directory of Open Access Journals (Sweden)

Tatia M C Lee

Full Text Available 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.

Short-distance matrix elements for $D$-meson mixing for 2+1 lattice QCD

Energy Technology Data Exchange (ETDEWEB)

Chang, Chia Cheng [Univ. of Illinois, Champaign, IL (United States)

2015-01-01

We study the short-distance hadronic matrix elements for D-meson mixing with partially quenched N_f = 2+1 lattice QCD. We use a large set of the MIMD Lattice Computation Collaboration's gauge configurations with a² tadpole-improved staggered sea quarks and tadpole-improved Lüscher-Weisz gluons. We use the a² tadpole-improved action for valence light quarks and the Sheikoleslami-Wohlert action with the Fermilab interpretation for the valence charm quark. Our calculation covers the complete set of five operators needed to constrain new physics models for D-meson mixing. We match our matrix elements to the MS-NDR scheme evaluated at 3 GeV. We report values for the Beneke-Buchalla-Greub-Lenz-Nierste choice of evanescent operators.

Valence electronic properties of porphyrin derivatives.

Science.gov (United States)

Stenuit, G; Castellarin-Cudia, C; Plekan, O; Feyer, V; Prince, K C; Goldoni, A; Umari, P

2010-09-28

We present a combined experimental and theoretical investigation of the valence electronic structure of porphyrin-derived molecules. The valence photoemission spectra of the free-base tetraphenylporphyrin and of the octaethylporphyrin molecule were measured using synchrotron radiation and compared with theoretical spectra calculated using the GW method and the density-functional method within the generalized gradient approximation. Only the GW results could reproduce the experimental data. We found that the contribution to the orbital energies due to electronic correlations has the same linear behavior in both molecules, with larger deviations in the vicinity of the HOMO level. This shows the importance of adequate treatment of electronic correlations in these organic systems.

Entanglement of the valence-bond-solid state on an arbitrary graph

International Nuclear Information System (INIS)

Xu Ying; Korepin, Vladimir E

2008-01-01

The Affleck-Kennedy-Lieb-Tasaki (AKLT) spin interacting model can be defined on an arbitrary graph. We explain the construction of the AKLT Hamiltonian. Given certain conditions, the ground state is unique and known as the valence-bond-solid (VBS) state. It can be used in measurement-based quantum computation as a resource state instead of the cluster state. We study the VBS ground state on an arbitrary connected graph. The graph is cut into two disconnected parts: the block and the environment. We study the entanglement between these two parts and prove that many eigenvalues of the density matrix of the block are zero. We describe a subspace of eigenvectors of the density matrix corresponding to non-zero eigenvalues. The subspace is the degenerate ground states of some Hamiltonian which we call the block Hamiltonian

Pressure-induced valence and structure change in some anti-Th3P4 structure rare earth compounds

International Nuclear Information System (INIS)

Werner, A.; Hochheimer, H.D.; Jayaraman, A.; Bucher, E.

1981-01-01

The anti-Th 3 P 4 structure compounds Yb 4 Bi 3 and Yb 4 Sb 3 have been investigated to 350 kbar by high pressure X-ray diffraction, using the diamond anvil cell. From the P-V data it is found that Yb 4 Bi 3 and Yb 4 Sb 3 are much more compressible, compared to Sm 4 Bi 3 before the valence transition. This suggests that a continuous change in the valence state of Yb takes place with pressure in the two compounds and that they may be in the mixed valent state already at ambient pressure. The ''collapsed'' anti-Th 3 P 4 structure becomes unstable in Yb 4 Bi 3 and Yb 4 Sb 3 and new lines appear at high pressure, that fit the NaCl structure. The latter structure change seems to occur also in the electronically collapsed Sm 4 Bi 3 . The results are presented and discussed. (Auth.)

Valence-to-core-detected X-ray absorption spectroscopy

DEFF Research Database (Denmark)

Hall, Eleanor R.; Pollock, Christopher J.; Bendix, Jesper

2014-01-01

X-ray absorption spectroscopy (XAS) can provide detailed insight into the electronic and geometric structures of transition-metal active sites in metalloproteins and chemical catalysts. However, standard XAS spectra inherently represent an average contribution from the entire coordination...... environment with limited ligand selectivity. To address this limitation, we have investigated the enhancement of XAS features using valence-to-core (VtC)-detected XAS, whereby XAS spectra are measured by monitoring fluorescence from valence-to-core X-ray emission (VtC XES) events. VtC emission corresponds...... to transitions from filled ligand orbitals to the metal 1s core hole, with distinct energetic shifts for ligands of differing ionization potentials. VtC-detected XAS data were obtained from multiple valence emission features for a series of well-characterized Mn model compounds; taken together, these data...

Composition-induced structural, electrical, and magnetic phase transitions in AX-type mixed-valence cobalt oxynitride epitaxial thin films

Energy Technology Data Exchange (ETDEWEB)

Takahashi, Jumpei; Oka, Daichi [Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu, Kawasaki 213-0012 (Japan); Hirose, Yasushi, E-mail: hirose@chem.s.u-tokyo.ac.jp; Yang, Chang; Fukumura, Tomoteru; Hasegawa, Tetsuya [Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu, Kawasaki 213-0012 (Japan); CREST, Japan Science and Technology Agency, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Nakao, Shoichiro [Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu, Kawasaki 213-0012 (Japan); CREST, Japan Science and Technology Agency, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Harayama, Isao; Sekiba, Daiichiro [University of Tsukuba Tandem Accelerator Complex (UTTAC), 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8577 (Japan)

2015-12-07

Synthesis of mid- to late-transition metal oxynitrides is generally difficult by conventional thermal ammonolysis because of thermal instability. In this letter, we synthesized epitaxial thin films of AX-type phase-pure cobalt oxynitrides (CoO{sub x}N{sub y}) by using nitrogen-plasma-assisted pulsed laser deposition and investigated their structural, electrical, and magnetic properties. The CoO{sub x}N{sub y} thin films with 0 ≤ y/(x + y) ≤ 0.63 grown on MgO (100) substrates showed a structural phase transition from rock salt (RS) to zinc blend at the nitrogen content y/(x + y) ∼ 0.5. As the nitrogen content increased, the room-temperature electrical resistivity of the CoO{sub x}N{sub y} thin films monotonically decreased from the order of 10{sup 5} Ω cm to 10{sup −4} Ω cm. Furthermore, we observed an insulator-to-metal transition at y/(x + y) ∼ 0.34 in the RS-CoO{sub x}N{sub y} phase, which has not yet been reported in Co{sup 2+}/Co{sup 3+} mixed-valence cobalt oxides with octahedral coordination. The low resistivity in the RS-CoO{sub x}N{sub y} phase, on the 10{sup −3} Ω cm order, may have originated from the intermediate spin state of Co{sup 3+} stabilized by the lowered crystal field symmetry of the CoO{sub 6−n}N{sub n} octahedra (n = 1, 2,…5). Magnetization measurements suggested that a magnetic phase transition occurred in the RS-CoO{sub x}N{sub y} films during the insulator-to-metal transition. These results demonstrate that low-temperature epitaxial growth is a promising approach for exploring novel electronic functionalities in oxynitrides.

Composition-induced structural, electrical, and magnetic phase transitions in AX-type mixed-valence cobalt oxynitride epitaxial thin films

International Nuclear Information System (INIS)

Takahashi, Jumpei; Oka, Daichi; Hirose, Yasushi; Yang, Chang; Fukumura, Tomoteru; Hasegawa, Tetsuya; Nakao, Shoichiro; Harayama, Isao; Sekiba, Daiichiro

2015-01-01

Synthesis of mid- to late-transition metal oxynitrides is generally difficult by conventional thermal ammonolysis because of thermal instability. In this letter, we synthesized epitaxial thin films of AX-type phase-pure cobalt oxynitrides (CoO x N y ) by using nitrogen-plasma-assisted pulsed laser deposition and investigated their structural, electrical, and magnetic properties. The CoO x N y thin films with 0 ≤ y/(x + y) ≤ 0.63 grown on MgO (100) substrates showed a structural phase transition from rock salt (RS) to zinc blend at the nitrogen content y/(x + y) ∼ 0.5. As the nitrogen content increased, the room-temperature electrical resistivity of the CoO x N y thin films monotonically decreased from the order of 10 5  Ω cm to 10 −4  Ω cm. Furthermore, we observed an insulator-to-metal transition at y/(x + y) ∼ 0.34 in the RS-CoO x N y phase, which has not yet been reported in Co 2+ /Co 3+ mixed-valence cobalt oxides with octahedral coordination. The low resistivity in the RS-CoO x N y phase, on the 10 −3  Ω cm order, may have originated from the intermediate spin state of Co 3+ stabilized by the lowered crystal field symmetry of the CoO 6−n N n octahedra (n = 1, 2,…5). Magnetization measurements suggested that a magnetic phase transition occurred in the RS-CoO x N y films during the insulator-to-metal transition. These results demonstrate that low-temperature epitaxial growth is a promising approach for exploring novel electronic functionalities in oxynitrides

Work Valence as a Predictor of Academic Achievement in the Family Context

Science.gov (United States)

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…

Emotions and false memories: valence or arousal?

Science.gov (United States)

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.

An Integrated Mixed Methods Research Design: Example of the Project Foreign Language Learning Strategies and Achievement: Analysis of Strategy Clusters and Sequences

OpenAIRE

Vlčková Kateřina

2014-01-01

The presentation focused on an so called integrated mixed method research design example on a basis of a Czech Science Foundation Project Nr. GAP407/12/0432 "Foreign Language Learning Strategies and Achievement: Analysis of Strategy Clusters and Sequences". All main integrated parts of the mixed methods research design were discussed: the aim, theoretical framework, research question, methods and validity threats. Prezentace se zaměřovala na tzv. integrovaný vícemetodový výzkumný design na...

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

Energy Technology Data Exchange (ETDEWEB)

Cieplicka-Oryńczak, N. [INFN sezione di Milano, Via Celoria 16, 20133 Milano (Italy); Institute of Nuclear Physics, Polish Academy of Sciences, PL-31342 Kraków (Poland); Fornal, B.; Szpak, B. [Institute of Nuclear Physics, Polish Academy of Sciences, PL-31342 Kraków (Poland); Leoni, S.; Bottoni, S. [INFN sezione di Milano, Via Celoria 16, 20133 Milano (Italy); Università degli Studi di Milano, Via Celoria 16, 20133 Milano (Italy); Bazzacco, D. [Dipartimento di Fisica e Astronomia dell’Università, I-35131 Padova (Italy); INFN Sezione di Padova, I-35131 Padova (Italy); Blanc, A.; Jentschel, M.; Köster, U.; Mutti, P.; Soldner, T. [Institute Laue-Langevin, 6, rue Jules Horowitz, 38042 Grenoble Cedex 9 (France); Bocchi, G. [Università degli Studi di Milano, Via Celoria 16, 20133 Milano (Italy); France, G. de [GANIL, Bd. Becquerel, BP 55027, 14076 CAEN Cedex 05 (France); Simpson, G. [LPSC, Université Joseph Fourier Grenoble 1, CNRS/IN2P3, Institut National Polytechnique de Grenoble, F-38026 Grenoble Cedex (France); Ur, C. [INFN Sezione di Padova, Via F. Marzolo 8, I-35131 Padova (Italy); Urban, W. [Faculty of Physics, University of Warsaw, ul. Hoża 69, 02-681, Warszawa (Poland)

2015-10-15

The low-spin structure of one-proton, one-neutron {sup 210}Bi nucleus was investigated in cold-neutron capture reaction on {sup 209}Bi. The γ-coincidence measurements were performed with use of EXILL array consisted of 16 HPGe detectors. The experimental results were compared to shell-model calculations involving valence particles excitations. The {sup 210}Bi nucleus offers the potential to test the effective proton-neutron interactions because most of the states should arise from the proton-neutron excitations. Additionally, it was discovered that a few states should come from the couplings of valence particles to the 3{sup −} octupole vibration in {sup 208}Pb which provides also the possibility of testing the calculations involving the core excitations.

Valency state changes in lanthanide-contained systems under high pressure

Energy Technology Data Exchange (ETDEWEB)

Jayaraman, A

1980-08-01

Changes in valency state induced by pressure in samarium sulphide SmS remind one of alchemy, as the mat black initial substance shines golden after the electron transition. The alchemist's dream is of course not realized, however the compound does exhibit an unusually interesting behaviour in the new state. The valency state of samarium as newly appeared fluctuated very rapidly between two electron configurations. Manipulation of the valency state by pressure or chemical substitution can basically change the physical properties of systems containing lanthanides. The phenomena are described and discussed in the following survey.

Topologically distinct classes of valence-bond solid states with their parent Hamiltonians

International Nuclear Information System (INIS)

Tu Honghao; Zhang Guangming; Xiang Tao; Liu Zhengxin; Ng Taikai

2009-01-01

We present a general method to construct one-dimensional translationally invariant valence-bond solid states with a built-in Lie group G and derive their matrix product representations. The general strategies to find their parent Hamiltonians are provided so that the valence-bond solid states are their unique ground states. For quantum integer-spin-S chains, we discuss two topologically distinct classes of valence-bond solid states: one consists of two virtual SU(2) spin-J variables in each site and another is formed by using two SO(2S+1) spinors. Among them, a spin-1 fermionic valence-bond solid state, its parent Hamiltonian, and its properties are discussed in detail. Moreover, two types of valence-bond solid states with SO(5) symmetries are further generalized and their respective properties are analyzed as well.

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

Science.gov (United States)

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

Transfer of chirality from adsorbed chiral molecules to the substrates highlighted by circular dichroism in angle-resolved valence photoelectron spectroscopy

DEFF Research Database (Denmark)

Contini, G.; Turchini, S.; Sanna, Simone

2012-01-01

Studies of self-assembled chiral molecules on achiral metallic surfaces have mostly focused on the determination of the geometry of adsorbates and their electronic structure. The aim of this paper is to provide direct information on the chirality character of the system and on the chirality...... transfer from molecules to substrate by means of circular dichroism in the angular distribution of valence photoelectrons for the extended domain of the chiral self-assembled molecular structure, formed by alaninol adsorbed on Cu(100). We show, by the dichroic behavior of a mixed molecule–copper valence...... state, that the presence of molecular chiral domains induces asymmetry in the interaction with the substrate and locally transfers the chiral character to the underlying metal atoms participating in the adsorption process; combined information related to the asymmetry of the initial electronic state...

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

OpenAIRE

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 be manipulated factorially. False memories increased with age for unpresented semantic associates of word lists, and net accuracy (the ratio of true...

Exploring the possibility to store the mixed oxygen-hydrogen cluster in clathrate hydrate in molar ratio 1:2 (O2+2H2).

Science.gov (United States)

Qin, Yan; Du, Qi-Shi; Xie, Neng-Zhong; Li, Jian-Xiu; Huang, Ri-Bo

2017-05-01

An interesting possibility is explored: storing the mixture of oxygen and hydrogen in clathrate hydrate in molar ratio 1:2. The interaction energies between oxygen, hydrogen, and clathrate hydrate are calculated using high level quantum chemical methods. The useful conclusion points from this study are summarized as follows. (1) The interaction energies of oxygen-hydrogen mixed cluster are larger than the energies of pure hydrogen molecular cluster. (2) The affinity of oxygen molecules with water molecules is larger than that of the hydrogen molecules with water molecules. (3) The dimension of O 2 -2H 2 interaction structure is smaller than the dimension of CO 2 -2H 2 interaction structure. (4) The escaping energy of oxygen molecules from the hydrate cell is larger than that of the hydrogen molecules. (5) The high affinity of the oxygen molecules with both the water molecules and the hydrogen molecules may promote the stability of oxygen-hydrogen mixture in the clathrate hydrate. Therefore it is possible to store the mixed (O 2 +2H 2 ) cluster in clathrate hydrate. Copyright © 2017 Elsevier Inc. All rights reserved.

Evolution of the electronic structure and properties of neutral and charged aluminum clusters: A comprehensive analysis

International Nuclear Information System (INIS)

Rao, B.K.; Jena, P.

1999-01-01

intensity distribution of the mass spectra. The unusual stability of Al 7 in neutral, cationic, and anionic form compared to its neighboring clusters is argued to be due to its likely existence in a mixed-valence state. copyright 1999 American Institute of Physics

NEVER forget: negative emotional valence enhances recapitulation.

Science.gov (United States)

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

2017-07-10

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.

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

Science.gov (United States)

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

π-Stacking, C-H/π, and halogen bonding interactions in bromobenzene and mixed bromobenzene-benzene clusters.

Science.gov (United States)

Reid, Scott A; Nyambo, Silver; Muzangwa, Lloyd; Uhler, Brandon

2013-12-19

Noncovalent interactions play an important role in many chemical and biochemical processes. Building upon our recent study of the homoclusters of chlorobenzene, where π-π stacking and CH/π interactions were identified as the most important binding motifs, in this work we present a study of bromobenzene (PhBr) and mixed bromobenzene-benzene clusters. Electronic spectra in the region of the PhBr monomer S0-S1 (ππ*) transition were obtained using resonant two-photon ionization (R2PI) methods combined with time-of-flight mass analysis. As previously found for related systems, the PhBr cluster spectra show a broad feature whose center is red-shifted from the monomer absorption, and electronic structure calculations indicate the presence of multiple isomers and Franck-Condon activity in low-frequency intermolecular modes. Calculations at the M06-2X/aug-cc-pVDZ level find in total eight minimum energy structures for the PhBr dimer: four π-stacked structures differing in the relative orientation of the Br atoms (denoted D1-D4), one T-shaped structure (D5), and three halogen bonded structures (D6-D8). The calculated binding energies of these complexes, corrected for basis set superposition error (BSSE) and zero-point energy (ZPE), are in the range of -6 to -24 kJ/mol. Time-dependent density functional theory (TDDFT) calculations predict that these isomers absorb over a range that is roughly consistent with the breadth of the experimental spectrum. To examine the influence of dipole-dipole interaction, R2PI spectra were also obtained for the mixed PhBr···benzene dimer, where the spectral congestion is reduced and clear vibrational structure is observed. This structure is well-simulated by Franck-Condon calculations that incorporate the lowest frequency intermolecular modes. Calculations find four minimum energy structures for the mixed dimer and predict that the binding energy of the global minimum is reduced by ~30% relative to the global minimum PhBr dimer

Effects of valence and divided attention on cognitive reappraisal processes.

Science.gov (United States)

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.

Effects of valence and divided attention on cognitive reappraisal processes

Science.gov (United States)

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

Sputtering and mixing of supported nanoparticles

International Nuclear Information System (INIS)

Jiménez-Sáez, J.C.; Pérez-Martín, A.M.C.; Jiménez-Rodríguez, J.J.

2013-01-01

Sputtering and mixing of Co nanoparticles supported in Cu(0 0 1) under 1-keV argon bombardment are studied using molecular-dynamics simulations. Particles of different initial size have been considered. The cluster height decreases exponentially with increasing fluence. In nanoparticles, sputtering yield is significantly enhanced compared to bulk. In fact, the value of this magnitude depends on the cluster height. A theoretical model for sputtering is introduced with acceptable results compared to those obtained by simulation. Discrepancies happen mainly for very small particles. Mixing rate at the interface is quantified; and besides, the influence of border effects for clusters of different initial size is assessed. Mixing rate and border length–surface area ratio for the initial interface show a proportionality relation. The phenomenon of ion-induced burrowing of metallic nanoparticles is analysed

Predicting the mean cycle time as a function of throughput and product mix for cluster tool workstations using EPT-based aggregate modeling

NARCIS (Netherlands)

Veeger, C.P.L.; Etman, L.F.P.; Herk, van J.; Rooda, J.E.

2009-01-01

Predicting the mean cycle time as a function of throughput and product mix is helpful in making the production planning for cluster tools. To predict the mean cycle time, detailed simulation models may be used. However, detailed models require much development time, and it may not be possible to

Relaxation processes in optically excites metal clusters; Relaxationsprozesse in optisch angeregten Metallclustern

Energy Technology Data Exchange (ETDEWEB)

Stanzel, J.

2007-08-10

The present work is concerned with the dynamics of optically excited metal clusters in the gas phase. Small mass-selected gold and tungsten cluster anions (Au{sup -}{sub n}, n=5-8, 14, 20 and W{sup -}{sub n}, n=3-14) are studied using femtosecond time-resolved photoelectron spectroscopy. Depending on the electronic structure in the valence region as well as on the optical excitation energy fundamentally different relaxation processes are observed. In small gold cluster anions excited with 1.56 eV an isolated electronically excited state is populated. The time-dependent measurements are strongly sizedependent and open insights into photoinduced geometry changes of the nuclear framework. Oscillatory vibrational wavepacket motion in Au{sup -}{sub 5}, an extremely longlived ({tau} >90 ns) electronically excited state in Au{sup -}{sub 6} as well as photoinduced melting in Au{sup -}{sub 7} and Au{sup -}{sub 8} is monitored in real time. By increasing the OPTICAL excitation energy to 3.12 eV a completely different scenario is observed. A multitude of electronically excited states can be reached upon optical excitation and as a consequence electronic relaxation processes that take place on a time scale of 1 ps are dominating. This is shown for Au{sup -}{sub 7}, Au{sup -}{sub 14} and Au{sup -}{sub 20}. Compared to gold clusters, tungsten clusters are characterized by a significantly higher electronic density of states in the valence region. Therefore electronic relaxation processes are much more likely and take place on a significantly faster time scale. The fast electronic relaxation processes are distinguished from pure vibrational relaxation. It is shown that already in the four atomic tungsten cluster W{sup -}{sub 4} electronic relaxation processes take place on a time scale of 30 fs. In all investigated tungsten cluster anions (W{sup -}{sub n}, n=3-14) an equilibrium between electronic and vibrational system is reached within around 1 ps after optical excitation which

Ethical and policy issues in cluster randomized trials: rationale and design of a mixed methods research study

Directory of Open Access Journals (Sweden)

Chaudhry Shazia H

2009-07-01

Full Text Available Abstract Background Cluster randomized trials are an increasingly important methodological tool in health research. In cluster randomized trials, intact social units or groups of individuals, such as medical practices, schools, or entire communities – rather than individual themselves – are randomly allocated to intervention or control conditions, while outcomes are then observed on individual cluster members. The substantial methodological differences between cluster randomized trials and conventional randomized trials pose serious challenges to the current conceptual framework for research ethics. The ethical implications of randomizing groups rather than individuals are not addressed in current research ethics guidelines, nor have they even been thoroughly explored. The main objectives of this research are to: (1 identify ethical issues arising in cluster trials and learn how they are currently being addressed; (2 understand how ethics reviews of cluster trials are carried out in different countries (Canada, the USA and the UK; (3 elicit the views and experiences of trial participants and cluster representatives; (4 develop well-grounded guidelines for the ethical conduct and review of cluster trials by conducting an extensive ethical analysis and organizing a consensus process; (5 disseminate the guidelines to researchers, research ethics boards (REBs, journal editors, and research funders. Methods We will use a mixed-methods (qualitative and quantitative approach incorporating both empirical and conceptual work. Empirical work will include a systematic review of a random sample of published trials, a survey and in-depth interviews with trialists, a survey of REBs, and in-depth interviews and focus group discussions with trial participants and gatekeepers. The empirical work will inform the concurrent ethical analysis which will lead to a guidance document laying out principles, policy options, and rationale for proposed guidelines. An

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

Science.gov (United States)

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…

In-clustering effects in InAlN and InGaN revealed by high pressure studies

DEFF Research Database (Denmark)

Gorczyca, I.; Suski, T.; Kaminska, A.

2010-01-01

results are compared with the results of photoluminescence measurements performed at high hydrostatic pressures on InAlN and InGaN quasi-bulk epilayers. We discuss the modification of the uppermost valence band due to formation of In clusters which, together with the related lattice relaxations, may......Electronic band structure calculations of InAlN and InGaN under pressure are presented for two different arrangements of the In atoms, uniform and clustered. The band gap pressure coefficients exhibit strong bowing, and the effect is especially large when indium atoms are clustered. The theoretical...

Mixed-valent and heavy fermions and related systems: Technical progress report, October 1, 1987-September 14, 1988

International Nuclear Information System (INIS)

Schlottmann, P.

1988-01-01

This paper discusses Ce-impurities in LaB 6 and LaAL 2 , critical behavior of ferromagnetic Heisenberg chains; integrable SU(2)---invariant model; soluble narrow-band model with possible relevance to heavy-fermions and resonating valence bonds, soluble variant of the two-impurity Anderson model; De Haas-van Alphen effect in the Anderson lattice for large orbital degeneracy; interactions mediated by spin-fluctuations in He 3 ; mixed-valence and heavy-fermion systems and high-temperature superconductivity

Direct double photoionization of the valence shell of Be

International Nuclear Information System (INIS)

Citrini, F.; Malegat, L.; Selles, P.; Kazansky, A.K.

2003-01-01

The hyperspherical R-matrix method with semiclassical outgoing waves is used to study the direct double photoionization (DPI) of the valence shell of the lightest alkaline earth-metal Be. The absolute fully integrated, singly, doubly, and triply differential cross sections obtained are compared with the single set of measurements available and with recent calculations based on the convergent close coupling and time-dependent close coupling methods. The level of agreement between all these data is very encouraging. A comparison is also made between the DPI of He and the direct DPI of the valence shell of Be. It confirms that the electron-electron correlations are stronger in the valence 2s shell of Be than in the 1s shell of He, thus contributing to a desirable clarification

Chromium valences in ureilite olivine and implications for ureilite petrogenesis

Science.gov (United States)

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

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

Science.gov (United States)

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.

Semiempirical search for oxide superconductors based on bond valence sums

International Nuclear Information System (INIS)

Tanaka, S.; Fukushima, N.; Niu, H.; Ando, K.

1992-01-01

Relationships between crystal structures and electronic states of layered transition-metal oxides are analyzed in the light of bond valence sums. Correlations between the superconducting transition temperature T c and the bond-valence-sum parameters are investigated for the high-T c cuprate compounds. Possibility of making nonsuperconducting oxides superconducting is discussed. (orig.)

Mobility of hydrogen-helium clusters in tungsten studied by molecular dynamics

Energy Technology Data Exchange (ETDEWEB)

Grigorev, Petr, E-mail: grigorievpit@gmail.com [SCK-CEN, Nuclear Materials Science Institute, Boeretang 200, Mol, 2400 (Belgium); Ghent University, Applied Physics EA17 FUSION-DC, St.Pietersnieuwstraat, 41 B4, B-9000, Gent (Belgium); Department of Experimental Nuclear Physics K-89, Institute of Physics, Nanotechnologies, and Telecommunications, Peter the Great St.Petersburg Polytechnic University, St. Petersburg (Russian Federation); Terentyev, Dmitry; Bonny, Giovanni [SCK-CEN, Nuclear Materials Science Institute, Boeretang 200, Mol, 2400 (Belgium); Zhurkin, Evgeny E. [Department of Experimental Nuclear Physics K-89, Institute of Physics, Nanotechnologies, and Telecommunications, Peter the Great St.Petersburg Polytechnic University, St. Petersburg (Russian Federation); Oost, Guido van [Ghent University, Applied Physics EA17 FUSION-DC, St.Pietersnieuwstraat, 41 B4, B-9000, Gent (Belgium); Noterdaeme, Jean-Marie [Ghent University, Applied Physics EA17 FUSION-DC, St.Pietersnieuwstraat, 41 B4, B-9000, Gent (Belgium); Max-Planck-Institut für Plasmaphysik, Garching (Germany)

2016-06-15

Tungsten is a primary candidate material for plasma facing components in fusion reactors. Interaction of plasma components with the material is unavoidable and will lead to degradation of the performance and the lifetime of the in-vessel components. In order to gain better understanding the mechanisms driving the material degradation at atomic level, atomistic simulations are employed. In this work we study migration, stability and self-trapping properties of pure helium and mixed helium-hydrogen clusters in tungsten by means of molecular dynamics simulations. We test two versions of an embedded atom model interatomic potential by comparing it with ab initio data regarding the binding properties of He clusters. By analysing the trajectories of the clusters during molecular dynamics simulations at finite temperatures we obtain the diffusion parameters. The results show that the diffusivity of mixed clusters is significantly lower, than that of pure helium clusters. The latter suggest that the formation of mixed clusters during mixed hydrogen helium plasma exposure will affect the helium diffusivity in the material.

How large are the consequences of covariate imbalance in cluster randomized trials: a simulation study with a continuous outcome and a binary covariate at the cluster level.

Science.gov (United States)

Moerbeek, Mirjam; van Schie, Sander

2016-07-11

The number of clusters in a cluster randomized trial is often low. It is therefore likely random assignment of clusters to treatment conditions results in covariate imbalance. There are no studies that quantify the consequences of covariate imbalance in cluster randomized trials on parameter and standard error bias and on power to detect treatment effects. The consequences of covariance imbalance in unadjusted and adjusted linear mixed models are investigated by means of a simulation study. The factors in this study are the degree of imbalance, the covariate effect size, the cluster size and the intraclass correlation coefficient. The covariate is binary and measured at the cluster level; the outcome is continuous and measured at the individual level. The results show covariate imbalance results in negligible parameter bias and small standard error bias in adjusted linear mixed models. Ignoring the possibility of covariate imbalance while calculating the sample size at the cluster level may result in a loss in power of at most 25 % in the adjusted linear mixed model. The results are more severe for the unadjusted linear mixed model: parameter biases up to 100 % and standard error biases up to 200 % may be observed. Power levels based on the unadjusted linear mixed model are often too low. The consequences are most severe for large clusters and/or small intraclass correlation coefficients since then the required number of clusters to achieve a desired power level is smallest. The possibility of covariate imbalance should be taken into account while calculating the sample size of a cluster randomized trial. Otherwise more sophisticated methods to randomize clusters to treatments should be used, such as stratification or balance algorithms. All relevant covariates should be carefully identified, be actually measured and included in the statistical model to avoid severe levels of parameter and standard error bias and insufficient power levels.

Size effects in van der Waals clusters studied by spin and angle-resolved electron spectroscopy and multi-coincidence ion imaging

International Nuclear Information System (INIS)

Rolles, D; Pesic, Z D; Zhang, H; Bilodeau, R C; Bozek, J D; Berrah, N

2007-01-01

We have studied the valence and inner-shell photoionization of free rare-gas clusters by means of angle and spin resolved photoelectron spectroscopy and momentum resolving electron-multi-ion coincidence spectroscopy. The electron measurements probe the evolution of the photoelectron angular distribution and spin polarization parameters as a function of photon energy and cluster size, and reveal a strong cluster size dependence of the photoelectron angular distributions in certain photon energy regions. In contrast, the spin polarization parameter of the cluster photoelectrons is found to be very close to the atomic value for all covered photon energies and cluster sizes. The ion imaging measurements, which probe the fragmentation dynamics of multiply charged van der Waals clusters, also exhibit a pronounced cluster size dependence

Crossover and valence band Kβ X-rays of chromium oxides

International Nuclear Information System (INIS)

Fazinic, Stjepko; Mandic, Luka; Kavcic, Matjaz; Bozicevic, Iva

2011-01-01

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

Electronic spectra of azaindole and its excited state mixing: A symmetry-adapted cluster configuration interaction study

Energy Technology Data Exchange (ETDEWEB)

Arulmozhiraja, Sundaram, E-mail: raja@cat.hokudai.ac.jp; Coote, Michelle L. [ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, The Australian National University, Canberra, 2601 ACT (Australia); Hasegawa, Jun-ya [Institute for Catalysis, Hokkaido University, Kita 21, Nishi 10, Kita-Ku, Sapporo 001-0021 (Japan)

2015-11-28

Electronic structures of azaindole were studied using symmetry-adapted cluster configuration interaction theory utilizing Dunning’s cc-pVTZ basis set augmented with appropriate Rydberg spd functions on carbon and nitrogen atoms. The results obtained in the present study show good agreement with the available experimental values. Importantly, and contrary to previous theoretical studies, the excitation energy calculated for the important n–π{sup ∗} state agrees well with the experimental value. A recent study by Pratt and co-workers concluded that significant mixing of π-π{sup ∗} and n-π{sup ∗} states leads to major change in the magnitude and direction of the dipole moment of the upper state vibrational level in the 0,0 + 280 cm{sup −1} band in the S{sub 1}←S{sub 0} transition when compared to that of the zero-point level of the S{sub 1} state. The present study, however, shows that all the four lowest lying excited states, {sup 1}L{sub b} π-π{sup ∗}, {sup 1}L{sub a} π-π{sup ∗}, n-π{sup ∗}, and π-σ{sup ∗}, cross each other in one way or another, and hence, significant state mixing between them is likely. The upper state vibrational level in the 0,0 + 280 cm{sup −1} band in the S{sub 1}←S{sub 0} transition benefits from this four-state mixing and this can explain the change in magnitude and direction of the dipole moment of the S{sub 1} excited vibrational level. This multistate mixing, and especially the involvement of π-σ{sup ∗} state in mixing, could also provide a route for hydrogen atom detachment reactions. The electronic spectra of benzimidazole, a closely related system, were also investigated in the present study.

Valence band variation in Si (110) nanowire induced by a covered insulator

International Nuclear Information System (INIS)

Hong-Hua, Xu; Xiao-Yan, Liu; Yu-Hui, He; Gang, Du; Ru-Qi, Han; Jin-Feng, Kang; Chun, Fan; Ai-Dong, Sun

2010-01-01

In this work, we investigate strain effects induced by the deposition of gate dielectrics on the valence band structures in Si (110) nanowire via the simulation of strain distribution and the calculation of a generalized 6×6k·p strained valence band. The nanowire is surrounded by the gate dielectric. Our simulation indicates that the strain of the amorphous SiO 2 insulator is negligible without considering temperature factors. On the other hand, the thermal residual strain in a nanowire with amorphous SiO 2 insulator which has negligible lattice misfit strain pushes the valence subbands upwards by chemical vapour deposition and downwards by thermal oxidation treatment. In contrast with the strain of the amorphous SiO 2 insulator, the strain of the HfO 2 gate insulator in Si (110) nanowire pushes the valence subbands upwards remarkably. The thermal residual strain by HfO 2 insulator contributes to the up-shifting tendency. Our simulation results for valence band shifting and warping in Si nanowires can provide useful guidance for further nanowire device design. (classical areas of phenomenology)

Segregation of information about emotional arousal and valence in horse whinnies.

Science.gov (United States)

Briefer, Elodie F; Maigrot, Anne-Laure; Mandel, Roi; Freymond, Sabrina Briefer; Bachmann, Iris; Hillmann, Edna

2015-04-21

Studying vocal correlates of emotions is important to provide a better understanding of the evolution of emotion expression through cross-species comparisons. Emotions are composed of two main dimensions: emotional arousal (calm versus excited) and valence (negative versus positive). These two dimensions could be encoded in different vocal parameters (segregation of information) or in the same parameters, inducing a trade-off between cues indicating emotional arousal and valence. We investigated these two hypotheses in horses. We placed horses in five situations eliciting several arousal levels and positive as well as negative valence. Physiological and behavioral measures collected during the tests suggested the presence of different underlying emotions. First, using detailed vocal analyses, we discovered that all whinnies contained two fundamental frequencies ("F0" and "G0"), which were not harmonically related, suggesting biphonation. Second, we found that F0 and the energy spectrum encoded arousal, while G0 and whinny duration encoded valence. Our results show that cues to emotional arousal and valence are segregated in different, relatively independent parameters of horse whinnies. Most of the emotion-related changes to vocalizations that we observed are similar to those observed in humans and other species, suggesting that vocal expression of emotions has been conserved throughout evolution.

Valence-Specific Laterality Effects in Vocal Emotion: Interactions with Stimulus Type, Blocking and Sex

Science.gov (United States)

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…

The power of emotional valence-from cognitive to affective processes in reading.

Science.gov (United States)

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.

Onset of Coulomb explosion in small silicon clusters exposed to strong-field laser pulses

Science.gov (United States)

Sayres, S. G.; Ross, M. W.; Castleman, A. W., Jr.

2012-05-01

It is now well established that, under intense laser illumination, clusters undergo enhanced ionization compared to their isolated atomic and molecular counterparts being subjected to the same pulses. This leads to extremely high charge states and concomitant Coulomb explosion. Until now, the cluster size necessary for ionization enhancement has not been quantified. Here, we demonstrate that through the comparison of ion signal from small covalently bound silicon clusters exposed to low intensity laser pulses with semi-classical theory, their ionization potentials (IPs) can be determined. At moderate laser intensities the clusters are not only atomized, but all valence electrons are removed from the cluster, thereby producing up to Si4+. The effective IPs for the production of the high charge states are shown to be ˜40% lower than the expected values for atomic silicon. Finally, the minimum cluster size responsible for the onset of the enhanced ionization is determined utilizing the magnitude of the kinetic energy released from the Coulomb explosion.

Modulation of motor-meaning congruity effects for valenced words

OpenAIRE

Brookshire, Geoffrey; Ivry, Richard; Casasanto, Daniel

2010-01-01

We investigated the extent to which emotionally valenced words automatically cue spatio-motor representations. Participants made speeded button presses, moving their hand upward or downward while viewing words with positive or negative valence. Only the color of the words was relevant to the response; on target trials, there was no requirement to read the words or process their meaning. In Experiment 1, upward responses were faster for positive words, and downward for negative words. This eff...

A data-driven approach to estimating the number of clusters in hierarchical clustering [version 1; referees: 2 approved, 1 approved with reservations

Directory of Open Access Journals (Sweden)

Antoine E. Zambelli

2016-12-01

Full Text Available DNA microarray and gene expression problems often require a researcher to perform clustering on their data in a bid to better understand its structure. In cases where the number of clusters is not known, one can resort to hierarchical clustering methods. However, there currently exist very few automated algorithms for determining the true number of clusters in the data. We propose two new methods (mode and maximum difference for estimating the number of clusters in a hierarchical clustering framework to create a fully automated process with no human intervention. These methods are compared to the established elbow and gap statistic algorithms using simulated datasets and the Biobase Gene ExpressionSet. We also explore a data mixing procedure inspired by cross validation techniques. We find that the overall performance of the maximum difference method is comparable or greater to that of the gap statistic in multi-cluster scenarios, and achieves that performance at a fraction of the computational cost. This method also responds well to our mixing procedure, which opens the door to future research. We conclude that both the mode and maximum difference methods warrant further study related to their mixing and cross-validation potential. We particularly recommend the use of the maximum difference method in multi-cluster scenarios given its accuracy and execution times, and present it as an alternative to existing algorithms.

Influence of emotional valence and arousal on the spread of activation in memory.

Science.gov (United States)

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.

Clustering high-dimensional mixed data to uncover sub-phenotypes: joint analysis of phenotypic and genotypic data.

Science.gov (United States)

McParland, D; Phillips, C M; Brennan, L; Roche, H M; Gormley, I C

2017-12-10

The LIPGENE-SU.VI.MAX study, like many others, recorded high-dimensional continuous phenotypic data and categorical genotypic data. LIPGENE-SU.VI.MAX focuses on the need to account for both phenotypic and genetic factors when studying the metabolic syndrome (MetS), a complex disorder that can lead to higher risk of type 2 diabetes and cardiovascular disease. Interest lies in clustering the LIPGENE-SU.VI.MAX participants into homogeneous groups or sub-phenotypes, by jointly considering their phenotypic and genotypic data, and in determining which variables are discriminatory. A novel latent variable model that elegantly accommodates high dimensional, mixed data is developed to cluster LIPGENE-SU.VI.MAX participants using a Bayesian finite mixture model. A computationally efficient variable selection algorithm is incorporated, estimation is via a Gibbs sampling algorithm and an approximate BIC-MCMC criterion is developed to select the optimal model. Two clusters or sub-phenotypes ('healthy' and 'at risk') are uncovered. A small subset of variables is deemed discriminatory, which notably includes phenotypic and genotypic variables, highlighting the need to jointly consider both factors. Further, 7 years after the LIPGENE-SU.VI.MAX data were collected, participants underwent further analysis to diagnose presence or absence of the MetS. The two uncovered sub-phenotypes strongly correspond to the 7-year follow-up disease classification, highlighting the role of phenotypic and genotypic factors in the MetS and emphasising the potential utility of the clustering approach in early screening. Additionally, the ability of the proposed approach to define the uncertainty in sub-phenotype membership at the participant level is synonymous with the concepts of precision medicine and nutrition. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Intermediate valence spectroscopy

International Nuclear Information System (INIS)

Gunnarsson, O.; Schoenhammer, K.

1987-01-01

Spectroscopic properties of intermediate valence compounds are studied using the Anderson model. Due to the large orbital and spin degeneracy N/sub f/ of the 4f-level, 1/N/sub f/ can be treated as a small parameter. This approach provides exact T = 0 results for the Anderson impurity model in the limit N/sub f/ → ∞, and by adding 1/N/sub f/ corrections some properties can be calculated accurately even for N/sub f/ = 1 or 2. In particular valence photoemission and resonance photoemission spectroscopies are studied. A comparison of theoretical and experimental spectra provides an estimate of the parameters in the model. Core level photoemission spectra provide estimates of the coupling between the f-level and the conduction states and of the f-level occupancy. With these parameters the model gives a fair description of other electron spectroscopies. For typical parameters the model predicts two structures in the f-spectrum, namely one structure at the f-level and one at the Fermi energy. The resonance photoemission calculation gives a photon energy dependence for these two peaks in fair agreement with experiment. The peak at the Fermi energy is partly due to a narrow Kondo resonance, resulting from many-body effects and the presence of a continuous, partly filled conduction band. This resonance is related to a large density of low-lying excitations, which explains the large susceptibility and specific heat observed for these systems at low temperatures. 38 references, 11 figures, 2 tables

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

International Nuclear Information System (INIS)

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

2011-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Kozyukhin, S., E-mail: sergkoz@igic.ras.ru [Russian Academy of Science, Institute of General and Inorganic Chemistry (Russian Federation); Golovchak, R. [Lviv Scientific Research Institute of Materials of SRC ' Carat' (Ukraine); Kovalskiy, A. [Lehigh University, Department of Materials Science and Engineering (United States); Shpotyuk, O. [Lviv Scientific Research Institute of Materials of SRC ' Carat' (Ukraine); Jain, H. [Lehigh University, Department of Materials Science and Engineering (United States)

2011-04-15

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

Age-related emotional bias in processing two emotionally valenced tasks.

Science.gov (United States)

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.

Novel Co(III)/Co(II) mixed valence compound [Co(bapen)Br2]2[CoBr4] (bapen = N,N‧-bis(3-aminopropyl)ethane-1,2-diamine): Synthesis, crystal structure and magnetic properties

Science.gov (United States)

Smolko, Lukáš; Černák, Juraj; Kuchár, Juraj; Miklovič, Jozef; Boča, Roman

2016-09-01

Green crystals of Co(III)/Co(II) mixed valence compound [Co(bapen)Br2]2[CoBr4] (bapen = N,N‧-bis(3-aminopropyl)ethane-1,2-diamine) were isolated from the aqueous system CoBr2 - bapen - HBr, crystallographically studied and characterized by elemental analysis and IR spectroscopy. Its ionic crystal structure is built up of [Co(bapen)Br2]+ cations and [CoBr4]2- anions. The Co(III) central atoms within the complex cations are hexacoordinated (donor set trans-N4Br2) with bromido ligands placed in the axial positions. The Co(II) atoms exhibit distorted tetrahedral coordination. Beside ionic forces weak Nsbnd H⋯Br intermolecular hydrogen bonding interactions contribute to the stability of the structure. Temperature variable magnetic measurements confirm the S = 3/2 behavior with the zero-field splitting of an intermediate strength: D/hc = 8.7 cm-1.

Photoion mass spectroscopy and valence photoionization of hypoxanthine, xanthine and caffeine

Energy Technology Data Exchange (ETDEWEB)

Feyer, Vitaliy, E-mail: vitaliy.feyer@elettra.trieste.it [Sincrotrone Trieste, in Area Science Park, I-34012 Basovizza (Trieste) (Italy); Plekan, Oksana [Sincrotrone Trieste, in Area Science Park, I-34012 Basovizza (Trieste) (Italy)] [Institute of Electron Physics, 21 Universitetska St., 88017 Uzhgorod (Ukraine); Richter, Robert [Sincrotrone Trieste, in Area Science Park, I-34012 Basovizza (Trieste) (Italy); Coreno, Marcello [CNR-IMIP, Area della Ricerca di Roma 1, CP10, I-00016 Monterotondo Scalo (Italy)] [CNR-Laboratorio Nazionale TASC-INFM, I-34012 Basovizza (Trieste) (Italy); Prince, Kevin C. [Sincrotrone Trieste, in Area Science Park, I-34012 Basovizza (Trieste) (Italy)] [CNR-Laboratorio Nazionale TASC-INFM, I-34012 Basovizza (Trieste) (Italy)

2009-03-30

Photoionization mass spectra of hypoxanthine, xanthine and caffeine were measured using the photoelectron-photoion coincidence technique and noble gas resonance radiation at energies from 8.4 to 21.2 eV for ionization. The fragmentation patterns for these compounds show that hydrogen cyanide is the main neutral loss species at higher photon energies, while photoionization below 16.67 eV led predominantly to the parent ion. The valence photoelectron spectra of this family of molecules were measured over an extended energy range, including the inner C, N and O 2s valence orbitals. The observed ion fragments were related to ionization of the valence orbitals.

Hot HB Stars in Globular Clusters: Physical Parameters and Consequences for Theory. 5; Radiative Levitation Versus Helium Mixing

Science.gov (United States)

Moehler, S.; Sweigart, A. V.; Landsman, W. B.; Heber, U.

2000-01-01

Atmospheric parameters (T(sub eff), log g), masses and helium abundances are derived for 42 hot horizontal branch (HB) stars in the globular cluster NGC6752. For 19 stars we derive magnesium and iron abundances as well and find that iron is enriched by a factor of 50 on average with respect to the cluster abundance whereas the magnesium abundances are consistent with the cluster abundance. Radiation pressure may levitate heavy elements like iron to the surface of the star in a diffusive process. Taking into account the enrichment of heavy elements in our spectroscopic analyses we find that high iron abundances can explain part, but not all, of the problem of anomalously low gravities along the blue HB. The blue HB stars cooler than about 15,100 K and the sdB stars (T(sub eff) greater than or = 20,000 K) agree well with canonical theory when analysed with metal-rich ([M/H] = +0.5) model atmospheres, but the stars in between these two groups remain offset towards lower gravities and masses. Deep Mixing in the red giant progenitor phase is discussed as another mechanism that may influence the position of the blue HB stars in the (T(sub eff), log g)-plane but not their masses.

Photoemission studies of mixed valent systems

International Nuclear Information System (INIS)

Parks, R.D.; Raaen, S.; denBoer, M.L.; Williams, G.P.

1984-01-01

Photoemission spectroscopy has been used to study a number of aspects of the mixed valent state (corresponding to non-integral 4f occupation) in rare earth systems. Deep core photoemission (e.g., from 3d or 4d levels) allows the measurement of the 4f occupancy and surface valence shifts, and, as well, the indirect measurement of the effect of solid state environment on the energy of hybridization between 4f electrons and conduction electrons. 4f-Derived photoemission has been used to study surface valance and chemical shifts and to infer the nature of the mixed valent ground state. A combination of 4f-derived photoemission and add-electron spectroscopy provides a measurement of the rf Coulomb correlation energy, an important parameter in the mixed valent problem. A review of these approaches will be presented, with emphasis on Ce-based systems, whose behavior falls outside the usual description of 4f-unstable systems

a Moessbauer Effect and Fenske-Hall Molecular Orbital Study of the Electronic Properties of Organoiron Clusters.

Science.gov (United States)

Buhl, Margaret Linn

The electronic properties of trinuclear iron, tetranuclear iron butterfly, iron-cobalt, and iron-copper clusters have been studied experimentally at 78K by the Mossbauer effect and theoretically by Fenske-Hall molecular orbital calculations. The Mossbauer effect isomer shift is very sensitive to the differences in the iron s-electron densities in these clusters and, as expected, decreases as the sum of the iron 4s Mulliken population and the Clementi and Raimondi effective nuclear charge increases. The molecular orbital wave functions and the Mulliken atomic charges are used to calculate the electric field gradient at the metal nuclei and the iron Mossbauer effect quadrupole splittings. The valence contribution was found to be the major component of the electric field gradient in all the clusters studied. In general the calculated value of Delta E_ {Q} is larger than the observed value, as a result of neglect of the valence Sternheimer factor, R. The metal charge depends upon its electronegativity and upon the nature of its Lewis base ligands. The carbonyl ligand carbon charge becomes more positive as the metal electronegativity increases. The oxygen charge becomes more negative as the anionic cluster charge increases, and in so doing, yields the maximum anionic charge separation. The electronic properties of the terminal carbonyl ligands are similar to those of carbon monoxide, whereas the electronic properties of the bridging carbonyl ligands are similar to those of the carbonyl group found in aldehydes and ketones.

Air void clustering.

Science.gov (United States)

2015-06-01

Air void clustering around coarse aggregate in concrete has been identified as a potential source of : low strengths in concrete mixes by several Departments of Transportation around the country. Research was : carried out to (1) develop a quantitati...

Molecular dynamics modelling of EGCG clusters on ceramide bilayers

Energy Technology Data Exchange (ETDEWEB)

Yeo, Jingjie; Cheng, Yuan; Li, Weifeng; Zhang, Yong-Wei [Institute of High Performance Computing, A*STAR, 138632 (Singapore)

2015-12-31

A novel method of atomistic modelling and characterization of both pure ceramide and mixed lipid bilayers is being developed, using only the General Amber ForceField. Lipid bilayers modelled as pure ceramides adopt hexagonal packing after equilibration, and the area per lipid and bilayer thickness are consistent with previously reported theoretical results. Mixed lipid bilayers are modelled as a combination of ceramides, cholesterol, and free fatty acids. This model is shown to be stable after equilibration. Green tea extract, also known as epigallocatechin-3-gallate, is introduced as a spherical cluster on the surface of the mixed lipid bilayer. It is demonstrated that the cluster is able to bind to the bilayers as a cluster without diffusing into the surrounding water.

The bidirectional congruency effect of brightness-valence metaphoric association in the Stroop-like and priming paradigms.

Science.gov (United States)

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.

Cerium valence change in the solid solutions Ce(Rh1-xRux)Sn

International Nuclear Information System (INIS)

Niehaus, Oliver; Riecken, Jan F.; Winter, Florian; Poettgen, Rainer; Muenster Univ.; Abdala, Paula M.; Chevalier, Bernard

2013-01-01

The solid solutions Ce(Rh 1-x Ru x )Sn were investigated by means of susceptibility measurements, specific heat, electrical resistivity, X-ray absorption spectroscopy (XAS), and 119 Sn Moessbauer spectroscopy. Magnetic measurements as well as XAS data show a cerium valence change in dependence on the ruthenium content. Higher ruthenium content causes an increase from 3.22 to 3.45 at 300 K. Furthermore χ and χ -1 data indicate valence fluctuation for cerium as a function of temperature. For example, Ce(Rh 0.8 Ru 0.2 )Sn exhibits valence fluctuations between 3.42 and 3.32 in the temperature range of 10 to 300 K. This could be proven by using the interconfiguration fluctuation (ICF) model introduced by Sales and Wohlleben. Cerium valence change does not influence the tin atoms as proven by 119 Sn Moessbauer spectroscopy, but it influences the electrical properties. Ce(Rh 0.9 Ru 0.1 )Sn behaves like a typical valence fluctuating compound, and higher ruthenium content causes an increase of the metallic behavior. (orig.)

Mixed-Valence Molecular Unit for Quantum Cellular Automata: Beyond the Born-Oppenheimer Paradigm through the Symmetry-Assisted Vibronic Approach.

Science.gov (United States)

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

2016-08-09

In this article, we focus on the electron-vibrational problem of the tetrameric mixed-valence (MV) complexes proposed for implementation as four-dot molecular quantum cellular automata (mQCA).1 Although the adiabatic approximation explored in ref 2 is an appropriate tool for the qualitative analysis of the basic characteristics of mQCA, like vibronic trapping of the electrons encoding binary information and cell-cell response, it loses its accuracy providing moderate vibronic coupling and fails in the description of the discrete pattern of the vibronic levels. Therefore, a precise solution of the quantum-mechanical vibronic problem is of primary importance for the evaluation of the shapes of the electron transfer optical absorption bands and quantitative analysis of the main parameters of tetrameric quantum cells. Here, we go beyond the Born-Oppenheimer paradigm and present a solution of the quantum-mechanical pseudo Jahn-Teller (JT) vibronic problem in bielectronic MV species (exemplified by the tetra-ruthenium complexes) based on the recently developed symmetry-assisted approach.3,4 The mathematical approach to the vibronic eigenproblem takes into consideration the point symmetry basis, and therefore, the total matrix of the JT Hamiltonian is blocked to the maximum extent. The submatrices correspond to the irreducible representations (irreps) of the point group. With this tool, we also extend the theory of the mQCA cell beyond the limit of prevailing Coulomb repulsion in the electronic pair (adopted in ref 2), and therefore, the general pseudo-JT problems for spin-singlet ((1)B1g, 2(1)A1g, (1)B2g, (1)Eu) ⊗ (b1g + eu) and spin-triplet states ((3)A2g, (3)B1g, 2(3)Eu) ⊗ (b1g + eu) in a square-planar bielectronic system are solved. The obtained symmetry-adapted electron-vibrational functions are employed for the calculation of the profiles (shape functions) of the charge transfer absorption bands in the tetrameric MV complexes and for the discussion of the

Tug of war between AO-hybridization and aromaticity in dictating structures of Li-doped alkali clusters

Science.gov (United States)

Alexandrova, Anastassia N.

2012-04-01

Hybridization of atomic orbitals is a widely appreciated phenomenon in organic chemistry. Here, we demonstrate that hybridization also can dramatically impact the shapes of small all-alkali metal clusters, and oppose σ-aromaticity in defining cluster shapes. The valence-iso-electronic LiNa4- and LiK4- clusters adopt different global minimum structures: LiNa4- is a planar C2v (1A1) species distorted from the perfect pentagon, and LiK4- is a planar square D4h (1A1g) species with Li being in the centre. This effect is rooted in the different degrees of the 2s-2p hybridization in Li in response to binding to Na versus K.

A model on valence state evaluation of TRU nuclides in reprocessing solutions

International Nuclear Information System (INIS)

Uchiyama, Gunzo; Fujine, Sachio; Yoshida, Zenko; Maeda, Mitsuru; Motoyama, Satoshi.

1998-02-01

A mathematical model was developed to evaluate the valence state of TRU nuclides in reprocessing process solutions. The model consists of mass balance equations, Nernst equations, reaction rate equations and electrically neutrality equations. The model is applicable for the valence state evaluation of TRU nuclides in both steady state and transient state conditions in redox equilibrium. The valence state which is difficult to measure under high radiation and multi component conditions is calculated by the model using experimentally measured data for the TRU nuclide concentrations, nitric acid and redox reagent concentrations, electrode potential and solution temperature. (author)

Valency stabilization of Polyvalent Iron Ions in Solution By some Organic additives during Gamma Irradiation

International Nuclear Information System (INIS)

Barakat, M.F.; Abdel Hamid, M.M.

2012-01-01

Valency stabilization of polyvalent ions in gamma irradiated aqueous solutions is sometimes necessary for the success of some chemical operations. In some previous publications valency stabilization of some polyvalent ions in solution upon gamma irradiation was achieved by using additives capable of interacting with the oxidizing or reducing species formed by water radiolysis in the medium. The results showed that the duration of valency stabilization depends on the concentration of the additives used.In the present work, a series of some organic additives has been used to investigate their capability in inducing valency stabilization of polyvalent iron ions when subjected to extended gamma irradiation periods. The results showed that the efficiency of valency stabilization depends on the amount and chemical structure of the organic additive used

Approach and withdrawal tendencies during written word processing: effects of task, emotional valence and emotional arousal

OpenAIRE

Citron, Francesca Maria Marina; Abugaber, David; Herbert, Cornelia

2016-01-01

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 behaviour (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 implic...

Robust continuous clustering.

Science.gov (United States)

Shah, Sohil Atul; Koltun, Vladlen

2017-09-12

Clustering is a fundamental procedure in the analysis of scientific data. It is used ubiquitously across the sciences. Despite decades of research, existing clustering algorithms have limited effectiveness in high dimensions and often require tuning parameters for different domains and datasets. We present a clustering algorithm that achieves high accuracy across multiple domains and scales efficiently to high dimensions and large datasets. The presented algorithm optimizes a smooth continuous objective, which is based on robust statistics and allows heavily mixed clusters to be untangled. The continuous nature of the objective also allows clustering to be integrated as a module in end-to-end feature learning pipelines. We demonstrate this by extending the algorithm to perform joint clustering and dimensionality reduction by efficiently optimizing a continuous global objective. The presented approach is evaluated on large datasets of faces, hand-written digits, objects, newswire articles, sensor readings from the Space Shuttle, and protein expression levels. Our method achieves high accuracy across all datasets, outperforming the best prior algorithm by a factor of 3 in average rank.

In-clustering induced anomalousbehavior of band gap in InAlN and InGaN

DEFF Research Database (Denmark)

Gorczyca, I.; Suski, T.; Christensen, Niels Egede

2010-01-01

Electronic band structure calculations of In containing ternary nitride alloys are presented showing a strong modification of the band gap, EG and its pressure coefficient, dEG/dp, as a function of In-content. Two different arrangements of In atoms are considered: uniform and clustered. It is shown...... that Indium clustering is the additional, large factor leading to the unusual bowings of the band gaps and their pressure coefficients. The theoretical results are compared with experimental data on variations of EG with In content. In the analysis of observed phenomena we point out the particular role...... of the uppermost valence band....

Changing the conversation: the influence of emotions on conversational valence and alcohol consumption.

Science.gov (United States)

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.

Vanadium K XANES of synthetic olivine: Valence determinations and crystal orientation effects

International Nuclear Information System (INIS)

Sutton, S.R.; Newville, M.

2005-01-01

Vanadium can exist in a large number of valence states in nature (2+?, 3+, 4+ and 5+) and determinations of V valence is therefore valuable in defining the oxidation states of earth and planetary materials over a large redox range. Synchrotron-based x-ray absorption near edge structure (XANES) spectroscopy is well-suited for measurements of V valence with ∼micrometer spatial resolution and ∼ppm elemental sensitivity. Applications of microXANES have been demonstrated for basaltic glasses. Applications to minerals are feasible but complicated by orientation effects (e.g. due to polarization of the synchrotron x-ray beam) and some results for spinel have been reported. Here we report initial results for olivine from laboratory crystallization ex-periments. The goal is to define the valence partition-ing between olivine and melt and quantify the magnitude of orientation effects, the latter tested by measuring grains at a variety of orientations in the same charge.

Ultra-small Ag clusters in zeolite A4: Antibacterial and thermochromic applications

Science.gov (United States)

Horta-Fraijo, P.; Cortez-Valadez, M.; Flores-Lopez, N. S.; Britto Hurtado, R.; Vargas-Ortiz, R. A.; Perez-Rodriguez, A.; Flores-Acosta, M.

2018-03-01

The physical and chemical properties of metal clusters depend on their atomic structure, therefore, it is important to determine the lowest-energy structures of the clusters in order to understand and utilize their properties. In this work, we use the Density Functional Theory (DFT) at the generalized gradient approximation level Becke's three-parameter and the gradient corrected functional of Lee, Yang and Puar (B3LYP) in combination with the basis set LANL2DZ (the effective core potentials and associated double-zeta valence) to determine some of the structural, electronic and vibrational properties of the planar silver clusters (Agn clusters n = 2-24). Additionally, the study reports the experimental synthesis of small silver clusters in synthetic zeolite A4. The synthesis was possible using the ion exchange method with some precursors like silver nitrate (AgNO3) and synthetic zeolite A4. The silver clusters in zeolite powder underwent thermal treatment at 450 °C to release the remaining water or humidity on it. The morphology of the particles was determined by Transmission Electron microscopy. The nanomaterials obtained show thermochromic properties. The structural parameters were correlated theoretically and experimentally.

Optoelectronic properties of valence-state-controlled amorphous niobium oxide

Science.gov (United States)

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.

Basic features of the pion valence-quark distribution function

Energy Technology Data Exchange (ETDEWEB)

Chang, Lei [CSSM, School of Chemistry and Physics, University of Adelaide, Adelaide, SA 5005 (Australia); Mezrag, Cédric; Moutarde, Hervé [Centre de Saclay, IRFU/Service de Physique Nucléaire, F-91191 Gif-sur-Yvette (France); Roberts, Craig D. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Rodríguez-Quintero, Jose [Departamento de Física Aplicada, Facultad de Ciencias Experimentales, Universidad de Huelva, Huelva E-21071 (Spain); Tandy, Peter C. [Center for Nuclear Research, Department of Physics, Kent State University, Kent, OH 44242 (United States)

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 a realistic comparison with experiment that allows us to highlight the basic features of the pion's measurable valence-quark distribution, q{sup π}(x); namely, at a characteristic hadronic scale, q{sup π}(x)∼(1−x){sup 2} for x≳0.85; and the valence-quarks carry approximately two-thirds of the pion's light-front momentum.

Spectroscopic determination of valence band parameters in InP

International Nuclear Information System (INIS)

Lewis, R.A.; Lough, B.C.C.

2003-01-01

Full text: The general form of the Hamiltonian for an electron or hole in a semiconductor has been given by Luttinger. The valence band is characterised by three parameters - γ 1 , γ 2 , γ 3 -now commonly known as the Luttinger parameters. Despite many investigations there is still considerable uncertainty regarding the Luttinger parameters of InP. The situation has been reviewed by Hackenberg et al. These authors themselves sought to determine the Luttinger parameters by hot-electron luminescence and discovered that many Luttinger parameter triplets were consistent with their data. We employ a spectroscopic approach to estimating valence-band parameters in InP. Calculations have been made for both the unperturbed energy levels and the energy levels in a magnetic field of acceptor impurities in semiconductors characterised by different Luttinger parameters. We compare our recent experimental data for the transitions associated with the Zn acceptor impurity in InP in magnetic fields up to 30 T to determine the most appropriate set of valence-band parameters for InP

Conduction Mechanism of Valence Change Resistive Switching Memory: A Survey

Directory of Open Access Journals (Sweden)

Ee Wah Lim

2015-09-01

Full Text Available Resistive switching effect in transition metal oxide (TMO based material is often associated with the valence change mechanism (VCM. Typical modeling of valence change resistive switching memory consists of three closely related phenomena, i.e., conductive filament (CF geometry evolution, conduction mechanism and temperature dynamic evolution. It is widely agreed that the electrochemical reduction-oxidation (redox process and oxygen vacancies migration plays an essential role in the CF forming and rupture process. However, the conduction mechanism of resistive switching memory varies considerably depending on the material used in the dielectric layer and selection of electrodes. Among the popular observations are the Poole-Frenkel emission, Schottky emission, space-charge-limited conduction (SCLC, trap-assisted tunneling (TAT and hopping conduction. In this article, we will conduct a survey on several published valence change resistive switching memories with a particular interest in the I-V characteristic and the corresponding conduction mechanism.

A facilitative effect of negative affective valence on working memory.

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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.

(Electronic structure and reactivities of transition metal clusters)

Energy Technology Data Exchange (ETDEWEB)

1992-01-01

The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

Medium-induced change of the optical response of metal clusters in rare-gas matrices

Science.gov (United States)

Xuan, Fengyuan; Guet, Claude

2017-10-01

Interaction with the surrounding medium modifies the optical response of embedded metal clusters. For clusters from about ten to a few hundreds of silver atoms, embedded in rare-gas matrices, we study the environment effect within the matrix random phase approximation with exact exchange (RPAE) quantum approach, which has proved successful for free silver clusters. The polarizable surrounding medium screens the residual two-body RPAE interaction, adds a polarization term to the one-body potential, and shifts the vacuum energy of the active delocalized valence electrons. Within this model, we calculate the dipole oscillator strength distribution for Ag clusters embedded in helium droplets, neon, argon, krypton, and xenon matrices. The main contribution to the dipole surface plasmon red shift originates from the rare-gas polarization screening of the two-body interaction. The large size limit of the dipole surface plasmon agrees well with the classical prediction.

A comparison of the bonding in organoiron clusters

International Nuclear Information System (INIS)

Buhl, M.L.; Long, G.J.

1994-01-01

The Moessbauer effect hyperfine parameters and the results of the Fenske-Hall molecular orbit (mo) calculations have been used to study the electronic properties of trinuclear iron, tetranuclear iron butterfly, Fe-Co, and Fe-Cu carbonyl clusters. The more negative Fe charge and the larger Fe 4s population in an Fe(CO) 4 fragment as compared with that in an Fe(CO) 3 or an Fe(CO) 2 fragment is a result of the CO ligands rather than the near-neighbor metals. The clusters which contain heterometals have more negative isomer shifts. The isomer shift correlated well with the sum of the Fe 4s orbital population and the Z eff these electrons experience. The mo wave functions and the atomic charges generally give a larger calculated ΔE Q than is observed, indicating the need to include Sternheimer factors in the calculation. The valence contribution dominates the EFG. (orig.)

The power of emotional valence – From cognitive to affective processes in reading

Directory of Open Access Journals (Sweden)

Ulrike eAltmann

2012-06-01

Full Text Available 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 3 Tesla MRI scanner. Results revealed a stronger engagement of affective ToM-related brain areas with increasingly negative story valence. Stories that were unpleasant, but simulatiously liked, selectively 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.

Redox-induced spin-state switching and mixed valency in quinonoid-bridged dicobalt complexes

Czech Academy of Sciences Publication Activity Database

Schweinfurth, D.; Rechkemmer, Y.; Hohloch, S.; Deibel, N.; Peremykin, I.; Fiedler, Jan; Marx, R.; Neugebauer, P.; van Slageren, J.; Sarkar, B.

2014-01-01

Roč. 20, č. 12 (2014), s. 3475-3486 ISSN 0947-6539 R&D Projects: GA ČR GA203/09/0705 Institutional support: RVO:61388955 Keywords : bridging ligand s * mixed -valent compounds * non-innocent ligand s Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.731, year: 2014

Separation of valence states in thin films with mixed V{sub 2}O{sub 5} and V{sub 7}O{sub 16} phases

Energy Technology Data Exchange (ETDEWEB)

Huotari, J., E-mail: jonihuot@ee.oulu.fi [Faculty of Information Technology and Electrical Engineering, University of Oulu, P.O. Box 4500, FI-90014 Oulu (Finland); Cao, W. [Research Centre for Molecular Materials, University of Oulu, P.O. Box 3000, FI-90014 Oulu (Finland); Niu, Y. [MAX-lab, Lund University, SE-221 00 Lund (Sweden); Lappalainen, J.; Puustinen, J. [Faculty of Information Technology and Electrical Engineering, University of Oulu, P.O. Box 4500, FI-90014 Oulu (Finland); Pankratov, V. [Research Centre for Molecular Materials, University of Oulu, P.O. Box 3000, FI-90014 Oulu (Finland); Lloyd Spetz, A. [Faculty of Information Technology and Electrical Engineering, University of Oulu, P.O. Box 4500, FI-90014 Oulu (Finland); Department of Physics, Chemistry and Biology, Linköping University, SE-581 83 Linköping (Sweden); Huttula, M. [Research Centre for Molecular Materials, University of Oulu, P.O. Box 3000, FI-90014 Oulu (Finland)

2016-08-15

Highlights: • Films have different XPS and NEXAFS spectra depending on the crystal structure. • Difference in oxygen vacancy concentration between the different films is identified. • Connection between high gas sensitivity and surface state of the films is revealed. - Abstract: Among the other applications, vanadium oxide thin films are considered to be excellent candidates for gas sensing. To understand the origins of the sensing capability, we carried out X-ray photoelectron and X-ray absorption spectroscopy measurements to determinate the surface valence states of thin films with mixed V{sub 7}O{sub 16} and V{sub 2}O{sub 5} compounds. Thin films were fabricated by pulsed laser deposition, and the crystal structure and symmetry of the deposited films was studied using grazing incidence X-ray diffraction and Raman spectroscopy. These results together with X-ray photoelectron and absorption spectra showed that the thin-film crystal structures varied between orthorhombic V{sub 2}O{sub 5} phase and another phase of triclinic V{sub 7}O{sub 16}. X-ray photoelectron spectroscopy was used to quantitatively confirm the high amount of V{sup 4+} ions on surfaces of the films, especially of films with V{sub 7}O{sub 16} phase present. This result was confirmed in the quantitative analysis of the V2p near-edge X-ray absorption spectra. Through the observed electronic structures, it was found that in addition to unique crystal structure and morphology, the enhanced gas sensitivity of these layers is attributed to the increase in the amount of surface oxygen vacancies.

Gas stripping and mixing in galaxy clusters: a numerical comparison study

Science.gov (United States)

Heß, Steffen; Springel, Volker

2012-11-01

The ambient hot intrahalo gas in clusters of galaxies is constantly fed and stirred by infalling galaxies, a process that can be studied in detail with cosmological hydrodynamical simulations. However, different numerical methods yield discrepant predictions for crucial hydrodynamical processes, leading for example to different entropy profiles in clusters of galaxies. In particular, the widely used Lagrangian smoothed particle hydrodynamics (SPH) scheme is suspected to strongly damp fluid instabilities and turbulence, which are both crucial to establish the thermodynamic structure of clusters. In this study, we test to which extent our recently developed Voronoi particle hydrodynamics (VPH) scheme yields different results for the stripping of gas out of infalling galaxies and for the bulk gas properties of cluster. We consider both the evolution of isolated galaxy models that are exposed to a stream of intracluster medium or are dropped into cluster models, as well as non-radiative cosmological simulations of cluster formation. We also compare our particle-based method with results obtained with a fundamentally different discretization approach as implemented in the moving-mesh code AREPO. We find that VPH leads to noticeably faster stripping of gas out of galaxies than SPH, in better agreement with the mesh-code than with SPH. We show that despite the fact that VPH in its present form is not as accurate as the moving mesh code in our investigated cases, its improved accuracy of gradient estimates makes VPH an attractive alternative to SPH.

The benefits and limitations of electrolyte mixing in vanadium flow batteries

International Nuclear Information System (INIS)

Zhang, Yunong; Liu, Le; Xi, Jingyu; Wu, Zenghua; Qiu, Xinping

2017-01-01

Highlights: •The benefits and limitations of electrolyte mixing method are studied in this work. •Different current densities and mix times are studied. •The VFB cycle number increases from 145 to 598 at 160 mA cm −2 by mixing the electrolytes. -- Abstract: Cycle life prolongation and discharge capacity regeneration have drawn enormous attention in the field of vanadium flow batteries (VFBs). Among all the methods, mixing the positive and negative electrolytes is the most efficient, but the study about the proper time and the effect of the mix method is relatively deficient. In this study, different mix times and current densities are chosen to explore the benefits and limitations of the mix method, also the mechanism of discharge capacity behavior is discussed. Through the mix method, not only the cycle number has been extended significantly, but also the voltage and energy efficiencies are recovered. Although the contribution of the mix method is restrained by the average valence of the mixed electrolytes, it can be alleviated by electrolysis. The mix method is economic, uncomplicated and can be employed in industrial applications.

Dependence of energy per molecule on sputtering yields with reactive gas cluster ions

International Nuclear Information System (INIS)

Toyoda, Noriaki; Yamada, Isao

2010-01-01

Gas cluster ions show dense energy deposition on a target surface, which result in the enhancement of chemical reactions. In reactive sputtering with gas cluster ions, the energy per atom or molecule plays an important role. In this study, the average cluster size (N, the number of atoms or molecules in a cluster ion) was controlled; thereby the dependences of the energy per molecule on the sputtering yields of carbon by CO 2 cluster ions and that of Si by SF 6 /Ar mixed gas cluster ions were investigated. Large CO 2 cluster ions with energy per molecule of 1 eV showed high reactive sputtering yield of an amorphous carbon film. However, these ions did not cause the formation of large craters on a graphite surface. It is possible to achieve very low damage etching by controlling the energy per molecule of reactive cluster ions. Further, in the case of SF 6 /Ar mixed cluster ions, it was found that reactive sputtering was enhanced when a small amount of SF 6 gas (∼10%) was mixed with Ar. The reactive sputtering yield of Si by one SF 6 molecule linearly increased with the energy per molecule.

The far from equilibrium structure of argon clusters doped with krypton or xenon.

Science.gov (United States)

Lindblad, A; Bergersen, H; Rander, T; Lundwall, M; Ohrwall, G; Tchaplyguine, M; Svensson, S; Björneholm, O

2006-04-28

Heterogeneous clusters created by doping Ar host clusters with Kr or Xe are shown to have radically different structures from the mixed clusters of the same type created by co-expansion of Ar-Kr or Ar-Xe gas mixtures. In contrast to the co-expansion case, the doped mixed clusters can be produced with Kr or Xe on the surface and Ar in the bulk. With the doping technique it is thus possible to control the surface composition of a specific cluster. A study of the cluster properties as a function of the doping pressure is also reported for the case of Ar clusters doped with Xe. The clusters have been studied by means of synchrotron radiation based X-ray photoelectron spectroscopy.

Contribution to the study of higher valency states of americium

International Nuclear Information System (INIS)

Langlet, Jean.

1976-01-01

Study of the chemistry of the higher valencies of americium in aqueous solutions and especially the autoreduction phenomenon. First a purification method of americium solutions is studied by precipitation, solvent extraction and ion exchange chromatography. Studies of higher valency states chemical properties are disturbed by the autoreduction phenomenon changing Am VI and Am V in Am III more stable. Stabilization of higher valency states, characterized by a steady concentration of Am VI in solution, can be done by complexation of Am VI and Am V ions or by a protecting effect of foreign ions. The original medium used has a complexing effect by SO 4 2- ions and a protecting effect by the system S 2 O 8 2- -Ag + consuming H 2 O 2 main reducing agent produced by water radiolysis. These effects are shown by the study of Am VI in acid and basic solutions. A mechanism of the stabilization effect is given [fr

Evaluative conditioning induces changes in sound valence

Directory of Open Access Journals (Sweden)

Anna C. Bolders

2012-04-01

Full Text Available Evaluative Conditioning (EC has hardly been tested in the auditory domain, but it is a potentially valuable research tool. In Experiment 1 we investigated whether the affective evaluation of short environmental sounds can be changed using affective words as unconditioned stimuli (US. Congruence effects on an affective priming task (APT for conditioned sounds demonstrated successful EC. Subjective ratings for sounds paired with negative words changed accordingly. In Experiment 2 we investigated whether the acquired valence remains stable after repeated presentation of the conditioned sound without the US or whether extinction occurs. The acquired affective value remained present, albeit weaker, even after 40 extinction trials. These results warrant the use of EC to study processing of short environmental sounds with acquired valence, even if this requires repeated stimulus presentations. This paves the way for studying processing of affective environmental sounds while effectively controlling low level-stimulus properties.

Beyond Valence and Magnitude: a Flexible Evaluative Coding System in the Brain

Science.gov (United States)

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

Electronic structures and valence band splittings of transition metals doped GaNs

International Nuclear Information System (INIS)

Lee, Seung-Cheol; Lee, Kwang-Ryeol; Lee, Kyu-Hwan

2007-01-01

For a practical viewpoint, presence of spin splitting of valence band in host semiconductors by the doping of transition metal (TM) ions is an essential property when designing a diluted magnetic semiconductors (DMS) material. The first principle calculations were performed on the electronic and magnetic structure of 3d transition metal doped GaN. V, Cr, and Mn doped GaNs could not be candidates for DMS materials since most of their magnetic moments is concentrated on the TM ions and the splittings of valence band were negligible. In the cases of Fe, Co, Ni, and Cu doped GaNs, on the contrary, long-ranged spin splitting of valence band was found, which could be candidates for DMS materials

Age effects in emotional prospective memory: cue valence differentially affects the prospective and retrospective component.

Science.gov (United States)

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

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.

Science.gov (United States)

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.

Study of aluminum-doped silicon clusters

International Nuclear Information System (INIS)

Zhan Shichang; Li Baoxing; Yang Jiansong

2007-01-01

Using full-muffin-tin-orbital molecular-dynamics (FP-LMTO-MD) method, we have investigated the effect of aluminum heteroatoms on the geometric structures and bond characteristics of Si n (n=5-10) clusters in detail. It is found that the geometric framework of the ground state structures for Si n (n=5-10) clusters change to some extent upon the substitution of Al atoms in some Si atoms. The effect of aluminum doping on the silicon clusters depends on the geometric structures of Si n (n=5-10) clusters. In particular, the calculations suggest that the aluminum doping would improve the bond strength of some Si-Si bonds in the mixed Si n - m Al m clusters

Theoretical studies on the catalytic oxidation of carbon monoxide on nickel clusters

Energy Technology Data Exchange (ETDEWEB)

Srivastava, A.K.; Kojima, I.; Miyazaki, E.

1986-01-01

Complete neglect of differential overlap (CNDO) molecular orbital calculations using the method of Anno and Sakai for the evaluation of the valence orbital ionization potential (VOIP) were performed with the aim of studying the oxidation of carbon monoxide on nickel clusters. A cluster surface was assumed to be preadsorbed with oxygen and the variation of various bond energies with the approach of a carbon monoxide molecule was studied for different models. Various possibilities for the reaction path are discussed in the light of the theoretical findings and it is suggested that at a low coverage of oxygen the reaction may follow a Langmuir-Hinshelwood path, whereas at a high coverage, an Eley-Rideal path might be more probable. 55 references, 13 figures.

Ligand-protected gold clusters: the structure, synthesis and applications

Science.gov (United States)

Pichugina, D. A.; Kuz'menko, N. E.; Shestakov, A. F.

2015-11-01

Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Aun with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au15 and Au25) and on anchorage to a support surface (Au25/SiO2, Au20/C, Au10/FeOx) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR)n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters MxAunLm (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR)x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active sites. The bibliography includes 345 references.

Approach and Withdrawal Tendencies during Written Word Processing: Effects of Task, Emotional Valence, and Emotional Arousal.

Science.gov (United States)

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

Pressure and irradiation effects on transport properties of samarium compounds with instable valence

International Nuclear Information System (INIS)

Morillo, J.

1981-01-01

Electron transport properties in samarium compounds with instable valence are studied in this thesis: from SmS in its integer valence phases at common pressure to SmB 6 compound IV at common pressure through SmSsub(1-x)Psub(x) (x 6 is presented [fr

Molecular invariants: atomic group valence

International Nuclear Information System (INIS)

Mundim, K.C.; Giambiagi, M.; Giambiagi, M.S. de.

1988-01-01

Molecular invariants may be deduced in a very compact way through Grassman algebra. In this work, a generalized valence is defined for an atomic group; it reduces to the Known expressions for the case of an atom in a molecule. It is the same of the correlations between the fluctions of the atomic charges qc and qd (C belongs to the group and D does not) around their average values. Numerical results agree with chemical expectation. (author) [pt

Verbal instructions targeting valence alter negative conditional stimulus evaluations (but do not affect reinstatement rates).

Science.gov (United States)

Luck, Camilla C; Lipp, Ottmar V

2018-02-01

Negative conditional stimulus (CS) valence acquired during fear conditioning may enhance fear relapse and is difficult to remove as it extinguishes slowly and does not respond to the instruction that unconditional stimulus (US) presentations will cease. We examined whether instructions targeting CS valence would be more effective. In Experiment 1, an image of one person (CS+) was paired with an aversive US, while another (CS-) was presented alone. After acquisition, participants were given positive information about the CS+ poser and negative information about the CS- poser. Instructions reversed the pattern of differential CS valence present during acquisition and eliminated differential electrodermal responding. In Experiment 2, we compared positive and negative CS revaluation by providing positive/negative information about the CS+ and neutral information about CS-. After positive revaluation, differential valence was removed and differential electrodermal responding remained intact. After negative revaluation, differential valence was strengthened and differential electrodermal responding was eliminated. Unexpectedly, the instructions did not affect the reinstatement of differential electrodermal responding.

Double-valence-fluctuating molecules and superconductivity

International Nuclear Information System (INIS)

Hirsch, J.E.; Scalapino, D.J.

1985-01-01

We discuss the possibility of ''double-valence-fluctuating'' molecules, having two ground-state configurations differing by two electrons. We propose a possible realization of such a molecule, and experimental ways to look for it. We argue that a weakly coupled array of such molecules should give rise to a strong-coupling Shafroth-Blatt-Butler superconductor, with a high transition temperature

Photoelectron angular distributions for states of any mixed character: An experiment-friendly model for atomic, molecular, and cluster anions

International Nuclear Information System (INIS)

Khuseynov, Dmitry; Blackstone, Christopher C.; Culberson, Lori M.; Sanov, Andrei

2014-01-01

We present a model for laboratory-frame photoelectron angular distributions in direct photodetachment from (in principle) any molecular orbital using linearly polarized light. A transparent mathematical approach is used to generalize the Cooper-Zare central-potential model to anionic states of any mixed character. In the limit of atomic-anion photodetachment, the model reproduces the Cooper-Zare formula. In the case of an initial orbital described as a superposition of s and p-type functions, the model yields the previously obtained s-p mixing formula. The formalism is further advanced using the Hanstorp approximation, whereas the relative scaling of the partial-wave cross-sections is assumed to follow the Wigner threshold law. The resulting model describes the energy dependence of photoelectron anisotropy for any atomic, molecular, or cluster anions, usually without requiring a direct calculation of the transition dipole matrix elements. As a benchmark case, we apply the p-d variant of the model to the experimental results for NO − photodetachment and show that the observed anisotropy trend is described well using physically meaningful values of the model parameters. Overall, the presented formalism delivers insight into the photodetachment process and affords a new quantitative strategy for analyzing the photoelectron angular distributions and characterizing mixed-character molecular orbitals using photoelectron imaging spectroscopy of negative ions

Photoelectron angular distributions for states of any mixed character: An experiment-friendly model for atomic, molecular, and cluster anions

Science.gov (United States)

Khuseynov, Dmitry; Blackstone, Christopher C.; Culberson, Lori M.; Sanov, Andrei

2014-09-01

We present a model for laboratory-frame photoelectron angular distributions in direct photodetachment from (in principle) any molecular orbital using linearly polarized light. A transparent mathematical approach is used to generalize the Cooper-Zare central-potential model to anionic states of any mixed character. In the limit of atomic-anion photodetachment, the model reproduces the Cooper-Zare formula. In the case of an initial orbital described as a superposition of s and p-type functions, the model yields the previously obtained s-p mixing formula. The formalism is further advanced using the Hanstorp approximation, whereas the relative scaling of the partial-wave cross-sections is assumed to follow the Wigner threshold law. The resulting model describes the energy dependence of photoelectron anisotropy for any atomic, molecular, or cluster anions, usually without requiring a direct calculation of the transition dipole matrix elements. As a benchmark case, we apply the p-d variant of the model to the experimental results for NO- photodetachment and show that the observed anisotropy trend is described well using physically meaningful values of the model parameters. Overall, the presented formalism delivers insight into the photodetachment process and affords a new quantitative strategy for analyzing the photoelectron angular distributions and characterizing mixed-character molecular orbitals using photoelectron imaging spectroscopy of negative ions.

The Blue Hook Populations of Massive Globular Clusters

Science.gov (United States)

Brown, Thomas

2006-07-01

Blue hook stars are a class of hot { 35,000 K} subluminous horizontal branch stars that have been recently discovered using HST ultraviolet images of the globular clusters omega Cen and NGC 2808. These stars occupy a region of the HR diagram that is unexplained by canonical stellar evolution theory. Using new theoretical evolutionary and atmospheric models, we have shown that the blue hook stars are very likely the progeny of stars that undergo extensive internal mixing during a late helium core flash on the white dwarf cooling curve. This "flash mixing" produces an enormous enhancement of the surface helium and carbon abundances, which suppresses the flux in the far ultraviolet. Although flash mixing is more likely to occur in stars that are born with high helium abundances, a high helium abundance, by itself, does not explain the presence of a blue hook population - flash mixing of the envelope is required. We propose ACS ultraviolet {SBC/F150LP and HRC/F250W} observations of the five additional globular clusters for which the presence of blue hook stars is suspected from longer wavelength observations. Like omega Cen and NGC 2808, these five targets are also among the most massive globular clusters, because less massive clusters show no evidence for blue hook stars. Because our targets span 1.5 dex in metallicity, we will be able to test our prediction that flash-mixing should be less drastic in metal-rich blue hook stars. In addition, our observations will test the hypothesis that blue hook stars only form in globular clusters massive enough to retain the helium-enriched ejecta from the first stellar generation. If this hypothesis is correct, then our observations will yield important constraints on the chemical evolution and early formation history in globular clusters, as well as the role of helium self-enrichment in producing blue horizontal branch morphologies and multiple main sequence turnoffs. Finally, our observations will provide new insight into the

Dissociable modulation of overt visual attention in valence and arousal revealed by topology of scan path.

Directory of Open Access Journals (Sweden)

Jianguang Ni

Full Text Available Emotional stimuli have evolutionary significance for the survival of organisms; therefore, they are attention-grabbing and are processed preferentially. The neural underpinnings of two principle emotional dimensions in affective space, valence (degree of pleasantness and arousal (intensity of evoked emotion, have been shown to be dissociable in the olfactory, gustatory and memory systems. However, the separable roles of valence and arousal in scene perception are poorly understood. In this study, we asked how these two emotional dimensions modulate overt visual attention. Twenty-two healthy volunteers freely viewed images from the International Affective Picture System (IAPS that were graded for affective levels of valence and arousal (high, medium, and low. Subjects' heads were immobilized and eye movements were recorded by camera to track overt shifts of visual attention. Algebraic graph-based approaches were introduced to model scan paths as weighted undirected path graphs, generating global topology metrics that characterize the algebraic connectivity of scan paths. Our data suggest that human subjects show different scanning patterns to stimuli with different affective ratings. Valence salient stimuli (with neutral arousal elicited faster and larger shifts of attention, while arousal salient stimuli (with neutral valence elicited local scanning, dense attention allocation and deep processing. Furthermore, our model revealed that the modulatory effect of valence was linearly related to the valence level, whereas the relation between the modulatory effect and the level of arousal was nonlinear. Hence, visual attention seems to be modulated by mechanisms that are separate for valence and arousal.

Cluster fusion-fission dynamics in the Singapore stock exchange

Science.gov (United States)

Teh, Boon Kin; Cheong, Siew Ann

2015-10-01

In this paper, we investigate how the cross-correlations between stocks in the Singapore stock exchange (SGX) evolve over 2008 and 2009 within overlapping one-month time windows. In particular, we examine how these cross-correlations change before, during, and after the Sep-Oct 2008 Lehman Brothers Crisis. To do this, we extend the complete-linkage hierarchical clustering algorithm, to obtain robust clusters of stocks with stronger intracluster correlations, and weaker intercluster correlations. After we identify the robust clusters in all time windows, we visualize how these change in the form of a fusion-fission diagram. Such a diagram depicts graphically how the cluster sizes evolve, the exchange of stocks between clusters, as well as how strongly the clusters mix. From the fusion-fission diagram, we see a giant cluster growing and disintegrating in the SGX, up till the Lehman Brothers Crisis in September 2008 and the market crashes of October 2008. After the Lehman Brothers Crisis, clusters in the SGX remain small for few months before giant clusters emerge once again. In the aftermath of the crisis, we also find strong mixing of component stocks between clusters. As a result, the correlation between initially strongly-correlated pairs of stocks decay exponentially with average life time of about a month. These observations impact strongly how portfolios and trading strategies should be formulated.

Analysis of earthquake clustering and source spectra in the Salton Sea Geothermal Field

Science.gov (United States)

Cheng, Y.; Chen, X.

2015-12-01

The Salton Sea Geothermal field is located within the tectonic step-over between San Andreas Fault and Imperial Fault. Since the 1980s, geothermal energy exploration has resulted with step-like increase of microearthquake activities, which mirror the expansion of geothermal field. Distinguishing naturally occurred and induced seismicity, and their corresponding characteristics (e.g., energy release) is important for hazard assessment. Between 2008 and 2014, seismic data recorded by a local borehole array were provided public access from CalEnergy through SCEC data center; and the high quality local recording of over 7000 microearthquakes provides unique opportunity to sort out characteristics of induced versus natural activities. We obtain high-resolution earthquake location using improved S-wave picks, waveform cross-correlation and a new 3D velocity model. We then develop method to identify spatial-temporally isolated earthquake clusters. These clusters are classified into aftershock-type, swarm-type, and mixed-type (aftershock-like, with low skew, low magnitude and shorter duration), based on the relative timing of largest earthquakes and moment-release. The mixed-type clusters are mostly located at 3 - 4 km depth near injection well; while aftershock-type clusters and swarm-type clusters also occur further from injection well. By counting number of aftershocks within 1day following mainshock in each cluster, we find that the mixed-type clusters have much higher aftershock productivity compared with other types and historic M4 earthquakes. We analyze detailed spatial variation of 'b-value'. We find that the mixed-type clusters are mostly located within high b-value patches, while large (M>3) earthquakes and other types of clusters are located within low b-value patches. We are currently processing P and S-wave spectra to analyze the spatial-temporal correlation of earthquake stress parameter and seismicity characteristics. Preliminary results suggest that the

Synthesis of an S T = 7 [Mn 3 ] Mixed-Valence Complex Based on 1,3-Propanediol Ligand Derivatives and Its One-Dimensional Assemblies

KAUST Repository

Huang, Jian

2013-10-07

Controlled organization of high-spin complexes and single-molecule magnets is a great challenge in molecular magnetism in order to study the effect of the intercomplex magnetic interactions on the intrinsic properties of a given magnetic object. In this work, a new ST = 7 trinuclear mixed-valence Mn complex, [MnIIIMnII 2(LA) 2(Br)4(CH3OH)6] ·Br· (CH3OH)1.5·(H2O)0.5 (1), is reported using a pyridinium-functionalized 1,3-propanediol ligand (H 2LABr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)pyridinium bromide). Using azido anions as bridging ligands and different pyridinium-functionalized 1,3-propanediol ligands (H2LBBr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-4-picolinium bromide; H 2LCBr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-3,5- lutidinium bromide), the linear [MnIIIMnII 2L2X4]+ building block has been assembled into one-dimensional coordination networks: [MnIIIMn II 2(LA)2(Br)4(CH 3OH)4(N3)]·((C2H 5)2O)1.25 (2∞), [MnIIIMn II 2(LB)2(Br)4(C 2H5OH)(CH3OH)(H2O) 2(N3)]·(H2O)0.25 (3∞), and [MnIIIMnII 2(LC) 2(Cl)3.8(Br)0.2(C2H 5OH)3(CH3OH)(N3)] (4∞). The syntheses, characterization, crystal structures, and magnetic properties of these new [Mn3]-based materials are reported. © 2013 American Chemical Society.

Valence of Facial Cues Influences Sheep Learning in a Visual Discrimination Task

Directory of Open Access Journals (Sweden)

Lucille G. A. Bellegarde

2017-11-01

Full Text Available Sheep are one of the most studied farm species in terms of their ability to process information from faces, but little is known about their face-based emotion recognition abilities. We investigated (a whether sheep could use images of sheep faces taken in situation of varying valence as cues in a simultaneous discrimination task and (b whether the valence of the situation affects their learning performance. To accomplish this, we photographed faces of sheep in three situations inducing emotional states of neutral (ruminating in the home pen or negative valence (social isolation or aggressive interaction. Sheep (n = 35 first had to learn a discrimination task with colored cards. Animals that reached the learning criterion (n = 16 were then presented with pairs of images of the face of a single individual taken in the neutral situation and in one of the negative situations. Finally, sheep had to generalize what they had learned to new pairs of images of faces taken in the same situation, but of a different conspecific. All sheep that learned the discrimination task with colored cards reached the learning criterion with images of faces. Sheep that had to associate a negative image with a food reward learned faster than sheep that had to associate a neutral image with a reward. With the exception of sheep from the aggression-rewarded group, sheep generalized this discrimination to images of faces of different individuals. Our results suggest that sheep can perceive the emotional valence displayed on faces of conspecifics and that this valence affects learning processes.

Comparison of Nickel XANES Spectra and Elemental Maps from a Ureilite, a LL3.8 Ordinary Chondrite, Two Carbonaceous Chondrites and Two Large Cluster IDPs

Science.gov (United States)

Wirick, S.; Flynn, G. J.; Sutton, S.; Zolensky, M. E.

2014-01-01

Nickel in the extraterrestrial world is commonly found in both Fe-Ni sulfide and Fe-Ni met-al forms [1] and in the pure metal state in the interior of iron meteorites where it is not easily oxidized. Ni is also found in olivine, pyroxene and glasses and in some melts the partitioning of Ni between the olivines and glass is controlled by the amount of S in the melt [2]. Its most common valence state is Ni(2+) but Ni also occurs as Ni(0), Ni(+), and Ni(3+) and rarely as Ni(2-), Ni(1-) and Ni(4+) [3]. It's valence state in olivines is Ni(2+) in octa-hedral coordination on the M1 site and rarely on the M2 site.[4]. The chemical sensitivity of X-ray absorp-tion near-edge structure (XANES) spectroscopy is well established and can be used to determine not only va-lence states but also coordination sites [5]. We report here Ni XANES spectroscopy and elemental maps collected from 2 carbonaceous chondrites, 2 large clus-ter IDPs, 1 ureilite and 1 LL3 orginary chondrite.Using XANES it may be possible to find a common trait in the large cluster IDPs that will also be found in mete-orite samples.

Infrared spectroscopy of ionic clusters

International Nuclear Information System (INIS)

Price, J.M.

1990-11-01

This thesis describes new experiments wherein the infrared vibrational predissociation spectra of a number of mass-selected ionic cluster systems have been obtained and analyzed in the 2600 to 4000 cm -1 region. The species studied include: the hydrated hydronium ions, H 3 O + (H 2 O) 3 -10 , ammoniated ammonium ions, NH 4 + (NH 3 ) 1 -10 and cluster ions involving both water and ammonia around an ammonium ion core, (mixed clusters) NH 4 + (NH 3 ) n (H 2 O) m (n+m=4). In each case, the spectra reveal well resolved structures that can be assigned to transitions arising from the vibrational motions of both the ion core of the clusters and the surrounding neutral solvent molecules. 154 refs., 19 figs., 8 tabs

Persistence of Mixed and Non-intermediate Valence in the High-Pressure Structure of Silver(I,III) Oxide, AgO: A Combined Raman, X-ray Diffraction (XRD), and Density Functional Theory (DFT) Study.

Science.gov (United States)

Grzelak, Adam; Gawraczyński, Jakub; Jaroń, Tomasz; Somayazulu, Maddury; Derzsi, Mariana; Struzhkin, Viktor; Grochala, Wojciech

2017-05-15

The X-ray diffraction data collected up to ca. 56 GPa and the Raman spectra measured up to 74.8 GPa for AgO, or Ag I Ag III O 2 , which is a prototypical mixed valence (disproportionated) oxide, indicate that two consecutive phase transitions occur: the first-order phase transition occurs between 16.1 GPa and 19.7 GPa, and a second-order phase transition occurs at ca. 40 GPa. All polymorphic forms host the square planar [Ag III O 4 ] units typical of low-spin Ag III . The disproportionated Imma form persists at least up to 74.8 GPa, as indicated by Raman spectra. Theoretical hybrid density functional theory (DFT) calculations show that the first-order transition is phonon-driven. AgO stubbornly remains disproportionated up to at least 100 GPa-in striking contrast to its copper analogue-and the fundamental band gap of AgO is ∼0.3 eV at this pressure and is weakly pressure-dependent. Metallization of AgO is yet to be achieved.

Clustering high dimensional data using RIA

Energy Technology Data Exchange (ETDEWEB)

Aziz, Nazrina [School of Quantitative Sciences, College of Arts and Sciences, Universiti Utara Malaysia, 06010 Sintok, Kedah (Malaysia)

2015-05-15

Clustering may simply represent a convenient method for organizing a large data set so that it can easily be understood and information can efficiently be retrieved. However, identifying cluster in high dimensionality data sets is a difficult task because of the curse of dimensionality. Another challenge in clustering is some traditional functions cannot capture the pattern dissimilarity among objects. In this article, we used an alternative dissimilarity measurement called Robust Influence Angle (RIA) in the partitioning method. RIA is developed using eigenstructure of the covariance matrix and robust principal component score. We notice that, it can obtain cluster easily and hence avoid the curse of dimensionality. It is also manage to cluster large data sets with mixed numeric and categorical value.

Reply to Isgur's comments on valence QCD

International Nuclear Information System (INIS)

Liu, K.F.

2000-01-01

With the goal of understanding the complexity of QCD and the role of symmetry in dynamics, the authors studied a field theory called Valence QCD (VQCD) in which the Z graphs are forbidden so that the Fock space is limited to the valence quarks. The authors calculated nucleon form factors, matrix elements, and hadron masses both with this theory and with quenched QCD on a set of lattices with the same gauge background. Comparing the results of the lattice calculations in these two theories, the authors drew conclusions regarding the SU(6) valence quark model and chiral symmetry. While recognizing the goal of VQCD, Nathan Isgur disagrees on some of the conclusions the authors have drawn. The foremost objection raised in section 2 is to their suggestion that the major part of the hyperfine splittings in baryons is due to Goldstone boson exchange and not one-gluon-exchange (OGE) interactions. The logic of Isgur's objection is that VQCD yields a spectroscopy vastly different from quenched QCD and therefore the structure of the hadrons (to which hyperfine splittings in a quark model are intimately tied) is also suspect so no definite conclusions are possible. To put this into perspective it should be emphasized at the outset that spectroscopy is only one aspect of hadron physics examined in section 1. The authors have studied the axial and scalar couplings of nucleon in terms of F A /D A and F S /D S , the neutron to proton magnetic moment ratio μn/μp, and various form factors. None of these results reveal any pathologies of hadron structure and turn out to be close to the SU(6) relations, as expected. In fact this is what motivated the study of valence degrees of freedom via VQCD. In section 2 the authors address specific issues related to spectroscopy in VQCD. Isgur also presented more general arguments against the idea of boson exchange as a contributor to hyperfine effects. A cornerstone of his discussion is the unifying aspect of OGE in a quark model picture. The

Valence and lowest Rydberg electronic states of phenol investigated by synchrotron radiation and theoretical methods

Energy Technology Data Exchange (ETDEWEB)

Limão-Vieira, P., E-mail: plimaovieira@fct.unl.pt; Ferreira da Silva, F.; Lange, E. [Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica (Portugal); Duflot, D. [Univ. Lille, UMR 8523–Physique des Lasers Atomes et Molécules, F-59000 Lille (France); CNRS, UMR 8523, F-59000 Lille (France); Jones, N. C.; Hoffmann, S. V. [ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Aarhus C (Denmark); Śmiałek, M. A. [Department of Control and Power Engineering, Faculty of Ocean Engineering and Ship Technology, Gdańsk University of Technology, Gabriela Narutowicza 11/12, 80-233 Gdańsk (Poland); Department of Physical Sciences, The Open University, Walton Hall, MK7 6AA Milton Keynes (United Kingdom); Jones, D. B. [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA 5001 (Australia); Brunger, M. J. [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA 5001 (Australia); Institute of Mathematical Sciences, University of Malaya, 50603 Kuala Lumpur (Malaysia)

2016-07-21

We present the experimental high-resolution vacuum ultraviolet (VUV) photoabsorption spectra of phenol covering for the first time the full 4.3–10.8 eV energy-range, with absolute cross sections determined. Theoretical calculations on the vertical excitation energies and oscillator strengths were performed using time-dependent density functional theory and the equation-of-motion coupled cluster method restricted to single and double excitations level. These have been used in the assignment of valence and Rydberg transitions of the phenol molecule. The VUV spectrum reveals several new features not previously reported in the literature, with particular reference to the 6.401 eV transition, which is here assigned to the 3sσ/σ{sup ∗}(OH)←3π(3a″) transition. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of phenol in the earth’s atmosphere (0–50 km).

Measurement of valence band structure in arbitrary dielectric films

International Nuclear Information System (INIS)

Uhm, Han S.; Choi, Eun H.

2012-01-01

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

Spectroscopy of particle-phonon coupled states in $^{133}$Sb by the cluster transfer reaction of $^{132}$Sn on $^{7}$Li

CERN Multimedia

We propose to investigate, with MINIBALL coupled to T-REX, the one-valence-proton $^{133}$Sb nucleus by the cluster transfer reaction of $^{132}$Sn on $^{7}$Li. The excited $^{133}$Sb will be populated by transfer of a triton into $^{132}$Sn, followed by the emission of an $\\alpha$-particle (detected in T-REX) and 2 neutrons. The aim of the experiment is to locate states arising from the coupling of the valence proton of $^{133}$Sb to the collective low-lying phonon excitations of $^{132}$Sn (in particular the 3$^−$). According to calculations in the weak-coupling approach, these states lie in the 4$\\, - \\,$5 MeV excitation energy region and in the spin interval 1/2$\\, - \\,$ 19/2, i.e., in the region populated by the cluster transfer reaction. The results will be used to perform advanced tests of different types of nuclear interactions, usually employed in the description of particle-phonon coupled excitations. States arising from couplings of the proton with simpler core excitations, involving few nucleons...

Influence of residual Ar+ in Ar cluster ion beam for DLC film formation

International Nuclear Information System (INIS)

Kitagawa, Teruyuki; Miyauchi, Kazuya; Toyoda, Noriaki; Kanda, Kazuhiro; Ikeda, Tokumi; Tsubakino, Harushige; Matsuo, Jiro; Matsui, Shinji; Yamada, Isao

2003-01-01

In order to study the influences of residual Ar monomer ion (Ar + ) on sp 2 content and hardness of diamond like carbon (DLC) films formed by Ar cluster ion beam assisted deposition, Ar cluster ion, Ar + and their mixed ions (Ar cluster ion and Ar + ) bombardments were performed during evaporation of C 60 . From near edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopy measurements, lower sp 2 content in the carbon films was obtained with Ar cluster ion bombardment than that with Ar + and mixed ion. Furthermore higher hardness and smooth surface were shown with Ar cluster ion bombardments. Therefore it was important to reduce Ar + in Ar cluster ion beams to obtain hard DLC films with flat surface

Approach and withdrawal tendencies during written word processing: effects of task, emotional valence and emotional arousal

Directory of Open Access Journals (Sweden)

Francesca M. M. Citron

2016-01-01

Full Text Available 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 behaviour (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 towards 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 labelled 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

Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

DEFF Research Database (Denmark)

Hockett, Paul; Bisgaard, Christer Z.; Clarkin, Owen J.

2011-01-01

Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems(1-6). By contrast, time-resolved structural-dynamics methods...... such as electron(7-10) or X-ray diffraction(11) and X-ray absorption(12) yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy(13-15) and high-harmonic generation(16......,17): in both cases, this sensitivity derives from the ionization-matrix element(18,19). Here we demonstrate a time-resolved molecular-frame photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during...

fK /f{pi} in Full QCD with Domain Wall Valence Quarks

Energy Technology Data Exchange (ETDEWEB)

Silas Beane; Paulo Bedaque; Konstantinos Orginos; Martin Savage

2007-05-01

We compute the ratio of pseudoscalar decay constants f{sub K}/f{sub {pi}} using domain-wall valence quarks and rooted improved Kogut-Susskind sea quarks. By employing continuum chiral perturbation theory, we extract the Gasser-Leutwyler low-energy constant L{sub 5}, and extrapolate f{sub K}/f{sub {pi}} to the physical point. We find: f{sub K}/f{sub {pi}} = 1.218 {+-} 0.002{sub -0.024}{sup +0.011} where the first error is statistical and the second error is an estimate of the systematic due to chiral extrapolation and fitting procedures. This value agrees within the uncertainties with the determination by the MILC collaboration, calculated using Kogut-Susskind valence quarks, indicating that systematic errors arising from the choice of lattice valence quark are small.

The use of symmetrized valence and relative motion coordinates for crystal potentials

DEFF Research Database (Denmark)

McMurry, H. L.; Hansen, Flemming Yssing

1980-01-01

Symmetrized valence coordinates are linear combinations of conventional valence coordinates which display the symmetry of a set of atoms bound by the valence bonds. Relative motion coordinates are relative translations, or relative rotations, of two or more strongly bonded groups of atoms among...... which relatively weak forces act. They are useful for expressing interactions between molecules in molecular crystals and should be chosen, also, to reflect the symmetry of the interacting groups. Since coordinates defined by these procedures possess elements of symmetry in common with the bonding...... interaction constants coupling coordinates of unlike symmetry with regard to the crystal point group are necessarily zero. They may be small, also, for coordinates which belong to different representations of the local symmetry when this is not the same as for the crystal. Procedures are given for defining...

The influence of valence and arousal on reasoning: Affective priming in the semantic verification task

Directory of Open Access Journals (Sweden)

Orlić Ana

2014-01-01

Full Text Available The aim of the present study was to examine the effects of affective valence and arousal on the reasoning process. Reasoning was measured using a semantic verification task and the influence of valence and arousal was tracked using the affective priming paradigm. Primes were photographs varied on two dimensions - emotional valence (positive, neutral, negative and arousal (high, low. Forty-nine psychology students participated in the experiment. Results showed that reaction time needed for semantic verification was significantly faster for positive-high arousing in comparison to positive-low arousing condition and for neutral high arousing in comparison to neutral-low arousing condition, but there were no significant differences in negative low and high arousing conditions. Also, significant differences were found among all three valences in high arousing conditions and there were no such differences in low arousing conditions. These results reveal the importance of both arousal and valence in the research on the influence of emotions on the reasoning process. [Projekat Ministarstva nauke Republike Srbije, br. 179033

Correlations in clusters and related systems. New perspectives on the many-body problem

International Nuclear Information System (INIS)

Connerade, J.P.

1996-01-01

The contents of the present volume are the proceedings of an Adriatico Research Conference, held at the International Centre for Theoretical Physics in Trieste from 26 to 29 July 1994. The theme of the conference covered many aspects of cooperative effects, beginning with giant resonances in many-electron systems, and particularly in new objects such as metallic clusters, in which collective electron dynamics are a novel feature. The relationship of these resonances with comparable features in nuclear and solid state physics was extensively discussed. Related effects, such as instabilities of valence both in clusters and in solids were explored. Clusters allow one to track the evolution of certain properties from the free atom to the solid state limits as a function of size. The giant resonances concerned not only intra-atomic excitations, but also correlated motions of all delocalized electrons within the cluster. Other systems with unusual properties, such as negative ions, in which correlations play an important role, were also considered. Finally, dynamical effects and the possible interactions between electron-electron correlations and high laser fields were envisaged

Neurons for hunger and thirst transmit a negative-valence teaching signal

Science.gov (United States)

Gong, Rong; Magnus, Christopher J.; Yu, Yang; Sternson, Scott M.

2015-01-01

Homeostasis is a biological principle for regulation of essential physiological parameters within a set range. Behavioural responses due to deviation from homeostasis are critical for survival, but motivational processes engaged by physiological need states are incompletely understood. We examined motivational characteristics and dynamics of two separate neuron populations that regulate energy and fluid homeostasis by using cell type-specific activity manipulations in mice. We found that starvation-sensitive AGRP neurons exhibit properties consistent with a negative-valence teaching signal. Mice avoided activation of AGRP neurons, indicating that AGRP neuron activity has negative valence. AGRP neuron inhibition conditioned preference for flavours and places. Correspondingly, deep-brain calcium imaging revealed that AGRP neuron activity rapidly reduced in response to food-related cues. Complementary experiments activating thirst-promoting neurons also conditioned avoidance. Therefore, these need-sensing neurons condition preference for environmental cues associated with nutrient or water ingestion, which is learned through reduction of negative-valence signals during restoration of homeostasis. PMID:25915020

The role of valence focus and appraisal overlap in emotion differentiation.

Science.gov (United States)

Erbas, Yasemin; Ceulemans, Eva; Koval, Peter; Kuppens, Peter

2015-06-01

Emotion differentiation refers to the level of specificity with which people distinguish between their emotional states and is considered to play an important role for psychological well-being. Yet, not much is known about what characterizes people high or low in emotion differentiation and what underlies these differences. In 2 studies involving experience sampling (Studies 1-2) and lab based (Study 2) methods, we investigated how emotion differentiation is related to individual differences in valence focus and the overlap in appraisal patterns between emotions. In line with expectations, results showed that high levels of both positive and negative emotion differentiation are related to lower levels of valence focus and lower levels of appraisal overlap between emotions. These findings suggest that individuals who are low in emotion differentiation mainly emphasize the valence aspect of emotions while individuals who are high in emotion differentiation make stronger distinctions between emotions in terms of their underlying appraisal profiles. (c) 2015 APA, all rights reserved).

Yb valence state in Yb{sub 5}Rh{sub 4}Ge{sub 10}

Energy Technology Data Exchange (ETDEWEB)

Sato, Hitoshi; Arita, Masashi; Shimada, Kenya; Namatame, Hirofumi; Taniguchi, Masaki [Hiroshima Synchrotron Radiation Center, Hiroshima University, Higashi-Hiroshima (Japan); Utsumi, Yuki [Synchrotron SOLEIL, L' Orme des Merisiers, Gif-sur-Yvette (France); Katoh, Kenichi [Department of Applied Physics, National Defense Academy, Yokosuka (Japan); Mimura, Kojiro [Graduate School of Engineering, Osaka Prefecture University, Sakai (Japan); Ueda, Shigenori [Synchrotron X-ray Station at SPring-8, National Institute for Materials Science, Hyogo (Japan); Quantum Beam Unit, National Institute for Materials Science, Tsukuba (Japan); Yamaoka, Hitoshi [RIKEN SPring-8 Center, Hyogo (Japan); Rousuli, Awabaikeli [Graduate School of Science, Hiroshima University, Higashi-Hiroshima (Japan); Umeo, Kazunori [NBARD, Hiroshima University, Higashi-Hiroshima (Japan)

2017-06-15

Temperature- and pressure-dependent Yb valence state in Yb{sub 5}Rh{sub 4}Ge{sub 10} has been investigated by means of Yb 3d hard X-ray photoemission spectroscopy (HAXPES) and Yb L{sub 3} absorption spectroscopy (XAS). The mean Yb valence derived from the Yb 3d HAXPES is estimated to be ∝2.78 at 300 K and decreases to ∝2.74 at 20 K. On the other hand, the Yb valence deduced from the Yb L{sub 3} XAS at 300 K is almost constant with ∝2.81 in the pressure range between 9.2 and 34.7 GPa. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Percolation and epidemics in random clustered networks

Science.gov (United States)

Miller, Joel C.

2009-08-01

The social networks that infectious diseases spread along are typically clustered. Because of the close relation between percolation and epidemic spread, the behavior of percolation in such networks gives insight into infectious disease dynamics. A number of authors have studied percolation or epidemics in clustered networks, but the networks often contain preferential contacts in high degree nodes. We introduce a class of random clustered networks and a class of random unclustered networks with the same preferential mixing. Percolation in the clustered networks reduces the component sizes and increases the epidemic threshold compared to the unclustered networks.

Interpersonal Valence Dimensions as Discriminators of Communication Contexts: An Empirical Assessment of Dyadic Linkages.

Science.gov (United States)

Garrison, John P.; And Others

The capability of 14 interpersonal dimensions to predict dyadic communication contexts was investigated in this study. Friend, acquaintance, co-worker, and family contexts were examined. The interpersonal valence construct, based on a coactive or mutual-causal paradigm, encompasses traditional source-valence components (credibility, power,…

Fourth-order perturbative extension of the single-double excitation coupled-cluster method

International Nuclear Information System (INIS)

Derevianko, Andrei; Emmons, Erik D.

2002-01-01

Fourth-order many-body corrections to matrix elements for atoms with one valence electron are derived. The obtained diagrams are classified using coupled-cluster-inspired separation into contributions from n-particle excitations from the lowest-order wave function. The complete set of fourth-order diagrams involves only connected single, double, and triple excitations and disconnected quadruple excitations. Approximately half of the fourth-order diagrams are not accounted for by the popular coupled-cluster method truncated at single and double excitations (CCSD). Explicit formulas are tabulated for the entire set of fourth-order diagrams missed by the CCSD method and its linearized version, i.e., contributions from connected triple and disconnected quadruple excitations. A partial summation scheme of the derived fourth-order contributions to all orders of perturbation theory is proposed

Enhanced stability of magic clusters: A case study of icosahedric Al12X, X=B, Al, Ga, C, Si, Ge, Ti, As

International Nuclear Information System (INIS)

Gong, X.G.; Kumar, V.

1992-10-01

We present results of the electronic structure and stability of some 40 valence electron icosahedric Al 12 X (X=B, Al, Ga, C, Si, Ge, Ti and As) clusters within the local spin density functional theory. It is shown that the stability of Al 13 cluster can be substantially enhanced by proper doping. For neutral clusters, substitution of C at the center of the icosahedron leads to the largest gain in energy. However, Al 12 B - is the most bounded in this family. These results are in agreement with the recent experiments which also find Al 12 B - to be highly abundant. (author). 12 refs, 4 figs, 2 tabs

The Relation Between Valence and Arousal in Subjective Experience Varies With Personality and Culture.

Science.gov (United States)

Kuppens, Peter; Tuerlinckx, Francis; Yik, Michelle; Koval, Peter; Coosemans, Joachim; Zeng, Kevin J; Russell, James A

2017-08-01

While in general arousal increases with positive or negative valence (a so-called V-shaped relation), there are large differences among individuals in how these two fundamental dimensions of affect are related in people's experience. In two studies, we examined two possible sources of this variation: personality and culture. In Study 1, participants (Belgian university students) recalled a recent event that was characterized by high or low valence or arousal and reported on their feelings and their personality in terms of the Five-Factor Model. In Study 2, participants from Canada, China/Hong Kong, Japan, Korea, and Spain reported on their feelings in a thin slice of time and on their personality. In Study 1, we replicated the V-shape as characterizing the relation between valence and arousal, and identified personality correlates of experiencing particular valence-arousal combinations. In Study 2, we documented how the V-shaped relation varied as a function of Western versus Eastern cultural background and personality. The results showed that the steepness of the V-shaped relation between valence and arousal increases with Extraversion within cultures, and with a West-East distinction between cultures. Implications for the personality-emotion link and research on cultural differences in affect are discussed. © 2016 Wiley Periodicals, Inc.

Photoabsorption in sodium clusters: first principles configuration interaction calculations

Science.gov (United States)

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

Air void clustering : [technical summary].

Science.gov (United States)

2015-06-01

Air void clustering around coarse aggregate in concrete has been : identified as a potential source of low strengths in concrete mixes by : several Departments of Transportation around the country. Research : was carried out to (1) develop a quantita...

Anisotropic p-f mixing mechanism explaining anomalous magnetic properties in Ce monopnictides

International Nuclear Information System (INIS)

Takahashi, H.; Kasuya, T.

1985-01-01

The indirect f-f-interaction derived from fourth-order perturbation theory with respect to the p-f mixing is calculated using the valence bands obtained by the APW band calculations. The type of the f-f-interactions is described as the coupling through the symmetry exchange under the cubic crystal field, which cannot be written as a simple bilinear type of 4f spin operator. It is necessary to consider the short-range-ordering effect as well as the non-linear effect of the p-f mixing to explain the fact that a type-I antiferromagnetic ordering is established by the second-order transition in CeBi. (author)

Music, emotion, and time perception: the influence of subjective emotional valence and arousal?

Science.gov (United States)

Droit-Volet, Sylvie; Ramos, Danilo; Bueno, José L. O.; Bigand, Emmanuel

2013-01-01

The present study used a temporal bisection task with short (2 s) stimulus durations to investigate the effect on time estimation of several musical parameters associated with emotional changes in affective valence and arousal. In order to manipulate the positive and negative valence of music, Experiments 1 and 2 contrasted the effect of musical structure with pieces played normally and backwards, which were judged to be pleasant and unpleasant, respectively. This effect of valence was combined with a subjective arousal effect by changing the tempo of the musical pieces (fast vs. slow) (Experiment 1) or their instrumentation (orchestral vs. piano pieces). The musical pieces were indeed judged more arousing with a fast than with a slow tempo and with an orchestral than with a piano timbre. In Experiment 3, affective valence was also tested by contrasting the effect of tonal (pleasant) vs. atonal (unpleasant) versions of the same musical pieces. The results showed that the effect of tempo in music, associated with a subjective arousal effect, was the major factor that produced time distortions with time being judged longer for fast than for slow tempi. When the tempo was held constant, no significant effect of timbre on the time judgment was found although the orchestral music was judged to be more arousing than the piano music. Nevertheless, emotional valence did modulate the tempo effect on time perception, the pleasant music being judged shorter than the unpleasant music. PMID:23882233

Music, Emotion and Time Perception: The influence of subjective emotional valence and arousal?

Directory of Open Access Journals (Sweden)

SYLVIE eDROIT-VOLET

2013-07-01

Full Text Available The present study used a temporal bisection task with short (< 2 s and long (> 2 s stimulus durations to investigate the effect on time estimation of several musical parameters associated with emotional changes in affective valence and arousal. In order to manipulate the positive and negative valence of music, Experiments 1 and 2 contrasted the effect of musical structure with pieces played normally and backwards, which were judged to be pleasant and unpleasant, respectively. This effect of valence was combined with a subjective arousal effect by changing the tempo of the musical pieces (fast vs. slow (Experiment 1 or their instrumentation (orchestral vs. piano pieces. The musical pieces were indeed judged more arousing with a fast than with a slow tempo and with an orchestral than with a piano timbre. In Experiment 3, affective valence was also tested by contrasting the effect of tonal (pleasant versus atonal (unpleasant versions of the same musical pieces. The results showed that the effect of tempo in music, associated with a subjective arousal effect, was the major factor that produced time distortions with time being judged longer for fast than for slow tempi. When the tempo was held constant, no significant effect of timbre on the time judgment was found although the orchestral music was judged to be more arousing than the piano music. Nevertheless, emotional valence did modulate the tempo effect on time perception, the pleasant music being judged shorter than the unpleasant music.

Music, emotion, and time perception: the influence of subjective emotional valence and arousal?

Science.gov (United States)

Droit-Volet, Sylvie; Ramos, Danilo; Bueno, José L O; Bigand, Emmanuel

2013-01-01

The present study used a temporal bisection task with short (2 s) stimulus durations to investigate the effect on time estimation of several musical parameters associated with emotional changes in affective valence and arousal. In order to manipulate the positive and negative valence of music, Experiments 1 and 2 contrasted the effect of musical structure with pieces played normally and backwards, which were judged to be pleasant and unpleasant, respectively. This effect of valence was combined with a subjective arousal effect by changing the tempo of the musical pieces (fast vs. slow) (Experiment 1) or their instrumentation (orchestral vs. piano pieces). The musical pieces were indeed judged more arousing with a fast than with a slow tempo and with an orchestral than with a piano timbre. In Experiment 3, affective valence was also tested by contrasting the effect of tonal (pleasant) vs. atonal (unpleasant) versions of the same musical pieces. The results showed that the effect of tempo in music, associated with a subjective arousal effect, was the major factor that produced time distortions with time being judged longer for fast than for slow tempi. When the tempo was held constant, no significant effect of timbre on the time judgment was found although the orchestral music was judged to be more arousing than the piano music. Nevertheless, emotional valence did modulate the tempo effect on time perception, the pleasant music being judged shorter than the unpleasant music.

Process evaluation of a cluster-randomised trial testing a pressure ulcer prevention care bundle: a mixed-methods study.

Science.gov (United States)

Roberts, Shelley; McInnes, Elizabeth; Bucknall, Tracey; Wallis, Marianne; Banks, Merrilyn; Chaboyer, Wendy

2017-02-13

As pressure ulcers contribute to significant patient burden and increased health care costs, their prevention is a clinical priority. Our team developed and tested a complex intervention, a pressure ulcer prevention care bundle promoting patient participation in care, in a cluster-randomised trial. The UK Medical Research Council recommends process evaluation of complex interventions to provide insight into why they work or fail and how they might be improved. This study aimed to evaluate processes underpinning implementation of the intervention and explore end-users' perceptions of it, in order to give a deeper understanding of its effects. A pre-specified, mixed-methods process evaluation was conducted as an adjunct to the main trial, guided by a framework for process evaluation of cluster-randomised trials. Data was collected across eight Australian hospitals but mainly focused on the four intervention hospitals. Quantitative and qualitative data were collected across the evaluation domains: recruitment, reach, intervention delivery and response to intervention, at both cluster and individual patient level. Quantitative data were analysed using descriptive and inferential statistics. Qualitative data were analysed using thematic analysis. In the context of the main trial, which found a 42% reduction in risk of pressure ulcer with the intervention that was not significant after adjusting for clustering and covariates, this process evaluation provides important insights. Recruitment and reach among clusters and individuals was high, indicating that patients, nurses and hospitals are willing to engage with a pressure ulcer prevention care bundle. Of 799 intervention patients in the trial, 96.7% received the intervention, which took under 10 min to deliver. Patients and nurses accepted the care bundle, recognising benefits to it and describing how it enabled participation in pressure ulcer prevention (PUP) care. This process evaluation found no major failures

Feedback Valence Affects Auditory Perceptual Learning Independently of Feedback Probability

Science.gov (United States)

Amitay, Sygal; Moore, David R.; Molloy, Katharine; Halliday, Lorna F.

2015-01-01

Previous studies have suggested that negative feedback is more effective in driving learning than positive feedback. We investigated the effect on learning of providing varying amounts of negative and positive feedback while listeners attempted to discriminate between three identical tones; an impossible task that nevertheless produces robust learning. Four feedback conditions were compared during training: 90% positive feedback or 10% negative feedback informed the participants that they were doing equally well, while 10% positive or 90% negative feedback informed them they were doing equally badly. In all conditions the feedback was random in relation to the listeners’ responses (because the task was to discriminate three identical tones), yet both the valence (negative vs. positive) and the probability of feedback (10% vs. 90%) affected learning. Feedback that informed listeners they were doing badly resulted in better post-training performance than feedback that informed them they were doing well, independent of valence. In addition, positive feedback during training resulted in better post-training performance than negative feedback, but only positive feedback indicating listeners were doing badly on the task resulted in learning. As we have previously speculated, feedback that better reflected the difficulty of the task was more effective in driving learning than feedback that suggested performance was better than it should have been given perceived task difficulty. But contrary to expectations, positive feedback was more effective than negative feedback in driving learning. Feedback thus had two separable effects on learning: feedback valence affected motivation on a subjectively difficult task, and learning occurred only when feedback probability reflected the subjective difficulty. To optimize learning, training programs need to take into consideration both feedback valence and probability. PMID:25946173

The extended variant of the bond valence-bond length correlation curve for boron(III)-oxygen bonds

International Nuclear Information System (INIS)

Sidey, Vasyl

2015-01-01

The extended variant of the bond valence (s)-bond length (r) correlation curve for boron(III)-oxygen bonds has been closely approximated using the three-parameter function s = [k/(r - l)] - m, where s is measured in valence units (vu), r is measured in Aa, k = 0.53 Aa.vu, l = 0.975(1) Aa and m = 0.32 vu. The function s = exp[(r 0 - r)/b] traditionally used in the modern bond valence model requires the separate set of the bond valence parameters (r 0 = 1.362 Aa; b = 0.23 Aa) in order to approximate the above s-r curve for the bonds shorter than ∝1.3 Aa.

Bond charge approximation for valence electron density in elemental semiconductors

International Nuclear Information System (INIS)

Bashenov, V.K.; Gorbachov, V.E.; Marvakov, D.I.

1985-07-01

The spatial valence electron distribution in silicon and diamond is calculated in adiabatic bond charge approximation at zero temperature when bond charges have the Gaussian shape and their tensor character is taken into account. An agreement between theory and experiment has been achieved. For this purpose Xia's ionic pseudopotentials and Schulze-Unger's dielectric function are used. By two additional parameters Asub(B) and Zsub(B)sup(') we describe the spatial extent of the bond charge and local-field corrections, respectively. The parameter Zsub(B)sup(') accounts for the ratio between the Coulomb and exchange correlation interactions of the valence electrons and its silicon and diamond values have different signs. (author)

Not always a matter of context: direct effects of red on arousal but context-dependent moderations on valence

Directory of Open Access Journals (Sweden)

Vanessa L. Buechner

2016-09-01

Full Text Available The arousal theory of color proposes that red is associated with arousal. Research on the color-in-context theory, in turn, states that the context in which red is perceived influences its valence-related meaning and behavioral responses to it. This study faces and integrates these theories by examining the influence of red on both arousal and valence perceptions of test-relevant and neutral stimuli, rendering a color 2 (red vs. blue × context 2 (test vs. neutral between-subjects design. Participants rated different pictures regarding their arousal and valence component, respectively. In line with the assumptions of both theories, red increased arousal perceptions of stimuli irrespective of their valence but a context × color interaction was found for valence perceptions: for participants viewing test-relevant pictures, red increased their perceptions of negativity compared to neutral pictures. The present study shows that both theories are actually compatible when differentiating the arousal and valence component.

Ligand-protected gold clusters: the structure, synthesis and applications

International Nuclear Information System (INIS)

Pichugina, D A; Kuz'menko, N E; Shestakov, A F

2015-01-01

Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Au n with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au 15 and Au 25 ) and on anchorage to a support surface (Au 25 /SiO 2 , Au 20 /C, Au 10 /FeO x ) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR) n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters M x Au n L m (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR) x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active

Open-Minded Midwifes, Literate Butchers, and Greedy Hooligans—The Independent Contributions of Stereotype Valence and Consistency on Evaluative Judgments

Science.gov (United States)

Schubert, Lisa; Körner, Anita; Lindau, Berit; Strack, Fritz; Topolinski, Sascha

2017-01-01

Do people evaluate an open-minded midwife less positively than a caring midwife? Both open-minded and caring are generally seen as positive attributes. However, consistency varies—the attribute caring is consistent with the midwife stereotype while open-minded is not. In general, both stimulus valence and consistency can influence evaluations. Six experiments investigated the respective influence of valence and consistency on evaluative judgments in the domain of stereotyping. In an impression formation paradigm, valence and consistency of stereotypic information about target persons were manipulated orthogonally and spontaneous evaluations of these target persons were measured. Valence reliably influenced evaluations. However, for strongly valenced stereotypes, no effect of consistency was observed. Parameters possibly preventing the occurrence of consistency effects were ruled out, specifically, valence of inconsistent attributes, processing priority of category information, and impression formation instructions. However, consistency had subtle effects on evaluative judgments if the information about a target person was not strongly valenced and experimental conditions were optimal. Concluding, in principle, both stereotype valence and consistency can play a role in evaluative judgments of stereotypic target persons. However, the more subtle influence of consistency does not seem to substantially influence evaluations of stereotyped target persons. Implications for fluency research and stereotype disconfirmation are discussed. PMID:29062289

Open-Minded Midwifes, Literate Butchers, and Greedy Hooligans-The Independent Contributions of Stereotype Valence and Consistency on Evaluative Judgments.

Science.gov (United States)

Schubert, Lisa; Körner, Anita; Lindau, Berit; Strack, Fritz; Topolinski, Sascha

2017-01-01

Do people evaluate an open-minded midwife less positively than a caring midwife? Both open-minded and caring are generally seen as positive attributes. However, consistency varies-the attribute caring is consistent with the midwife stereotype while open-minded is not. In general, both stimulus valence and consistency can influence evaluations. Six experiments investigated the respective influence of valence and consistency on evaluative judgments in the domain of stereotyping. In an impression formation paradigm, valence and consistency of stereotypic information about target persons were manipulated orthogonally and spontaneous evaluations of these target persons were measured. Valence reliably influenced evaluations. However, for strongly valenced stereotypes, no effect of consistency was observed. Parameters possibly preventing the occurrence of consistency effects were ruled out, specifically, valence of inconsistent attributes, processing priority of category information, and impression formation instructions. However, consistency had subtle effects on evaluative judgments if the information about a target person was not strongly valenced and experimental conditions were optimal. Concluding, in principle, both stereotype valence and consistency can play a role in evaluative judgments of stereotypic target persons. However, the more subtle influence of consistency does not seem to substantially influence evaluations of stereotyped target persons. Implications for fluency research and stereotype disconfirmation are discussed.

Open-Minded Midwifes, Literate Butchers, and Greedy Hooligans—The Independent Contributions of Stereotype Valence and Consistency on Evaluative Judgments

Directory of Open Access Journals (Sweden)

Lisa Schubert

2017-10-01

Full Text Available Do people evaluate an open-minded midwife less positively than a caring midwife? Both open-minded and caring are generally seen as positive attributes. However, consistency varies—the attribute caring is consistent with the midwife stereotype while open-minded is not. In general, both stimulus valence and consistency can influence evaluations. Six experiments investigated the respective influence of valence and consistency on evaluative judgments in the domain of stereotyping. In an impression formation paradigm, valence and consistency of stereotypic information about target persons were manipulated orthogonally and spontaneous evaluations of these target persons were measured. Valence reliably influenced evaluations. However, for strongly valenced stereotypes, no effect of consistency was observed. Parameters possibly preventing the occurrence of consistency effects were ruled out, specifically, valence of inconsistent attributes, processing priority of category information, and impression formation instructions. However, consistency had subtle effects on evaluative judgments if the information about a target person was not strongly valenced and experimental conditions were optimal. Concluding, in principle, both stereotype valence and consistency can play a role in evaluative judgments of stereotypic target persons. However, the more subtle influence of consistency does not seem to substantially influence evaluations of stereotyped target persons. Implications for fluency research and stereotype disconfirmation are discussed.

Valence of facial cues influences sheep learning in a visual discrimination task

OpenAIRE

Bellegarde, Lucille; Erhard, Hans; Weiss, A.; Boissy, Alain; Haskell, M.J.

2017-01-01

Sheep are one of the most studied farm species in terms of their ability to process information from faces, but little is known about their face-based emotion recognition abilities. We investigated (a) whether sheep could use images of sheep faces taken in situation of varying valence as cues in a simultaneous discrimination task and (b) whether the valence of the situation affects their learning performance. To accomplish this, we photographed faces of sheep in three situations inducing emot...

Valence of Facial Cues Influences Sheep Learning in a Visual Discrimination Task

OpenAIRE

Lucille G. A. Bellegarde; Lucille G. A. Bellegarde; Lucille G. A. Bellegarde; Hans W. Erhard; Alexander Weiss; Alain Boissy; Marie J. Haskell

2017-01-01

Sheep are one of the most studied farm species in terms of their ability to process information from faces, but little is known about their face-based emotion recognition abilities. We investigated (a) whether sheep could use images of sheep faces taken in situation of varying valence as cues in a simultaneous discrimination task and (b) whether the valence of the situation affects their learning performance. To accomplish this, we photographed faces of sheep in three situations inducing emot...

Nature of the valence band states in Bi2(Ca, Sr, La)3Cu2O8

International Nuclear Information System (INIS)

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

1990-01-01

We have used photoemission spectroscopy to examine the symmetry of the occupied states of the valence band for the La doped superconductor Bi 2 (Ca, Sr, La) 3 Cu 2 O 8 . While the oxygen states near the bottom of the 7 eV wide valence band exhibit predominantly O 2p z symmetry, the states at the top of the valence band extending to the Fermi level are found to have primarily O 2p x and O 2p y character. We have also examined anomalous intensity enhancements in the valence band feature 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 O2s transitions to unoccupied O2p states

Looking behaviour and preference for artworks: the role of emotional valence and location.

Science.gov (United States)

Kreplin, Ute; Thoma, Volker; Rodway, Paul

2014-10-01

The position of an item influences its evaluation, with research consistently finding that items occupying central locations are preferred and have a higher subjective value. The current study investigated whether this centre-stage effect (CSE) is a result of bottom-up gaze allocation to the central item, and whether it is affected by item valence. Participants (n=50) were presented with three images of artistic paintings in a row and asked to choose the image they preferred. Eye movements were recorded for a subset of participants (n=22). On each trial the three artworks were either similar but different, or were identical and with positive valence, or were identical and with negative valence. The results showed a centre-stage effect, with artworks in the centre of the row preferred, but only when they were identical and of positive valence. Significantly greater gaze allocation to the central and left artwork was not mirrored by equivalent increases in preference choices. Regression analyses showed that when the artworks were positive and identical the participants' last fixation predicted preference for the central art-work, whereas the fixation duration predicted preference if the images were different. Overall the result showed that item valence, rather than level of gaze allocation, influences the CSE, which is incompatible with the bottom-up gaze explanation. We propose that the centre stage heuristic, which specifies that the best items are in the middle, is able to explain these findings and the centre-stage effect. Copyright © 2014 Elsevier B.V. All rights reserved.

Two Parallel Pathways Assign Opposing Odor Valences during Drosophila Memory Formation

Directory of Open Access Journals (Sweden)

Daisuke Yamazaki

2018-02-01

Full Text Available During olfactory associative learning in Drosophila, odors activate specific subsets of intrinsic mushroom body (MB neurons. Coincident exposure to either rewards or punishments is thought to activate extrinsic dopaminergic neurons, which modulate synaptic connections between odor-encoding MB neurons and MB output neurons to alter behaviors. However, here we identify two classes of intrinsic MB γ neurons based on cAMP response element (CRE-dependent expression, γCRE-p and γCRE-n, which encode aversive and appetitive valences. γCRE-p and γCRE-n neurons act antagonistically to maintain neutral valences for neutral odors. Activation or inhibition of either cell type upsets this balance, toggling odor preferences to either positive or negative values. The mushroom body output neurons, MBON-γ5β′2a/β′2mp and MBON-γ2α′1, mediate the actions of γCRE-p and γCRE-n neurons. Our data indicate that MB neurons encode valence information, as well as odor information, and this information is integrated through a process involving MBONs to regulate learning and memory.

Organ donation video messaging: differential appeal, emotional valence, and behavioral intention.

Science.gov (United States)

Rodrigue, J R; Fleishman, A; Vishnevsky, T; Fitzpatrick, S; Boger, M

2014-10-01

Video narratives increasingly are used to draw the public's attention to the need for more registered organ donors. We assessed the differential impact of donation messaging videos on appeal, emotional valence, and organ donation intentions in 781 non-registered adults. Participants watched six videos (four personal narratives, one informational video without personal narrative, and one unrelated to donation) with or without sound (subtitled), randomly sequenced to minimize order effects. We assessed appeal, emotional valence, readiness to register as organ donors, and donation information-seeking behavior. Compared to other video types, one featuring a pediatric transplant recipient (with or without sound) showed more favorable appeal (p emotional valence (p emotion (OR = 1.05, 95% CI = 1.03, 1.07, p < 0.001) were significant multivariable predictors of clicking through to the donation website. Brief, one-min videos can have a very dramatic and positive impact on willingness to consider donation and behavioral intentions to register as an organ donor. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Enhanced conflict-driven cognitive control by emotional arousal, not by valence.

Science.gov (United States)

Zeng, Qinghong; Qi, Senqing; Li, Miaoyun; Yao, Shuxia; Ding, Cody; Yang, Dong

2017-09-01

Emotion is widely agreed to have two dimensions, valence and arousal. Few studies have explored the effect of emotion on conflict adaptation by considering both of these, which could have dissociate influence. The present study aimed to fill the gap as to whether emotional valence and arousal would exert dissociable influence on conflict adaptation. In the experiments, we included positive, neutral, and negative conditions, with comparable arousal between positive and negative conditions. Both positive and negative conditions have higher arousal than neutral ones. In Experiment 1, by using a two-colour-word Flanker task, we found that conflict adaptation was enhanced in both positive and negative contexts compared to a neutral context. Furthermore, this effect still existed when controlling stimulus-response repetitions in Experiment 2, which used a four-colour-word Flanker task. The findings suggest emotional arousal enhances conflict adaptation, regardless of emotional valence. Thus, future studies should consider emotional arousal when studying the effect of emotion on conflict adaptation. Moreover, the unique role of the emotional context in conflict-driven cognitive control is emphasised.

Vection Modulates Emotional Valence of Autobiographical Episodic Memories

Science.gov (United States)

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

2013-01-01

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

Group IB Organometallic Chemistry XIX.Synthesis and characterization of mixed-organocopper cluster compounds R4R'2Cu6 containing aryl and acetylide ligands.

NARCIS (Netherlands)

Koten, G. van; Hoedt, R.W.M. ten; Noltes, J.G.

1977-01-01

Mixed-organocopper cluster compounds Ar4Cu6(CCR)2 (Ar = 2-Me2NC6H4, R = phenyl, 4-tolyl, 2,4-xylyl or mesityl) have been prepared in high yield by the ligand-substitution reaction of Ar4Cu6Br2 with two equivalents of LiCCR. Ar4Cu6(CCC6H4CH3-4)2 has also been prepared via the aryl¡ªarylacetylide

Valence holes observed in nanodiamonds dispersed in water

Science.gov (United States)

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

Infrared spectroscopy of ionic clusters

Energy Technology Data Exchange (ETDEWEB)

Price, J.M. (California Univ., Berkeley, CA (USA). Dept. of Chemistry Lawrence Berkeley Lab., CA (USA))

1990-11-01

This thesis describes new experiments wherein the infrared vibrational predissociation spectra of a number of mass-selected ionic cluster systems have been obtained and analyzed in the 2600 to 4000 cm{sup {minus}1} region. The species studied include: the hydrated hydronium ions, H{sub 3}O{sup +} (H{sub 2}O){sub 3 {minus}10}, ammoniated ammonium ions, NH{sub 4}{sup +}(NH{sub 3}){sub 1 {minus}10} and cluster ions involving both water and ammonia around an ammonium ion core, (mixed clusters) NH{sub 4}{sup +}(NH{sub 3}){sub n}(H{sub 2}O){sub m} (n+m=4). In each case, the spectra reveal well resolved structures that can be assigned to transitions arising from the vibrational motions of both the ion core of the clusters and the surrounding neutral solvent molecules. 154 refs., 19 figs., 8 tabs.

Name-valence and physical attractiveness in Facebook: their compensatory effects on friendship acceptance.

Science.gov (United States)

Greitemeyer, Tobias; Kunz, Irene

2013-01-01

Name-valence and physical attractiveness have been shown to be associated with how people respond toward others, in that people judge and behave more positively toward individuals with positive names and individuals who are physically attractive. The present research examined whether Facebook users are more likely to accept friendship requests from other Facebook users with positive (relative to negative) names and who are physically attractive (relative to being moderately attractive). In fact, both name-valence and physical attractiveness affected friendship acceptance. Moreover, results revealed that name-valence can be compensated by physical attractiveness (and vice versa). Acceptance rates of requests from users with positive names who are moderately attractive, as well as requests from users with negative names who are attractive did not significantly differ from those with positive names who are attractive.

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

Science.gov (United States)

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.

Atomic contributions to the valence band photoelectron spectra of metal-free, iron and manganese phthalocyanines

Energy Technology Data Exchange (ETDEWEB)

Bidermane, I., E-mail: ieva.bidermane@physics.uu.se [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden); Institut des Nanosciences de Paris, UPMC Univ. Paris 06, CNRS UMR 7588, F-75005 Paris (France); Brumboiu, I.E. [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden); Totani, R. [Department of Physical and Chemical Sciences, University of L’Aquila, Via Vetoio, Coppito, I-67010 L’Aquila (Italy); Grazioli, C. [CNR-IOM, Laboratorio TASC, ss. 14 km. 163.5, Basovizza, 34149 Trieste (Italy); Departement of Chemical and Pharmaceutical Sciences, University of Trieste (Italy); Shariati-Nilsson, M.N.; Herper, H.C.; Eriksson, O.; Sanyal, B. [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden); Ressel, B. [University of Nova Gorica, Vipavska Cesta 11c, 5270 Ajdovščina (Slovenia); Simone, M. de [CNR-IOM, Laboratorio TASC, ss. 14 km. 163.5, Basovizza, 34149 Trieste (Italy); Lozzi, L. [Department of Physical and Chemical Sciences, University of L’Aquila, Via Vetoio, Coppito, I-67010 L’Aquila (Italy); Brena, B.; Puglia, C. [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden)

2015-11-15

Highlights: • In detail comparison between the valence band structure of H{sub 2}Pc, FePc and MnPc. • Comparison between the gas phase samples and thin evaporated films on Au (1 1 1). • Detailed analysis of the atomic orbital contributions to the valence band features. • DFT/HSE06 study of the valence band electronic structure of H{sub 2}Pc, FePc and MnPc. - Abstract: The present work reports a photoelectron spectroscopy study of the low-energy region of the valence band of metal-free phthalocyanine (H{sub 2}Pc) compared with those of iron phthalocyanine (FePc) and manganese phthalocyanine (MnPc). We have analysed in detail the atomic orbital composition of the valence band both experimentally, by making use of the variation in photoionization cross-sections with photon energy, and theoretically, by means of density functional theory. The atomic character of the Highest Occupied Molecular Orbital (HOMO), reflected on the outermost valence band binding energy region, is different for MnPc as compared to the other two molecules. The peaks related to the C 2p contributions, result in the HOMO for H{sub 2}Pc and FePc and in the HOMO-1 for MnPc as described by the theoretical predictions, in very good agreement with the experimental results. The DFT simulations, discerning the atomic contribution to the density of states, indicate how the central metal atom interacts with the C and N atoms of the molecule, giving rise to different partial and total density of states for these three Pc molecules.

The chemical bond in inorganic chemistry the bond valence model

CERN Document Server

Brown, I David

2016-01-01

The bond valence model is a version of the ionic model in which the chemical constraints are expressed in terms of localized chemical bonds formed by the valence charge of the atoms. Theorems derived from the properties of the electrostatic flux predict the rules obeyed by both ionic and covalent bonds. They make quantitative predictions of coordination number, crystal structure, bond lengths and bond angles. Bond stability depends on the matching of the bonding strengths of the atoms, while the conflicting requirements of chemistry and space lead to the structural instabilities responsible for the unusual physical properties displayed by some materials. The model has applications in many fields ranging from mineralogy to molecular biology.

Preferential site occupancy observed in coexpanded argon-krypton clusters

International Nuclear Information System (INIS)

Lundwall, M.; Bergersen, H.; Lindblad, A.; Oehrwall, G.; Svensson, S.; Bjoerneholm, O.; Tchaplyguine, M.

2006-01-01

Free heterogeneous argon-krypton clusters have been produced by coexpansion and investigated by means of x-ray photoelectron spectroscopy. By examining cluster surface and bulk binding energy shifts, relative intensities, and peak widths, we show that in the mixed argon-krypton clusters the krypton atoms favor the bulk and argon atoms are pushed to the surface. Furthermore, we show that krypton atoms in the surface layer occupy high-coordination sites and that heterogeneous argon-krypton clusters produced by coexpansion show the same surface structure as argon host clusters doped with krypton. These observations are supported by site-dependent calculations of chemical shifts

New Observational Evidence of Flash Mixing on the White Dwarf Cooling Curve

Science.gov (United States)

Brown, T. M.; Lanz, T.; Sweigart, A. V.; Cracraft, Misty; Hubeny, Ivan; Landsman, W. B.

2011-01-01

Blue hook stars are a class of subluminous extreme horizontal branch stars that were discovered in UV images of the massive globular clusters w Cen and NGC 2808. These stars occupy a region of the HR diagram that is unexplained by canonical stellar evolution theory. Using new theoretical evolutionary and atmospheric models, we have shown that the blue hook stars are very likely the progeny of stars that undergo extensive internal mixing during a late helium-core flash on the white dwarf cooling curve. This "flash mixing" produces hotter-than-normal EHB stars with atmospheres significantly enhanced in helium and carbon. The larger bolometric correction, combined with the decrease in hydrogen opacity, makes these stars appear sub luminous in the optical and UV. Flash mixing is more likely to occur in stars born with a high helium abundance, due to their lower mass at the main sequence turnoff. For this reason, the phenomenon is more common in those massive globular clusters that show evidence for secondary populations enhanced in helium. However, a high helium abundance does not, by itself, explain the presence of blue hook stars in massive globular clusters. Here, we present new observational evidence for flash mixing, using recent HST observations. These include UV color-magnitude diagrams of six massive globular clusters and far-UV spectroscopy of hot subdwarfs in one of these clusters (NGC 2808).

Modeling of correlated data with informative cluster sizes: An evaluation of joint modeling and within-cluster resampling approaches.

Science.gov (United States)

Zhang, Bo; Liu, Wei; Zhang, Zhiwei; Qu, Yanping; Chen, Zhen; Albert, Paul S

2017-08-01

Joint modeling and within-cluster resampling are two approaches that are used for analyzing correlated data with informative cluster sizes. Motivated by a developmental toxicity study, we examined the performances and validity of these two approaches in testing covariate effects in generalized linear mixed-effects models. We show that the joint modeling approach is robust to the misspecification of cluster size models in terms of Type I and Type II errors when the corresponding covariates are not included in the random effects structure; otherwise, statistical tests may be affected. We also evaluate the performance of the within-cluster resampling procedure and thoroughly investigate the validity of it in modeling correlated data with informative cluster sizes. We show that within-cluster resampling is a valid alternative to joint modeling for cluster-specific covariates, but it is invalid for time-dependent covariates. The two methods are applied to a developmental toxicity study that investigated the effect of exposure to diethylene glycol dimethyl ether.

Sex, Age, and Emotional Valence: Revealing Possible Biases in the 'Reading the Mind in the Eyes' Task.

Science.gov (United States)

Kynast, Jana; Schroeter, Matthias L

2018-01-01

The 'Reading the Mind in the Eyes' test (RMET) assesses a specific socio-cognitive ability, i.e., the ability to identify mental states from gaze. The development of this ability in a lifespan perspective is of special interest. Whereas former investigations were limited mainly to childhood and adolescence, the focus has been shifted towards aging, and psychiatric and neurodegenerative diseases recently. Although the RMET is frequently applied in developmental psychology and clinical settings, stimulus characteristics have never been investigated with respect to potential effects on test performance. Here, we analyzed the RMET stimulus set with a special focus on interrelations between sex, age and emotional valence. Forty-three persons rated age and emotional valence of the RMET picture set. Differences in emotional valence and age ratings between male and female items were analyzed. The linear relation between age and emotional valence was tested over all items, and separately for male and female items. Male items were rated older and more negative than female stimuli. Regarding male RMET items, age predicted emotional valence: older age was associated with negative emotions. Contrary, age and valence were not linearly related in female pictures. All ratings were independent of rater characteristics. Our results demonstrate a strong confound between sex, age, and emotional valence in the RMET. Male items presented a greater variability in age ratings compared to female items. Age and emotional valence were negatively associated among male items, but no significant association was found among female stimuli. As personal attributes impact social information processing, our results may add a new perspective on the interpretation of previous findings on interindividual differences in RMET accuracy, particularly in the field of developmental psychology, and age-associated neuropsychiatric diseases. A revision of the RMET might be afforded to overcome confounds

Emotional Valence, Arousal, and Threat Ratings of 160 Chinese Words among Adolescents.

Science.gov (United States)

Ho, Samuel M Y; Mak, Christine W Y; Yeung, Dannii; Duan, Wenjie; Tang, Sandy; Yeung, June C; Ching, Rita

2015-01-01

This study was conducted to provide ratings of valence/pleasantness, arousal/excitement, and threat/potential harm for 160 Chinese words. The emotional valence classification (positive, negative, or neutral) of all of the words corresponded to that of the equivalent English language words. More than 90% of the participants, junior high school students aged between 12 and 17 years, understood the words. The participants were from both mainland China and Hong Kong, thus the words can be applied to adolescents familiar with either simplified (e.g. in mainland China) or traditional Chinese (e.g. in Hong Kong) with a junior secondary school education or higher. We also established eight words with negative valence, high threat, and high arousal ratings to facilitate future research, especially on attentional and memory biases among individuals prone to anxiety. Thus, the new emotional word list provides a useful source of information for affective research in the Chinese language.

Improved R2* liver iron concentration assessment using a novel fuzzy c-mean clustering scheme

International Nuclear Information System (INIS)

Saiviroonporn, Pairash; Viprakasit, Vip; Krittayaphong, Rungroj

2015-01-01

In thalassemia patients, R2* liver iron concentration (LIC) measurement is a common clinical tool for assessing iron overload and for determining necessary chelator dose and evaluating its efficacy. Despite the importance of accurate LIC measurement, existing methods suffer from LIC variability, especially at the severe iron overload range due to inclusion of vessel parts in LIC calculation. In this study, we build upon previous Fuzzy C-Mean (FCM) clustering work to formulate a scheme with superior performance in segmenting vessel pixels from the parenchyma. Our method (MIX-FCM) combines our novel 2D-FCM with the existing 1D-FCM algorithm. This study further assessed possible optimal clustering parameters (OP scheme) and proposed a semi-automatic (SA) scheme for routine clinical application. Segmentation of liver parenchyma and vessels was performed on T2* images and their LIC maps in 196 studies from 147 thalassemia major patients. We used manual segmentation as the reference. 1D-FCM clustering was performed on the acquired image alone and 2D-FCM used both the acquired image and its LIC data. To execute the MIX-FCM method, the best outcome (OP-MIX-FCM) was selected from the aforementioned methods and was compared to the SA-MIX-FCM scheme. We used the percent value of the normalized interquartile range (nIQR) to its median to evaluate the variability of all methods. 2D-FCM clustering is more effective than 1D-FCM clustering at the severe overload range only, but inferior for other ranges (where 1D-FCM provides suitable results). This complementary performance between the two methods allows MIX-FCM to improve results for all ranges. OP-MIX-FCM clustering error was 2.1 ± 2.3 %, compared with 10.3 ± 9.9 % and 7.0 ± 11.9 % from 1D- and 2D-FCM clustering, respectively. SA-MIX-FCM result was comparable to OP-MIX-FCM result, with both schemes showing ability to decrease overall nIQR by approximately 30 %. Our proposed 2D-FCM algorithm is not as superior to 1D-FCM as

Quadrupole and octupole collectivity and cluster structures in neon isotopes

Science.gov (United States)

Marević, P.; Ebran, J.-P.; Khan, E.; Nikšić, T.; Vretenar, D.

2018-02-01

The lowest positive- and negative-parity bands of 20Ne and neutron-rich even-even Ne isotopes are investigated using a theoretical framework based on energy density functionals. Starting from a self-consistent relativistic Hartree-Bogoliubov calculation of axially symmetric and reflection-asymmetric deformation energy surfaces, the collective symmetry-conserving states are built using projection techniques and the generator coordinate method. Overall a good agreement with the experimental excitation energies and transition rates is obtained. In particular, the model provides an accurate description of the excitation spectra and transition probabilities in 20Ne. The contribution of cluster configurations to the low-energy states is discussed, as well as the transitional character of the ground state. The analysis is extended to 22Ne and the shape-coexisting isotope 24Ne, and to the drip-line nuclei 32Ne and 34Ne. The role of valence neutrons in the formation of molecular-type bonds between clusters is discussed.

Nonideal mixing of phosphatidylserine and phosphatidylcholine in the fluid lamellar phase.

Science.gov (United States)

Huang, J; Swanson, J E; Dibble, A R; Hinderliter, A K; Feigenson, G W

1993-02-01

The mixing of phosphatidylserine (PS) and phosphatidylcholine (PC) in fluid bilayer model membranes was studied by measuring binding of aqueous Ca2+ ions. The measured [Ca2+]aq was used to derive the activity coefficient for PS, gamma PS, in the lipid mixture. For (16:0, 18:1) PS in binary mixtures with either (16:0, 18:1)PC, (14:1, 14:1)PC, or (18:1, 18:1)PC, gamma PS > 1; i.e., mixing is nonideal, with PS and PC clustered rather than randomly distributed, despite the electrostatic repulsion between PS headgroups. To understand better this mixing behavior, Monte Carlo simulations of the PS/PC distributions were performed, using Kawasaki relaxation. The excess energy was divided into an electrostatic term Uel and one adjustable term including all other nonideal energy contributions, delta Em. Uel was calculated using a discrete charge theory. Kirkwood's coupling parameter method was used to calculate the excess free energy of mixing, delta GEmix, hence In gamma PS,calc. The values of In gamma PS,calc were equalized by adjusting delta Em in order to find the simulated PS/PC distribution that corresponded to the experimental results. We were thus able to compare the smeared charge calculation of [Ca2+]surf with a calculation ("masked evaluation method") that recognized clustering of the negatively charged PS: clustering was found to have a modest effect on [Ca2+]surf, relative to the smeared charge model. Even though both PS and PC tend to cluster, the long-range nature of the electrostatic repulsion reduces the extent of PS clustering at low PS mole fraction compared to PC clustering at an equivalent low PC mole fraction.

Temperature effects in the valence fluctuation of europium intermetallic compounds

International Nuclear Information System (INIS)

Menezes, O.L.T. de; Troper, A.; Gomes, A.A.

1978-03-01

A previously reported model for valence fluctuations in europium compound in order to account for thermal occupation effect. Experimental results are critically discussed and new experiments are suggested

Pion and kaon valence-quark parton quasidistributions

Science.gov (United States)

Xu, Shu-Sheng; Chang, Lei; Roberts, Craig D.; Zong, Hong-Shi

2018-05-01

Algebraic Ansätze for the Poincaré-covariant Bethe-Salpeter wave functions of the pion and kaon are used to calculate their light-front wave functions, parton distribution amplitudes, parton quasidistribution amplitudes, valence parton distribution functions, and parton quasidistribution functions (PqDFs). The light-front wave functions are broad, concave functions, and the scale of flavor-symmetry violation in the kaon is roughly 15%, being set by the ratio of emergent masses in the s - and u -quark sectors. Parton quasidistribution amplitudes computed with longitudinal momentum Pz=1.75 GeV provide a semiquantitatively accurate representation of the objective parton distribution amplitude, but even with Pz=3 GeV , they cannot provide information about this amplitude's end point behavior. On the valence-quark domain, similar outcomes characterize PqDFs. In this connection, however, the ratio of kaon-to-pion u -quark PqDFs is found to provide a good approximation to the true parton distribution function ratio on 0.4 ≲x ≲0.8 , suggesting that with existing resources computations of ratios of parton quasidistributions can yield results that support empirical comparison.

The role of order-disorder transitions in the quest for molecular multiferroics: structural and magnetic neutron studies of a mixed valence iron(II)-iron(III) formate framework.

Science.gov (United States)

Cañadillas-Delgado, Laura; Fabelo, Oscar; Rodríguez-Velamazán, J Alberto; Lemée-Cailleau, Marie-Hélène; Mason, Sax A; Pardo, Emilio; Lloret, Francesc; Zhao, Jiong-Peng; Bu, Xian-He; Simonet, Virginie; Colin, Claire V; Rodríguez-Carvajal, Juan

2012-12-05

Neutron diffraction studies have been carried out to shed light on the unprecedented order-disorder phase transition (ca. 155 K) observed in the mixed-valence iron(II)-iron(III) formate framework compound [NH(2)(CH(3))(2)](n)[Fe(III)Fe(II)(HCOO)(6)](n). The crystal structure at 220 K was first determined from Laue diffraction data, then a second refinement at 175 K and the crystal structure determination in the low temperature phase at 45 K were done with data from the monochromatic high resolution single crystal diffractometer D19. The 45 K nuclear structure reveals that the phase transition is associated with the order-disorder of the dimethylammonium counterion that is weakly anchored in the cavities of the [Fe(III)Fe(II)(HCOO)(6)](n) framework. In the low-temperature phase, a change in space group from P31c to R3c occurs, involving a tripling of the c-axis due to the ordering of the dimethylammonium counterion. The occurrence of this nuclear phase transition is associated with an electric transition, from paraelectric to antiferroelectric. A combination of powder and single crystal neutron diffraction measurements below the magnetic order transition (ca. 37 K) has been used to determine unequivocally the magnetic structure of this Néel N-Type ferrimagnet, proving that the ferrimagnetic behavior is due to a noncompensation of the different Fe(II) and Fe(III) magnetic moments.

The Synthesis of NiO/TiO2 Heterostructures and Their Valence Band Offset Determination

Directory of Open Access Journals (Sweden)

Z. H. Ibupoto

2014-01-01

Full Text Available In this work, a heterojunction based on p-type NiO/n-type TiO2 nanostructures has been prepared on the fluorine doped tin oxide (FTO glass substrate by hydrothermal method. Scanning electron microscopy (SEM and X-Ray diffraction techniques were used for the morphological and crystalline arrays characterization. The X-ray photoelectron spectroscopy was employed to determine the valence-band offset (VBO of the NiO/TiO2 heterojunction prepared on FTO glass substrate. The core levels of Ni 2p and Ti 2p were utilized to align the valence-band offset of p-type NiO/n-type TiO2 heterojunction. The valence band offset was found to be ∼0.41 eV and the conduction band was calculated about ∼0.91 eV. The ratio of conduction band offset and the valence-band offset was found to be 2.21.

Distinct populations of neurons respond to emotional valence and arousal in the human subthalamic nucleus.

Science.gov (United States)

Sieger, Tomáš; Serranová, Tereza; Růžička, Filip; Vostatek, Pavel; Wild, Jiří; Štastná, Daniela; Bonnet, Cecilia; Novák, Daniel; Růžička, Evžen; Urgošík, Dušan; Jech, Robert

2015-03-10

Both animal studies and studies using deep brain stimulation in humans have demonstrated the involvement of the subthalamic nucleus (STN) in motivational and emotional processes; however, participation of this nucleus in processing human emotion has not been investigated directly at the single-neuron level. We analyzed the relationship between the neuronal firing from intraoperative microrecordings from the STN during affective picture presentation in patients with Parkinson's disease (PD) and the affective ratings of emotional valence and arousal performed subsequently. We observed that 17% of neurons responded to emotional valence and arousal of visual stimuli according to individual ratings. The activity of some neurons was related to emotional valence, whereas different neurons responded to arousal. In addition, 14% of neurons responded to visual stimuli. Our results suggest the existence of neurons involved in processing or transmission of visual and emotional information in the human STN, and provide evidence of separate processing of the affective dimensions of valence and arousal at the level of single neurons as well.

Theoretical calculations of valence states in Fe-Mo compounds

International Nuclear Information System (INIS)

Estrada, F; Navarro, O; Noverola, H; Suárez, J R; Avignon, M

2014-01-01

The half-metallic ferromagnetic double perovskite compound Sr 2 FeMoO 6 is considered as an important material for spintronic applications. It appears to be fundamental to understand the role of electronic parameters controlling the half-metallic ground state. Fe-Mo double perovskites usually present some degree of Fe/Mo disorder which generally increases with doping. In this work, we study the valence states of Fe-Mo cations in the off-stoichiometric system Sr 2 Fe 1+x Mo 1−x O 6 (−1 ≤ x ≤ 1/3) with disorder. Our results for Fe and Mo valence states are obtained using the Green functions and the renormalization perturbation expansion method. The model is based on a correlated electron picture with localized Fe-spins and conduction Mo-electrons interacting with the local spins via a double-exchange-type mechanism

Interactions of energetic particles and clusters with solids

International Nuclear Information System (INIS)

Averback, R.S.; Hsieh, Horngming; Benedek, R.

1990-12-01

Ion beams are being applied for surface modifications of materials in a variety of different ways: ion implantation, ion beam mixing, sputtering, and particle or cluster beam-assisted deposition. Fundamental to all of these processes is the deposition of a large amount of energy, generally some keV's, in a localized area. This can lead to the production of defects, atomic mixing, disordering and in some cases, amorphization. Recent results of molecular dynamics computer simulations of energetic displacement cascades in Cu and Ni with energies up to 5 keV suggest that thermal spikes play an important role in these processes. Specifically, it will be shown that many aspects of defect production, atomic mixing and ''cascade collapse'' can be understood as a consequence of local melting of the cascade core. Included in this discussion will be the possible role of electron-phonon coupling in thermal spike dynamics. The interaction of energetic clusters of atoms with solid surfaces has also been studied by molecular dynamics simulations. this process is of interest because a large amount of energy can be deposited in a small region and possibly without creating point defects in the substrate or implanting cluster atoms. The simulations reveal that the dynamics of the collision process are strongly dependent on cluster size and energy. Different regimes where defect production, local melting and plastic flow dominate will be discussed. 43 refs., 7 figs

Gastrointestinal absorption of large amounts of plutonium. Effect of valency state on transfer

International Nuclear Information System (INIS)

Lataillade, G.; Duserre, C.; Metivier, H.; Madic, C.; CEA Centre d'Etudes Nucleaires de Fontenay-aux-Roses, 92

1989-01-01

The gastrointestinal absorption of Pu, ingested in valency state III, IV, V or VI was studied in baboons. For each state, the absorption of Pu from masses ranging from 1 to 7 mg per kg of body weight was compared with that from masses ranging from 5 to 45 μg per kg of body weight. The mass ingested did not affect the gastrointestinal absorption of Pu(IV) or PU(VI), but for Pu(V) and to a lesser extent Pu(III), absorption clearly increased about 150-fold and 7-fold respectively, when large masses of Pu were ingested. When small masses were ingested, the valency state did not affect absorption. The increased Pu absorption observed after ingestion of large masses of Pu(V) or (III) might be due to the weak hydrolysis of these valency states. (author)

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

Science.gov (United States)

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

Linkage of molecular units in the chemistry of niobium and tantalum cluster halides

International Nuclear Information System (INIS)

Perrin, C.; Sergent, M.

1991-01-01

In low valency niobium and tantalum halides, interunit linkages are observed between the (Me 6 X 12 )X 6 units. They are insulators and interesting magnetic properties are observed, due to the intrinsic potential magnetism of the Me 6 cluster and depending on the inserted cations, for instance rare earths in MM'Nb 6 Cl 18 (M = monovalent cation, M' = rare earth). Of special interest are the niobium iodides which exhibit (Me 6 X 8 )X 6 units, an exception in the niobium chemistry; interesting properties have been reported for some of these iodides

Prévalence des dyslipidémies au laboratoire de biochimie du CHU ...

African Journals Online (AJOL)

Le cholestérol total, le cholestérol HDL, le cholestérol LDL ainsi que les triglycérides ont été dosés grâce à des méthodes enzymatiques sur un automate de Biochimie de type Cobas Integra 400 (Roche Diagnostics). Résultats: la prévalence des dyslipidémies dans notre population d'étude est de 39,30%. Les prévalences ...

Production and characterization of supersonic carbon cluster beams

International Nuclear Information System (INIS)

Rohlfing, E.A.; Cox, D.M.; Kaldor, A.

1984-01-01

Laser vaporization of a substrate within the throat of a pulsed nozzle is used to generate a supersonic beam of carbon clusters. The neutral cluster beam is probed downstream by UV laser photoionization with time-of-flight mass analysis of the resulting photoions. Using graphite as the substrate, carbon clusters C/sub n/ for n = 1--190 have been produced having a distinctly bimodal cluster size distribution: (i) Both even and odd clusters for C/sub n/, 1 + /sub n/ signals are interpreted on the basis of cluster formation and stability arguments. Ionizing laser power dependences taken at several different photon energies are used to roughly bracket the carbon cluster ionization potentials, and, at high laser intensity, to observe the onset of multiphoton fragmentation. By treating the graphite rod with KOH, a greatly altered carbon cluster distribution with mixed carbon/potassium clusters of formula K 2 C/sub 2n/ is produced

Valence Scaling of Dynamic Facial Expressions Is Altered in High-Functioning Subjects with Autism Spectrum Disorders: An FMRI Study

Science.gov (United States)

Rahko, Jukka S.; Paakki, Jyri-Johan; Starck, Tuomo H.; Nikkinen, Juha; Pauls, David L.; Katsyri, Jari V.; Jansson-Verkasalo, Eira M.; Carter, Alice S.; Hurtig, Tuula M.; Mattila, Marja-Leena; Jussila, Katja K.; Remes, Jukka J.; Kuusikko-Gauffin, Sanna A.; Sams, Mikko E.; Bolte, Sven; Ebeling, Hanna E.; Moilanen, Irma K.; Tervonen, Osmo; Kiviniemi, Vesa

2012-01-01

FMRI was performed with the dynamic facial expressions fear and happiness. This was done to detect differences in valence processing between 25 subjects with autism spectrum disorders (ASDs) and 27 typically developing controls. Valence scaling was abnormal in ASDs. Positive valence induces lower deactivation and abnormally strong activity in ASD…

Dissociable effects of valence and arousal on different subtypes of old/new effect: Evidence from event-related potentials

Directory of Open Access Journals (Sweden)

Huifang eXu

2015-12-01

Full Text Available Here we utilized the study-test paradigm combined with recognition confidence assessment and behavioral and event-related potential (ERP measurements to investigate the effects of valence and arousal on the different subtypes of the old-new effect. We also test the effect of valence and arousal at encoding stage to investigate the underlying mechanism of the effect of the two emotional dimension on different retrieval process. In order to test the effects of valence and arousal on old/new effect precisely, we used the subject-oriented orthogonal design which manipulated valence and arousal independently according to subjects’ verbal reporting to investigate the effects of valence and arousal on old/new effect respectively. Three subtypes of old/new effect were obtained in the test phase, which were FN400, LPC, and late positivity over right frontal. They are supposed to be associated with familiarity, recollection, and post-retrieval processes respectively according to previous studies. For the FN400 component, valence affected mid-frontal negativity from 350 to 500 ms. Pleasant items evoked an enhanced ERP old/new effect relative to unpleasant items. However, arousal only affected LPC amplitude from 500 to 800ms. The old/new effect for high-arousal items was greater than for low-arousal items. Valence also affected the amplitude of a positive-going slow wave at right frontal sites from 800 to 1000 ms, possibly serving as an index of post-retrieval processing. At encoding stage, the valence and arousal also have dissociable effect on the frontal slow wave between 350-800ms and the centro-parietal positivity in 500-800ms. The pleasant items evoked a more positive frontal slow wave relative to unpleasant ones, and the high arousal items evoked a larger centro-parietal positivity relative to low arousal ones. These results suggest that valence and arousal may differentially impact these different memory processes: valence affects familiarity and

Static and dynamical valence-charge-density properties of GaAs

International Nuclear Information System (INIS)

Pietsch, U.

1993-01-01

Owing to the close neighbourhood of Ga and As in Mendeleev's table, GaAs shows two fundamental classes of X-ray structure amplitudes distinguished by their extremely different scattering power. They are differently sensitive to the valence electron density (VED) redistribution caused by the chemical bond and must be measured by different experimental methods. Using such data, both the VED and the difference electron densities (DED) are calculated here. Comparison with theoretical densities shows that the VED is characterized by covalent, ionic and metallic contributions. The DED constructed from GaAs and Ge data demonstrates the electronic response caused by a ''protonic'' charge transfer between both f.c.c. sublattices as well as the transition from a purely covalent to a mixed covalent-ionic bond. Especially the charge-density accumulation between nearest neighbours (bond charge (BC)) depends on the distance between the bonding atoms and changes under the influence of any lattice deformation. This phenomenon is described by a BC-transfer model. Its direct experimental proof is given by measuring the variation of the scattering power of weak reflections under the influence of an external electric field. This experiment demonstrates that the ionicity of the bond changes in addition to the BC variation. (orig.)

Identifying Facial Emotions: Valence Specific Effects and an Exploration of the Effects of Viewer Gender

Science.gov (United States)

Jansari, Ashok; Rodway, Paul; Goncalves, Salvador

2011-01-01

The valence hypothesis suggests that the right hemisphere is specialised for negative emotions and the left hemisphere is specialised for positive emotions (Silberman & Weingartner, 1986). It is unclear to what extent valence-specific effects in facial emotion perception depend upon the gender of the perceiver. To explore this question 46…

Inducing changes in arousal and valence: comparison of two mood induction procedures.

Science.gov (United States)

Jallais, Christophe; Gilet, Anne-Laure

2010-02-01

This research examined the relative effectiveness of two mood induction procedures (MIPs) for inducing four specific moods varying along the dimensions of both valence and arousal. Participants were randomly assigned either to an autobiographical recall or to a music and guided imagery MIP and underwent a happiness, serenity, anger, or sadness mood induction. The findings confirmed the effectiveness of the two MIPs in producing changes on both the valence and arousal dimensions of mood. The results also revealed an unexpected greater efficiency of the autobiographical recall than of the combined procedure.

Effect of an in-plane ligand on the electronic structures of bromo-bridged nano-wire Ni-Pd mixed-metal complexes, [Ni(1-x)Pd(x)(bn)2Br]Br2 (bn = 2S,3S-diaminobutane).

Science.gov (United States)

Sasaki, Mari; Wu, Hashen; Kawakami, Daisuke; Takaishi, Shinya; Kajiwara, Takashi; Miyasaka, Hitoshi; Breedlove, Brian K; Yamashita, Masahiro; Kishida, Hideo; Matsuzaki, Hiroyuki; Okamoto, Hiroshi; Tanaka, Hisaaki; Kuroda, Shinichi

2009-08-03

Single crystals of quasi-one-dimensional bromo-bridged Ni-Pd mixed-metal complexes with 2S,3S-diaminobutane (bn) as an in-plane ligand, [Ni(1-x)Pd(x)(bn)(2)Br]Br(2), were obtained by using an electrochemical oxidation method involving mixed methanol/2-propanol (1:1) solutions containing different ratios of [Ni(II)(bn)(2)]Br(2) and [Pd(II)(bn)(2)]Br(2). To investigate the competition between the electron-correlation of the Ni(III) states, or Mott-Hubbard states (MH), and the electron-phonon interaction of the Pd(II)-Pd(IV) mixed valence states, or charge-density-wave states (CDW), in the Ni-Pd mixed-metal compounds, X-ray structure analyses, X-ray oscillation photograph, and Raman, IR, ESR, and single-crystal reflectance spectra were analyzed. In addition, the local electronic structures of Ni-Pd mixed-metal single crystals were directly investigated by using scanning tunneling microscopy (STM) at room temperature and ambient pressure. The oxidation states of [Ni(1-x)Pd(x)(bn)(2)Br]Br(2) changed from a M(II)-M(IV) mixed valence state to a M(III) MH state at a critical mixing ratio (x(c)) of approximately 0.8, which is lower than that of [Ni(1-x)Pd(x)(chxn)(2)Br]Br(2) (chxn = 1R,2R-diaminocyclohexane) (x(c) approximately 0.9) reported previously. The lower value of x(c) for [Ni(1-x)Pd(x)(bn)(2)Br]Br(2) can be explained by the difference in their CDW dimensionalities because the three-dimensional CDW ordering in [Pd(bn)(2)Br]Br(2) observed by using X-ray diffuse scattering stabilizes the Pd(II)-Pd(IV) mixed valence state more than two-dimensional CDW ordering in [Pd(chxn)(2)Br]Br(2) does, which has been reported previously.

Voice and Valency in San Luis Potosi Huasteco

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Munoz Ledo Yanez, Veronica

2014-01-01

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

Approximate treatment of semicore states in GW calculations with application to Au clusters.

Science.gov (United States)

Xian, Jiawei; Baroni, Stefano; Umari, P

2014-03-28

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G0W0 level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore states are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au20 and Au32, that would be otherwise very difficult to deal with.

Approximate treatment of semicore states in GW calculations with application to Au clusters

Energy Technology Data Exchange (ETDEWEB)

Xian, Jiawei [SISSA – Scuola Internazionale Superiore di Studi Avanzati, Via Bonomea 265, I-34136 Trieste (Italy); Baroni, Stefano [SISSA – Scuola Internazionale Superiore di Studi Avanzati, Via Bonomea 265, I-34136 Trieste (Italy); CNR-IOM Democritos, Theory-Elettra group, Trieste (Italy); Umari, P., E-mail: paolo.umari@unipd.it [CNR-IOM Democritos, Theory-Elettra group, Trieste (Italy); Dipartimento di Fisica e Astronomia, Università di Padova, Via Marzolo 8, I-35131 Padova (Italy)

2014-03-28

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G{sub 0}W{sub 0} level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore states are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au{sub 20} and Au{sub 32}, that would be otherwise very difficult to deal with.

Approximate treatment of semicore states in GW calculations with application to Au clusters

International Nuclear Information System (INIS)

Xian, Jiawei; Baroni, Stefano; Umari, P.

2014-01-01

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G 0 W 0 level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore states are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au 20 and Au 32 , that would be otherwise very difficult to deal with

Transfer of newly acquired stimulus valence between identities in dissociative identity disorder (DID).

Science.gov (United States)

Huntjens, Rafaële J C; Peters, Madelon L; Postma, Albert; Woertman, Liesbeth; Effting, Marieke; van der Hart, Onno

2005-02-01

Patients with Dissociative Identity Disorder (DID) frequently report episodes of interidentity amnesia, that is amnesia for events experienced by other identities. The goal of the present experiment was to test the implicit transfer of trauma-related information between identities in DID. We hypothesized that whereas declarative information may transfer from one identity to another, the emotional connotation of the memory may be dissociated, especially in the case of negative, trauma-related emotional valence. An evaluative conditioning procedure was combined with an affective priming procedure, both performed by different identities. In the evaluative conditioning procedure, previously neutral stimuli come to refer to a negative or positive connotation. The affective priming procedure was used to test the transfer of this acquired valence to an identity reporting interidentity amnesia. Results indicated activation of stimulus valence in the affective priming task, that is transfer of emotional material between identities.

Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals.

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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.

Diffusion escape through a cluster of small absorbing windows

Energy Technology Data Exchange (ETDEWEB)

Holcman, D [Department of Mathematics, Weizmann Institute of Science, Rehovot 76100 (Israel); Schuss, Z [Department of Mathematics, Tel-Aviv University, Tel-Aviv 69978 (Israel)

2008-04-18

We study the first eigenvalue of the Laplace equation in a bounded domain in R{sup d} (d=2,3) with mixed Neumann-Dirichlet (Zaremba) boundary conditions. The Neumann condition is imposed on most of the boundary and the Dirichlet boundary consists of a cluster of small windows. When the windows are well separated the first eigenvalue is asymptotically the sum of eigenvalues of mixed problems with a single Dirichlet window. However, when two or more Dirichlet windows cluster tightly together they interact nonlinearly. We compare our asymptotic approximation of the eigenvalue to the escape rate of simulated Brownian particles through the small windows.

Unlearning of Mixed States in the Hopfield Model —Extensive Loading Case—

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Hayashi, Kao; Hashimoto, Chinami; Kimoto, Tomoyuki; Uezu, Tatsuya

2018-05-01

We study the unlearning of mixed states in the Hopfield model for the extensive loading case. Firstly, we focus on case I, where several embedded patterns are correlated with each other, whereas the rest are uncorrelated. Secondly, we study case II, where patterns are divided into clusters in such a way that patterns in any cluster are correlated but those in two different clusters are not correlated. By using the replica method, we derive the saddle point equations for order parameters under the ansatz of replica symmetry. The same equations are also derived by self-consistent signal-to-noise analysis in case I. In both cases I and II, we find that when the correlation between patterns is large, the network loses its ability to retrieve the embedded patterns and, depending on the parameters, a confused memory, which is a mixed state and/or spin glass state, emerges. By unlearning the mixed state, the network acquires the ability to retrieve the embedded patterns again in some parameter regions. We find that to delete the mixed state and to retrieve the embedded patterns, the coefficient of unlearning should be chosen appropriately. We perform Markov chain Monte Carlo simulations and find that the simulation and theoretical results agree reasonably well, except for the spin glass solution in a parameter region due to the replica symmetry breaking. Furthermore, we find that the existence of many correlated clusters reduces the stabilities of both embedded patterns and mixed states.

Sex, Age, and Emotional Valence: Revealing Possible Biases in the ‘Reading the Mind in the Eyes’ Task

Directory of Open Access Journals (Sweden)

Jana Kynast

2018-04-01

Full Text Available The ‘Reading the Mind in the Eyes’ test (RMET assesses a specific socio-cognitive ability, i.e., the ability to identify mental states from gaze. The development of this ability in a lifespan perspective is of special interest. Whereas former investigations were limited mainly to childhood and adolescence, the focus has been shifted towards aging, and psychiatric and neurodegenerative diseases recently. Although the RMET is frequently applied in developmental psychology and clinical settings, stimulus characteristics have never been investigated with respect to potential effects on test performance. Here, we analyzed the RMET stimulus set with a special focus on interrelations between sex, age and emotional valence. Forty-three persons rated age and emotional valence of the RMET picture set. Differences in emotional valence and age ratings between male and female items were analyzed. The linear relation between age and emotional valence was tested over all items, and separately for male and female items. Male items were rated older and more negative than female stimuli. Regarding male RMET items, age predicted emotional valence: older age was associated with negative emotions. Contrary, age and valence were not linearly related in female pictures. All ratings were independent of rater characteristics. Our results demonstrate a strong confound between sex, age, and emotional valence in the RMET. Male items presented a greater variability in age ratings compared to female items. Age and emotional valence were negatively associated among male items, but no significant association was found among female stimuli. As personal attributes impact social information processing, our results may add a new perspective on the interpretation of previous findings on interindividual differences in RMET accuracy, particularly in the field of developmental psychology, and age-associated neuropsychiatric diseases. A revision of the RMET might be afforded to

Sex, Age, and Emotional Valence: Revealing Possible Biases in the ‘Reading the Mind in the Eyes’ Task

Science.gov (United States)

Kynast, Jana; Schroeter, Matthias L.

2018-01-01

The ‘Reading the Mind in the Eyes’ test (RMET) assesses a specific socio-cognitive ability, i.e., the ability to identify mental states from gaze. The development of this ability in a lifespan perspective is of special interest. Whereas former investigations were limited mainly to childhood and adolescence, the focus has been shifted towards aging, and psychiatric and neurodegenerative diseases recently. Although the RMET is frequently applied in developmental psychology and clinical settings, stimulus characteristics have never been investigated with respect to potential effects on test performance. Here, we analyzed the RMET stimulus set with a special focus on interrelations between sex, age and emotional valence. Forty-three persons rated age and emotional valence of the RMET picture set. Differences in emotional valence and age ratings between male and female items were analyzed. The linear relation between age and emotional valence was tested over all items, and separately for male and female items. Male items were rated older and more negative than female stimuli. Regarding male RMET items, age predicted emotional valence: older age was associated with negative emotions. Contrary, age and valence were not linearly related in female pictures. All ratings were independent of rater characteristics. Our results demonstrate a strong confound between sex, age, and emotional valence in the RMET. Male items presented a greater variability in age ratings compared to female items. Age and emotional valence were negatively associated among male items, but no significant association was found among female stimuli. As personal attributes impact social information processing, our results may add a new perspective on the interpretation of previous findings on interindividual differences in RMET accuracy, particularly in the field of developmental psychology, and age-associated neuropsychiatric diseases. A revision of the RMET might be afforded to overcome confounds

Missing continuous outcomes under covariate dependent missingness in cluster randomised trials.

Science.gov (United States)

Hossain, Anower; Diaz-Ordaz, Karla; Bartlett, Jonathan W

2017-06-01

Attrition is a common occurrence in cluster randomised trials which leads to missing outcome data. Two approaches for analysing such trials are cluster-level analysis and individual-level analysis. This paper compares the performance of unadjusted cluster-level analysis, baseline covariate adjusted cluster-level analysis and linear mixed model analysis, under baseline covariate dependent missingness in continuous outcomes, in terms of bias, average estimated standard error and coverage probability. The methods of complete records analysis and multiple imputation are used to handle the missing outcome data. We considered four scenarios, with the missingness mechanism and baseline covariate effect on outcome either the same or different between intervention groups. We show that both unadjusted cluster-level analysis and baseline covariate adjusted cluster-level analysis give unbiased estimates of the intervention effect only if both intervention groups have the same missingness mechanisms and there is no interaction between baseline covariate and intervention group. Linear mixed model and multiple imputation give unbiased estimates under all four considered scenarios, provided that an interaction of intervention and baseline covariate is included in the model when appropriate. Cluster mean imputation has been proposed as a valid approach for handling missing outcomes in cluster randomised trials. We show that cluster mean imputation only gives unbiased estimates when missingness mechanism is the same between the intervention groups and there is no interaction between baseline covariate and intervention group. Multiple imputation shows overcoverage for small number of clusters in each intervention group.

Nuclear masses and the number of valence nucleons

International Nuclear Information System (INIS)

Mendoza-Temis, J.; Frank, A.; Hirsch, J.G.; Lopez Vieyra, J.C.; Morales, I.; Barea, J.; Van Isacker, P.; Velazquez, V.

2008-01-01

An improved version of the liquid drop model is presented. The addition of two terms, linear and quadratic in the total number of valence nucleons (particles or holes), improves the description of atomic masses, which can be fitted with an r.m.s. error of 1.2 MeV. Predictions are analysed an compared with those of established models

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

Science.gov (United States)

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.

Effect of oxygen clusters on optics, magnetism, and conductivity of (In2O3)0.9(SrO)0.1

Science.gov (United States)

Okunev, V. D.; Szymczak, H.; Szymczak, R.; Gierłowski, P.; Glot, A. B.; Bondarchuk, A. N.; Burkhovetski, V. V.

2016-04-01

We show that in In2O3-SrO ceramics with disordered structure and oxygen clusters in nanovoids, the band tails of valence and conduction bands form "negative" gap. Two types of magnetism are observed. One of them caused by formation of the "dangling bond+O2- ion" centers has been found in the samples saturated with oxygen. Another type is associated with the presence of dangling bonds in the oxygen-depleted samples. At Tconductivity of the samples. At T<54.8 K, the effects related to magnetic phase transitions in the clusters of crystalline oxygen are observed. The changes in resistance of the samples in the range of T=5-300 K correspond to the Mott's law at a dependence of local activation energy on the phase state of oxygen clusters.

Clustering Teachers' Motivations for Teaching

Science.gov (United States)

Visser-Wijnveen, Gerda J.; Stes, Ann; Van Petegem, Peter

2014-01-01

The motivation to teach is a powerful, yet neglected, force in teaching at institutes of higher education. A better understanding of academics' motivations for teaching is necessary. The aim of this mixed-method study was to identify groups with distinctively different motivations for teaching. Six clusters were identified: expertise, duty,…

Magnetic-field control of quantum critical points of valence transition.

Science.gov (United States)

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

2008-06-13

We study the mechanism of how critical end points of first-order valence transitions are controlled by a magnetic field. We show that the critical temperature is suppressed to be a quantum critical point (QCP) by a magnetic field, and unexpectedly, the QCP exhibits nonmonotonic field dependence in the ground-state phase diagram, giving rise to the emergence of metamagnetism even in the intermediate valence-crossover regime. The driving force of the field-induced QCP is clarified to be cooperative phenomena of the Zeeman and Kondo effects, which create a distinct energy scale from the Kondo temperature. This mechanism explains the peculiar magnetic response in CeIrIn(5) and the metamagnetic transition in YbXCu(4) for X=In as well as the sharp contrast between X=Ag and Cd.

Thermodynamic basis for cluster kinetics

DEFF Research Database (Denmark)

Hu, Lina; Bian, Xiufang; Qin, Xubo

2006-01-01

Due to the inaccessibility of the supercooled region of marginal metallic glasses (MMGs) within the experimental time window, we study the cluster kinetics above the liquidus temperature, Tl, to acquire information on the fragility of the MMG systems. Thermodynamic basis for the stability...... of locally ordered structure in the MMG liquids is discussed in terms of the two-order-parameter model. It is found that the Arrhenius activation energy of clusters, h, is proportional to the chemical mixing enthalpy of alloys, Hchem. Fragility of the MMG forming liquids can be described by the ratio...

The effects of valence and arousal on the neural activity leading to subsequent memory

OpenAIRE

Mickley Steinmetz, Katherine R.; Kensinger, Elizabeth A.

2009-01-01

This study examined how valence and arousal affect the processes linked to subsequent memory for emotional information. While undergoing an fMRI scan, participants viewed neutral pictures and emotional pictures varying by valence and arousal. After the scan, participants performed a recognition test. Subsequent memory for negative or high arousal information was associated with occipital and temporal activity, while memory for positive or low arousal information was associated with frontal ac...

Valence electron momentum distributions in cadmium

International Nuclear Information System (INIS)

Frost, L.; Weigold, E.; Mitroy, J.

1982-08-01

The valence 5s and 4d electron momentum distributions in cadmium have been measured using noncoplanar symmetric (e, 2e) electron coincidence spectroscopy at a total energy of 1200eV. They are in close agreement with Hartree-Fock momentum distributions both in shape and relative magnitudes. Some satellite lines of very low intensity have been detected. A CI calculation of the Cd ground state and several Cd + ion states has been carried out to predict cross reactions for the ground state and various satellite transitions. The predictions are in agreement with the data

Sub-20 nm Stable Micelles Based on a Mixture of Coiled-Coils: A Platform for Controlled Ligand Presentation.

Science.gov (United States)

Ang, JooChuan; Ma, Dan; Jung, Benson T; Keten, Sinan; Xu, Ting

2017-11-13

Ligand-functionalized, multivalent nanoparticles have been extensively studied for biomedical applications from imaging agents to drug delivery vehicles. However, the ligand cluster size is usually heterogeneous and the local valency is ill-defined. Here, we present a mixed micelle platform hierarchically self-assembled from a mixture of two amphiphilic 3-helix and 4-helix peptide-polyethylene glycol (PEG)-lipid hybrid conjugates. We demonstrate that the local multivalent ligand cluster size on the micelle surface can be controlled based on the coiled-coil oligomeric state. The oligomeric states of mixed peptide bundles were found to be in their individual native states. Similarly, mixed micelles indicate the orthogonal self-association of coiled-coil amphiphiles. Using differential scanning calorimetry, fluorescence recovery spectroscopy, and coarse-grained molecular dynamics simulation, we studied the distribution of coiled-coil bundles within the mixed micelles and observed migration of coiled-coils into nanodomains within the sub-20 nm mixed micelle. This report provides important insights into the assembly and formation of nanophase-separated micelles with precise control over the local multivalent state of ligands on the micelle surface.

Solvent extraction of irradiated neptunium targets. I. Valence stabilization

International Nuclear Information System (INIS)

Thompson, G.H.; Thompson, M.C.

1977-01-01

Solvent extraction of 237 Np and 238 Pu from irradiated neptunium is being investigated as a possible replacement for the currently used anion exchange process at the Savannah River Plant. Solvent extraction would reduce separations costs and waste volume and increase the production rate. The major difficulty in solvent extraction processing is maintaining neptunium and plutonium in the extractable IV or VI valence states during initial extraction. This study investigated the stability of these states. Results show that: The extractable M(IV) valence states of neptunium and plutonium are mutually unstable in plant dissolver solution (2 g/l 237 Np, 0.4 g/l 238 Pu, 1.2M Al 3+ , 4.6M NO 3 - , and 1M H + ). The reaction rates producing inextractable species from extractable M(IV) or M(VI) are fast enough that greater than or equal to 99.9 percent extractable species in 237 Np-- 238 Pu mixtures cannot be maintained for a practicable processing period

The olfactory tubercle encodes odor valence in behaving mice.

Science.gov (United States)

Gadziola, Marie A; Tylicki, Kate A; Christian, Diana L; Wesson, Daniel W

2015-03-18

Sensory information acquires meaning to adaptively guide behaviors. Despite odors mediating a number of vital behaviors, the components of the olfactory system responsible for assigning meaning to odors remain unclear. The olfactory tubercle (OT), a ventral striatum structure that receives monosynaptic input from the olfactory bulb, is uniquely positioned to transform odor information into behaviorally relevant neural codes. No information is available, however, on the coding of odors among OT neurons in behaving animals. In recordings from mice engaged in an odor discrimination task, we report that the firing rate of OT neurons robustly and flexibly encodes the valence of conditioned odors over identity, with rewarded odors evoking greater firing rates. This coding of rewarded odors occurs before behavioral decisions and represents subsequent behavioral responses. We predict that the OT is an essential region whereby odor valence is encoded in the mammalian brain to guide goal-directed behaviors. Copyright © 2015 the authors 0270-6474/15/354515-13$15.00/0.

Atomic and electronic structure of clusters from car-Parrinello method

International Nuclear Information System (INIS)

Kumar, V.

1994-06-01

With the development of ab-initio molecular dynamics method, it has now become possible to study the static and dynamical properties of clusters containing up to a few tens of atoms. Here I present a review of the method within the framework of the density functional theory and pseudopotential approach to represent the electron-ion interaction and discuss some of its applications to clusters. Particular attention is focussed on the structure and bonding properties of clusters as a function of their size. Applications to clusters of alkali metals and Al, non-metal - metal transition in divalent metal clusters, molecular clusters of carbon and Sb are discussed in detail. Some results are also presented on mixed clusters. (author). 121 refs, 24 ifigs

Quantum computational capability of a 2D valence bond solid phase

International Nuclear Information System (INIS)

Miyake, Akimasa

2011-01-01

Highlights: → Our model is the 2D valence bond solid phase of a quantum antiferromagnet. → Universal quantum computation is processed by measurements of quantum correlations. → An intrinsic complexity of strongly-correlated quantum systems could be a resource. - Abstract: Quantum phases of naturally-occurring systems exhibit distinctive collective phenomena as manifestation of their many-body correlations, in contrast to our persistent technological challenge to engineer at will such strong correlations artificially. Here we show theoretically that quantum correlations exhibited in the 2D valence bond solid phase of a quantum antiferromagnet, modeled by Affleck, Kennedy, Lieb, and Tasaki (AKLT) as a precursor of spin liquids and topological orders, are sufficiently complex yet structured enough to simulate universal quantum computation when every single spin can be measured individually. This unveils that an intrinsic complexity of naturally-occurring 2D quantum systems-which has been a long-standing challenge for traditional computers-could be tamed as a computationally valuable resource, even if we are limited not to create newly entanglement during computation. Our constructive protocol leverages a novel way to herald the correlations suitable for deterministic quantum computation through a random sampling, and may be extensible to other ground states of various 2D valence bond phases beyond the AKLT state.

Effects of emotional valence and arousal on the voice perception network

Science.gov (United States)

Kotz, Sonja A.; Belin, Pascal

2017-01-01

Abstract Several theories conceptualise emotions along two main dimensions: valence (a continuum from negative to positive) and arousal (a continuum that varies from low to high). These dimensions are typically treated as independent in many neuroimaging experiments, yet recent behavioural findings suggest that they are actually interdependent. This result has impact on neuroimaging design, analysis and theoretical development. We were interested in determining the extent of this interdependence both behaviourally and neuroanatomically, as well as teasing apart any activation that is specific to each dimension. While we found extensive overlap in activation for each dimension in traditional emotion areas (bilateral insulae, orbitofrontal cortex, amygdalae), we also found activation specific to each dimension with characteristic relationships between modulations of these dimensions and BOLD signal change. Increases in arousal ratings were related to increased activations predominantly in voice-sensitive cortices after variance explained by valence had been removed. In contrast, emotions of extreme valence were related to increased activations in bilateral voice-sensitive cortices, hippocampi, anterior and midcingulum and medial orbito- and superior frontal regions after variance explained by arousal had been accounted for. Our results therefore do not support a complete segregation of brain structures underpinning the processing of affective dimensions. PMID:28449127

Orbital momentum distribution and binding energies for the complete valence shell of molecular bromine

International Nuclear Information System (INIS)

Frost, L.; Grisogono, A.M.; Weigold, E.

1987-08-01

The binding energy spectrum of Br 2 has been recorded in both the outer and inner valence regions using electron momentum spectroscopy. The measurements are compared with the results of several Green's function calculations using different approximations and based on both polarized and unpolarized wave functions. The inner valence region, observed for the first time, is found to exhibit complex structure that is shown to be due to many-body effects, thus indicating a breakdown of the simple MO picture for ionization in this region. Momentum distributions for the three outer valence orbitals are also measured and compared with spherically averaged calculations using the target Hartree-Fock and plane wave impulse approximations. The effect of polarization functions in the basis set is investigated. Orbital density maps in both momentum and position space have been calculated and compared with the experimental measurements

Effects of self-relevant cues and cue valence on autobiographical memory specificity in dysphoria.

Science.gov (United States)

Matsumoto, Noboru; Mochizuki, Satoshi

2017-04-01

Reduced autobiographical memory specificity (rAMS) is a characteristic memory bias observed in depression. To corroborate the capture hypothesis in the CaRFAX (capture and rumination, functional avoidance, executive capacity and control) model, we investigated the effects of self-relevant cues and cue valence on rAMS using an adapted Autobiographical Memory Test conducted with a nonclinical population. Hierarchical linear modelling indicated that the main effects of depression and self-relevant cues elicited rAMS. Moreover, the three-way interaction among valence, self-relevance, and depression scores was significant. A simple slope test revealed that dysphoric participants experienced rAMS in response to highly self-relevant positive cues and low self-relevant negative cues. These results partially supported the capture hypothesis in nonclinical dysphoria. It is important to consider cue valence in future studies examining the capture hypothesis.

Orbital momentum distributions and binding energies for the complete valence shell of molecular iodine

International Nuclear Information System (INIS)

Grisogono, A.M.; Pascual, R.; Weigold, E.

1988-03-01

The complete valence shell binding energy spectrum (8-43eV) of I 2 has been measured by using electron momentum spectroscopy at 1000eV. The complete inner valence region, corresponding to ionization from the 10 σ u and 10 σ g orbitals, has been measured for the first time and shows extensive splitting of the ionization strength due to electron correlation effects in the ion. Many-body calculations using the Green's function method have been carried out and are compared with the data. Momentum distributions, measured in both the outer and inner valence regions, are compared with those given by SCF orbital wave functions calculated with a number of different basis sets. Computed orbital position and momentum density maps for oriented I 2 molecules are discussed in comparison with the measured and calculated spherically averaged momentum distributions

Metal clusters on supported argon layers; Metallcluster auf dielektrischen Substraten

Energy Technology Data Exchange (ETDEWEB)

Faber, Bernhard

2011-10-21

The deposition of small sodium clusters on supported Ar(001)-surfaces is simulated. Theoretical description is achieved by a hierarchical model consisting of time-dependent DFT and molecular dynamics. The valence electrons of the sodium atoms are considered by Kohn-Sham-Scheme with self interaction correction. The interaction of argon atoms and sodium ions is described by atom-atom potentials whereas the coupling to the QM electrons is done by local pseudo-potentials. A decisive part of the model is the dynamical polarizability of the rare-gas atoms. The optional metal support is considered by the method of image charges. The influence of the forces caused by image charges and the influence of the number of argon monolayers on structure, optical response and deposition dynamics of Na{sub 6} and Na{sub 8} is investigated. There is very little influence on cluster structure and only a small shift of the cluster perpendicular to the surface. Concerning optical response the position of the Mie plasmon peak stays robust whereas the details of spectral fragmentation react very sensitively to changes. The forces caused by image charges of the metal support play only a little role with the dynamics of deposition while the thickness of the argon surface strongly influences the dissipation. (orig.)

Magnetic-field-induced valence transition in rare-earth systems

Indian Academy of Sciences (India)

In the present work we investigate the scaling behavior observed experimentally based on an electronic model which has not yet been attempted. 2. The model and approximation. The Hamiltonian of the periodic Anderson model (PAM) with Falicov–Kimball term used to describe both continuous and discontinuous valence ...

Coordination-resolved local bond contraction and electron binding-energy entrapment of Si atomic clusters and solid skins

Energy Technology Data Exchange (ETDEWEB)

Bo, Maolin; Huang, Yongli; Zhang, Ting [Key Laboratory of Low-Dimensional Materials and Application Technologies, Xiangtan University, Hunan 411105 (China); Wang, Yan, E-mail: ywang8@hnust.edu.cn, E-mail: ecqsun@ntu.edu.sg [Key Laboratory of Low-Dimensional Materials and Application Technologies, Xiangtan University, Hunan 411105 (China); School of Information and Electronic Engineering, Hunan University of Science and Technology, Hunan 411201 (China); Zhang, Xi [School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Li, Can [Center for Coordination Bond Engineering, School of Materials Science and Engineering, China Jiliang University, Hangzhou 330018 (China); Sun, Chang Q., E-mail: ywang8@hnust.edu.cn, E-mail: ecqsun@ntu.edu.sg [Key Laboratory of Low-Dimensional Materials and Application Technologies, Xiangtan University, Hunan 411105 (China); School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Center for Coordination Bond Engineering, School of Materials Science and Engineering, China Jiliang University, Hangzhou 330018 (China)

2014-04-14

Consistency between x-ray photoelectron spectroscopy measurements and density-function theory calculations confirms our bond order-length-strength notation-incorporated tight-binding theory predictions on the quantum entrapment of Si solid skin and atomic clusters. It has been revealed that bond-order deficiency shortens and strengthens the Si-Si bond, which results in the local densification and quantum entrapment of the core and valence electrons. Unifying Si clusters and Si(001) and (111) skins, this mechanism has led to quantification of the 2p binding energy of 96.089 eV for an isolated Si atom, and their bulk shifts of 2.461 eV. Findings evidence the significance of atomic undercoordination that is of great importance to device performance.

Valence-band splitting energies in wurtzite InP nanowires: Photoluminescence spectroscopy and ab initio calculations

Science.gov (United States)

Gadret, E. G.; Dias, G. O.; Dacal, L. C. O.; de Lima, M. M., Jr.; Ruffo, C. V. R. S.; Iikawa, F.; Brasil, M. J. S. P.; Chiaramonte, T.; Cotta, M. A.; Tizei, L. H. G.; Ugarte, D.; Cantarero, A.

2010-09-01

We investigated experimentally and theoretically the valence-band structure of wurtzite InP nanowires. The wurtzite phase, which usually is not stable for III-V phosphide compounds, has been observed in InP nanowires. We present results on the electronic properties of these nanowires using the photoluminescence excitation technique. Spectra from an ensemble of nanowires show three clear absorption edges separated by 44 meV and 143 meV, respectively. The band edges are attributed to excitonic absorptions involving three distinct valence-bands labeled: A, B, and C. Theoretical results based on “ab initio” calculation gives corresponding valence-band energy separations of 50 meV and 200 meV, respectively, which are in good agreement with the experimental results.

Symmetry-adapted-cluster configuration-interaction and equation-of-motion coupled-cluster studies of electronically excited states of copper tetrachloride and copper tetrabromide dianions

International Nuclear Information System (INIS)

Ehara, Masahiro; Piecuch, Piotr; Lutz, Jesse J.; Gour, Jeffrey R.

2012-01-01

Graphical abstract: Electronically excited states of CuCl 4 2- and CuBr 4 2- are determined using the scalar relativistic symmetry-adapted-cluster configuration-interaction and equation-of-motion coupled-cluster calculations. The results are compared with experimental spectra. Highlights: ► Electronic spectra of CuCl 4 2- and CuBr 4 2- are examined by SAC-CI and EOMCC methods. ► Relativistic SAC-CI and EOMCC results are compared with experimental spectra. ► An assignment of bands in the CuCl 4 2- and CuBr 4 2- absorption spectra is obtained. ► Relativistic effects affect excitation energies and ground-state geometries. ► The effect of relativity on the oscillator strengths is generally small. - Abstract: The valence excitation spectra of the copper tetrachloride and copper tetrabromide open-shell dianions, CuCl 4 2- and CuBr 4 2- , respectively, are investigated by a variety of symmetry-adapted-cluster configuration-interaction (SAC-CI) and equation-of-motion coupled-cluster (EOMCC) methods. The valence excited states of the CuCl 4 2- and CuBr 4 2- species that correspond to transitions from doubly occupied molecular orbitals (MOs) to a singly occupied MO (SOMO), for which experimental spectra are available, are examined with the ionized (IP) variants of the SAC-CI and EOMCC methods. The higher-energy excited states of CuCl 4 2- and CuBr 4 2- that correspond to transitions from SOMO to unoccupied MOs, which have not been characterized experimentally, are determined using the electron-attached (EA) SAC-CI and EOMCC approaches. An emphasis is placed on the scalar relativistic SAC-CI and EOMCC calculations based on the spin-free part of the second-order Douglass–Kroll–Hess Hamiltonian (DKH2) and on a comparison of the results of the IP and EA SAC-CI and EOMCC calculations with up to 2-hole-1-particle (2h-1p) and 2-particle-1-hole (2p-1h) excitations, referred to as the IP-SAC-CI SD-R and IP-EOMCCSD(2h-1p) methods in the IP case and EA-SAC-CI SD-R and EA

Magnetic re-entrance in intermediate valence compounds

International Nuclear Information System (INIS)

Allub, R.; Machiavelli, O.; Balseiro, C.; Alascio, B.

1980-01-01

The possibility is explored of magnetic re-entrance in intermediate valence compounds. Using a simplified Anderson-Lattice model the pressure-temperature magnetic phase diagram is obtained. This diagram shows that for some value of the microscopic parameters the temperature induced two transitions (non-magnetic to magnetically ordered to paramagnetic). The magnetization and the average occupation number of the localized state are calculated. Estimations of the observability of the effect in systems like CeAl 2 are made. (author)

Ab initio study of interstitial cluster interaction with Re, Os, and Ta in W

Energy Technology Data Exchange (ETDEWEB)

Setyawan, Wahyu, E-mail: wahyu.setyawan@pnnl.gov; Nandipati, Giridhar; Kurtz, Richard J.

2017-02-15

The stability of tungsten self-interstitial atom (SIA) clusters is studied using first-principles methods. Clusters from one to seven SIAs are systematically explored from 1264 unique configurations. Finite-size effect of the simulation cell is corrected based on the scaling of formation energy versus inverse volume cell. Furthermore, the accuracy of the calculations is improved by treating the 5p semicore states as valence states. Configurations of the three most stable clusters in each cluster size n are presented, which consist of parallel [111] dumbbells. The evolution of these clusters leading to small dislocation loops is discussed. The binding energy of size-n clusters is analyzed relative to an n → (n-1) + 1 dissociation and is shown to increase with size. Extrapolation for n > 7 is presented using a dislocation loop model. In addition, the interaction of these clusters with a substitutional Re, Os, or Ta solute is explored by replacing one of the dumbbells with the solute. Re and Os strongly attract these clusters, but Ta strongly repels. The strongest interaction is found when the solute is located on the periphery of the cluster rather than in the middle. The magnitude of this interaction decreases with cluster size. Empirical fits to describe the trend of the solute binding energy are presented. - Highlights: • Systematic DFT exploration of tungsten SIA clusters from 1264 configurations. • Detailed structures of several most stable clusters are presented. • Novel finding of the trend of solute binding of Re, Os, and Ta with SIA clusters. • Empirical models that describe the trends of the solute binding energies.

Ab initio study of interstitial cluster interaction with Re, Os, and Ta in W

International Nuclear Information System (INIS)

Setyawan, Wahyu; Nandipati, Giridhar; Kurtz, Richard J.

2017-01-01

The stability of tungsten self-interstitial atom (SIA) clusters is studied using first-principles methods. Clusters from one to seven SIAs are systematically explored from 1264 unique configurations. Finite-size effect of the simulation cell is corrected based on the scaling of formation energy versus inverse volume cell. Furthermore, the accuracy of the calculations is improved by treating the 5p semicore states as valence states. Configurations of the three most stable clusters in each cluster size n are presented, which consist of parallel [111] dumbbells. The evolution of these clusters leading to small dislocation loops is discussed. The binding energy of size-n clusters is analyzed relative to an n → (n-1) + 1 dissociation and is shown to increase with size. Extrapolation for n > 7 is presented using a dislocation loop model. In addition, the interaction of these clusters with a substitutional Re, Os, or Ta solute is explored by replacing one of the dumbbells with the solute. Re and Os strongly attract these clusters, but Ta strongly repels. The strongest interaction is found when the solute is located on the periphery of the cluster rather than in the middle. The magnitude of this interaction decreases with cluster size. Empirical fits to describe the trend of the solute binding energy are presented. - Highlights: • Systematic DFT exploration of tungsten SIA clusters from 1264 configurations. • Detailed structures of several most stable clusters are presented. • Novel finding of the trend of solute binding of Re, Os, and Ta with SIA clusters. • Empirical models that describe the trends of the solute binding energies.

Confidence Intervals for Assessing Heterogeneity in Generalized Linear Mixed Models

Science.gov (United States)

Wagler, Amy E.

2014-01-01

Generalized linear mixed models are frequently applied to data with clustered categorical outcomes. The effect of clustering on the response is often difficult to practically assess partly because it is reported on a scale on which comparisons with regression parameters are difficult to make. This article proposes confidence intervals for…

AGN Heating in Simulated Cool-core Clusters

Energy Technology Data Exchange (ETDEWEB)

Li, Yuan; Ruszkowski, Mateusz [Department of Astronomy, University of Michigan, 1085 S. University Avenue, Ann Arbor, MI 48109 (United States); Bryan, Greg L., E-mail: yuanlium@umich.edu [Department of Astronomy, Columbia University, Pupin Physics Laboratories, New York, NY 10027 (United States)

2017-10-01

We analyze heating and cooling processes in an idealized simulation of a cool-core cluster, where momentum-driven AGN feedback balances radiative cooling in a time-averaged sense. We find that, on average, energy dissipation via shock waves is almost an order of magnitude higher than via turbulence. Most of the shock waves in the simulation are very weak shocks with Mach numbers smaller than 1.5, but the stronger shocks, although rare, dissipate energy more effectively. We find that shock dissipation is a steep function of radius, with most of the energy dissipated within 30 kpc, more spatially concentrated than radiative cooling loss. However, adiabatic processes and mixing (of post-shock materials and the surrounding gas) are able to redistribute the heat throughout the core. A considerable fraction of the AGN energy also escapes the core region. The cluster goes through cycles of AGN outbursts accompanied by periods of enhanced precipitation and star formation, over gigayear timescales. The cluster core is under-heated at the end of each cycle, but over-heated at the peak of the AGN outburst. During the heating-dominant phase, turbulent dissipation alone is often able to balance radiative cooling at every radius but, when this is occurs, shock waves inevitably dissipate even more energy. Our simulation explains why some clusters, such as Abell 2029, are cooling dominated, while in some other clusters, such as Perseus, various heating mechanisms including shock heating, turbulent dissipation and bubble mixing can all individually balance cooling, and together, over-heat the core.