Smoothed nonparametric tests and approximations of <Emphasis Type="Italic">p</Emphasis>-values

We propose new smoothed sign and Wilcoxon’s signed rank tests that are based on kernel estimators of the underlying distribution function of the data. We discuss the approximations of the p-values and asymptotic properties of these tests. The new smoothed tests are equivalent to the ordinary sign and Wilcoxon’s tests in the sense of Pitman’s asymptotic relative efficiency, and the differences between the ordinary and new tests converge to zero in probability. Under the null hypothesis, the main terms of the asymptotic expectations and variances of the tests do not depend on the underlying distribution. Although the smoothed tests are not distribution-free, making use of the specific kernel enables us to obtain the Edgeworth expansions, being free of the underlying distribution.     

Scattering of O? from a graphite surface

Recently an extensive series of measurements has been presented for the angular distributions of oxygen molecules scattered from a graphite surface. Incident translational energies ranged from 291 to 614 meV with surface temperatures from 150 to 500 K. The measurements were taken with a fixed angle of 90° between the source beam and the detector and the angular distributions consisted of a single broad peak with the most probable intensity located at an angle slightly larger than the 45° specular position. Analysis with the hard cubes model for atom-surface scattering indicated that the scattering is primarily a single collision event with a surface having a collective effective mass much larger than a single carbon atom. Limited analysis with a classical diatomic molecular scattering theory was also presented. In this paper a more complete analysis using the classical diatomic molecular scattering theory is presented. The energy and temperature dependence of the observed angular distributions are well described as single collision events with a surface having an effective mass of 1.8 carbon graphite rings. In agreement with the earlier analysis and with other experiments, this suggests a large cooperative response of the carbon atoms in the outermost graphene layer.     

Scattering of CO and N(2) molecules by a graphite surface

Measurements of angular distributions for the scattering of well-defined incident beams of CO and N(2) molecules from a graphite surface are presented. The measurements were carried out over a range of graphite surface temperatures from 150 to 400?K and a range of incident translational energies from 275 to over 600?meV. The behavior of the widths, positions and relative intensities of the angular distributions for both CO and N(2) were found to be quite similar. The experimental measurements are discussed in comparison with calculations using a classical mechanical model that describes single collisions with a surface. Based on the behavior of the angular distributions as functions of temperature and incident translational energy, and the agreement between measured data and calculations of the single-collision model, it is concluded that the scattering process is predominantly a single collision with a collective surface for which the effective mass is significantly larger than that of a single carbon atom. This conclusion is consistent with that of earlier experiments for molecular beams of O(2) molecules and Xe atoms scattering from graphite. Further calculations are carried out with the theoretical molecular scattering model in order to predict translational and rotational energy transfers to and from the molecule during scattering events under similar initial conditions.     

Topological surface states in lead-based ternary telluride Pb(Bi(1-x)Sb(x))2Te4

We have performed angle-resolved photoemission spectroscopy on Pb(Bi(1-x)Sb(x))2Te4, which is a member of lead-based ternary tellurides and has been theoretically proposed as a candidate for a new class of three-dimensional topological insulators. In PbBi2Te4, we found a topological surface state with a hexagonally deformed Dirac-cone band dispersion, indicating that this material is a strong topological insulator with a single topological surface state at the Brillouin-zone center. Partial replacement of Bi with Sb causes a marked change in the Dirac carrier concentration, leading to the sign change of Dirac carriers from n type to p type. The Pb(Bi(1-x)Sb(x))2Te4 system with tunable Dirac carriers thus provides a new platform for investigating exotic topological phenomena.     

Direct evidence for the dirac-cone topological surface states in the ternary chalcogenide TlBiSe₂

We have performed angle-resolved photoemission spectroscopy on TlBiSe?, which is a member of the ternary chalcogenides theoretically proposed as candidates for a new class of three-dimensional topological insulators. We found direct evidence for a nontrivial surface metallic state showing an "X"-shaped energy dispersion within the bulk-band gap. The present result unambiguously establishes that TlBiSe? is a strong topological insulator with a single Dirac cone at the Brillouin-zone center. The observed bulk-band gap of 0.35 eV is the largest among known topological insulators, making TlBiSe? the most promising material for studying room-temperature topological phenomena.     

Down-mixing of multi-channel audio for sound field reproduction based on spatial covariance

This article describes a method for automatic down-mixing multi-channel audio content on the basis of spatial covariance. Such a down-mixing method should be able to convert the signal of the original multi-channel audio system into that for an alternative system with the lesser number of channels, while maintaining the spatial impression of sound. Moreover, it should take into account the listener’s position and transfer function. Wave surface control and convolving the head related transfer function are techniques used in sound field control or reproduction. We consider that the spatial impressions of a sound field, which we perceive through our ears, are reproduced by preserving the relative relationship between observation points even if the wave surface is not completely controlled. Takahashi et al. proposed a new sound field reproduction method that we named “SOund field Reproduction based on sPAtial Covariance” (SORPAC). SORPAC can control the point-to-point covariance in a sound field. We expect that this sound field reproduction method based on spatial covariance can be applied to down-mixing of multi-channel content because SORPAC does not require the listener’s position or transfer function. This article describes SORPAC and its characteristics. We used SORPAC for down-mixing audio content. We confirmed that SORPAC-based down-mixing could accurately reproduce the interaural cross correlation (IACC) in relation to the listener’s position.     

Detailed analysis of the charge transfer complex N,N‐dimethylaniline–SO2 by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N‐dimethylaniline (DMA) and sulfur dioxide (SO₂). The formation of a deep red oil by the reaction of SO₂ with DMA is an evidence of the charge transfer (CT) nature of the DMA–SO₂ interaction. The DMA–SO₂ normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm⁻¹, which are enhanced when resonance is approached. These bands are assigned to ν_s(SO₂) and ν(ϕ N) vibrational modes, respectively, confirming the interaction between SO₂ and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO₂ with the ring π electrons, which gives rise to a π–π* low‐energy CT electronic transition, as confirmed by time‐dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA–SO₂ spectrum at the B3LYP/6‐311 + + g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO₂. Copyright © 2009 John Wiley & Sons, Ltd.     

Iridium complex-catalyzed [2+2+2] cycloaddition of alpha,omega-diynes with monoynes and monoenes

[reaction: see text] [Ir(cod)Cl]2/DPPE was found to be a new catalyst for the cycloaddition of alpha,omega-diynes with monoynes to give polysubstituted benzene derivatives in high yields. Internal monoynes as well as terminal monoynes could be used. The reaction tolerates a broad range of functional groups such as alcohol, amine, alkene, ether, halogen, and nitrile. The reaction of 1,6-octadiyne derivatives with 1-alkynes gives ortho products and meta products. The regioselectivity could be controlled by the choice of ligand. The reaction with DPPE was meta selective, with meta selectivity of up to 82%. The reaction with DPPF was ortho selective, with ortho selectivity of up to 88%. We propose a mechanism to account for this regioselective cycloaddition. [Ir(cod)Cl](2)/DPPE also catalyzed the cycloaddition of alpha,omega-diynes with 2,5-dihydrofuran to give bicyclic cyclohexadiene derivatives. The reaction with 2,3-dihydrofuran and n-butyl vinyl ether gave benzene derivatives instead of cyclohexadiene derivatives. We also propose a mechanism to account for this novel aromatization that includes cleavage of the C-O bond.     

Volume and viscosity of Zr–Cu–Al glass-forming liquid alloys

We examined the volume and viscosity of Zr–Cu–Al glass-forming liquid alloys to clarify the origin of a frozen free volume in glassy alloys. Since an excess free volume imparts toughness and ductility to glassy alloys, we attempted to increase this volume in glass structures so that they could be used as engineering materials. The maximum frozen excess free volume was observed in the ternary eutectic composition of the Zr–Cu–Al alloy system; however, its origin remains unclear. We attempted to reveal the mechanism of the formation of the frozen excess free volume in Zr–Cu–Al glassy alloys.     

Two-Temperature Two-Dimensional Non Chemical Equilibrium Modeling of Ar–CO<Subscript>2</Subscript>–H<Subscript>2</Subscript> Induction Thermal Plasmas at Atmospheric Pressure

Here the authors developed a two-dimensional two-temperature chemical non-equilibrium (2T-NCE) model of Ar–CO₂–H₂ inductively coupled thermal plasmas (ICTP) around atmospheric pressure (760 torr). Assuming 22 different particles in this model and by solving mass conservation equations for each particle, considering diffusion, convection and net production terms resulting from 198 chemical reactions, chemical non-equilibrium effects were taken into account. Species density of each particle or simply particle composition was also derived from the mass conservation equation of each one taking the non chemical equilibrium effect into account. Transport and thermodynamic properties of Ar–CO₂–H₂ thermal plasmas were self-consistently calculated using the first order approximation of the Chapman–Enskog method at each iteration point implementing the local particle composition and temperature. Calculations at reduced pressure (500 and 300 torr) were also done to investigate the effect of pressure on non-equilibrium condition. Results obtained by the present model were compared with results from one temperature chemical equilibrium (1T-CE) model, one-temperature chemically non equilibrium (1T-NCE) model and finally with 2T-NCE model of Ar–N₂–H₂ plasmas. Investigation shows that consideration of non-chemical equilibrium causes the plasma volume radially wider than CE model due to particle diffusion. At low pressure with same input power, presence of diffusion is relatively stronger than at high pressure. Comparison of present reactive model with non-reactive Ar–N₂–H₂ plasmas shows that maximum temperature reaches higher in reactive C–H–O molecular system than non-reactive plasmas due to extra contribution of reaction heat.