Density functional theory analysis of reactivity of PtxPdy alloy clusters

We investigate the reactivity of various Pt_xPd_y combinations (with x + y = 10 and various x:y ratios) towards the adsorption of specific intermediates of the oxygen reduction, using the B3PW91 hybrid density functional theory. The reactivity is shown to be not only sensitive to the composition of the cluster, but also to the atomic distribution. The calculations indicate that two different ensembles: one ordered and one randomly mixed, with overall composition Pt₃Pd₇ are thermodynamically more favorable than pure Pt₁₀ for the oxygen reduction reaction. The reasons for this behavior are clearly explained in terms of the atomic and electronic distribution, which makes the Pd atoms to act as electron donors both to Pt atoms and to the adsorbates, thus the reactivity of the Pd atoms in such environment becomes intermediate between Pt and Pd. Moreover, it is found that in a mixed Pt₃Pd₇ state the electronic distribution makes the average atom more similar to Pt than to Pd, whereas in an ordered Pt₃Pd₇ cluster, the average atom is more similar to Pd than to Pt.     

Epitaxy of AlxGa1−xSb films from a molten metal.

Conclusions Crystallization from a solution of antimony in a gallium-aluminum melt has been used to produce epitaxial Al_xGa_1–xSb films with x=0 to 0.4; isothermal (T = 450, 500, 550°C) and isoconcentration (0; 1; 2.4 at. % Al) sections have been drawn for the liquidus surface on the composition plane. X-ray microspectral analysis has been used to examine the composition of the Al_xGa_1–xSb films in relation to aluminum content in the melt, as well as the distribution of Al and Ga over the epitaxial film. These films had a perfect structure. The results enable one to determine the solution composition needed to grow Al_xGa_1–xSb epitaxial films at 450–550°C on gallium antimonide substrates, and it is shown to be possible to make heterostructures in the Al_xGa_1–xSb-GaSb system.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, Vol. 16, No. 9, pp. 146–148, September.We are indebted to Zh. I. Alferov and V. I. Shveikin for attention and support in this work.     

Sutherland models for complex reflection groups

There are known to be integrable Sutherland models associated to every real root system, or, which is almost equivalent, to every real reflection group. Real reflection groups are special cases of complex   reflection groups. In this paper we associate certain integrable Sutherland models to the classical family of complex reflection groups. Internal degrees of freedom are introduced, defining dynamical spin chains, and the freezing limit taken to obtain static chains of Haldane–Shastry type. By considering the relation of these models to the usual BCN$B{C}_N$ case, we are led to systems with both real and complex reflection groups as symmetries. We demonstrate their integrability by means of new Dunkl operators, associated to wreath products of dihedral groups.     

Detection and Characterization of Boric Acid and Borate Ion Binding to Cytochrome c Using Multiple Quantum Filtered NMR

The application of multiple quantum filtered (MQF) NMR to the identification and characterization of the binding of ligands containing quadrupolar nuclei to proteins is demonstrated. Using relaxation times measured by MQF NMR multiple binding of boric acid and borate ion to ferri and ferrocytochrome c was detected. Borate ion was found to have two different binding sites. One of them was in slow exchange, k_diss = 20 ± 3 s⁻¹ at 5°C and D₂O solution, in agreement with previous findings by ¹H NMR (G. Taler et al., 1998, Inorg. Chim. Acta 273, 388–392). The triple quantum relaxation of the borate in this site was found to be governed by dipolar interaction corresponding to an average B–H distance of 2.06 ± 0.07 Å. Other, fast exchanging sites for borate and boric acid could be detected only by MQF NMR. The binding equilibrium constants at these sites at pH 9.7 were found to be 1800 ± 200 M⁻¹ and 2.6 ± 1.5 M⁻¹ for the borate ion and boric acid, respectively. Thus, detection of binding by MQF NMR proved to be sensitive to fast exchanging ligands as well as to very weak binding that could not be detected using conventional methods.     

On the relaxation time of Gauss's continued-fraction map I. The Hilbert space approach (Koopmanism)

It is shown thatU ^*, the adjoint of Koopman's isometric operatorUf(x) =f(Tx) corresponding to the mapTx=x ^–1 (mod 1) of the unit interval, is isomorphic to a symmetric integral operator when restricted to a Hilbert space of holomorphic functionsf This result, also obtained by Babenko in a different setting, allows us to derive new trace formulas. Using generalized Temple's inequalities, we determine the relaxation time of the above system with great accuracy. In contrast to a widespread belief, it appears to be unrelated to the entropy of the mapT.     

Renormalization-group improvement of effective actions beyond summation of leading logarithms

Invariance of the effective action under changes of the renormalization scale μ leads to relations between those (presumably calculated) terms independent of μ at a given order of perturbation theory and those higher-order terms dependent on logarithms of μ. This relationship leads to differential equations for a sequence of functions, the solutions of which give closed form expressions for the sum of all leading logs, next to leading logs, and subsequent subleading logarithmic contributions to the effective action. The renormalization group is thus shown to provide information about a model beyond the scale dependence of the model's couplings and masses. This procedure is illustrated using the φ₆³ model and Yang–Mills theory. In the latter instance, it is also shown by using a modified summation procedure that the μ dependence of the effective action resides solely in a multiplicative factor of g²(μ) (the running coupling). This approach is also shown to lead to a novel expansion for the running coupling in terms of the one-loop coupling that does not require an order-by-order redefinition of the scale factor ΛQCD. Finally, logarithmic contributions of the instanton size to the effective action of an SU(2) gauge theory are summed, allowing a determination of the asymptotic dependence on the instanton size ρ as ρ goes to infinity to all orders in the SU(2) coupling constant.     

Effect of Sr content on structure and electrical properties of La1−x Sr x MnO3 from ITSOFC cathode view point

The samples belonging to La_1−x Sr _x MnO₃ series, prepared by combustion route without using fuel, exhibit crystal structural phase transition with the change in Sr content. Less than 40 mol% Sr is partially substituted in the crystal structure of LaMnO₃. The structural phase transition from rhombohedral to cubic, cubic to tetragonal, and tetragonal to orthorhombic takes place on 40, 60, and 80 mol% addition of Sr. The highest electrical conductivity in La_0.4Sr_0.6MnO₃ is understood to be due to the maximum concentration of polaron. The polarons are formed due to the conversion of Mn³⁺ to Mn⁴⁺ so as to achieve electroneutrality after substitution of Sr²⁺ for La³⁺.     

Configuration interaction calculations for the ground and excited states of ozone and its positive ion: Energy locations and transition probabilities

Large-scale configuration interaction calculations (including energy extrapolation) are reported for the various states of ozone and its positive ion. The first four dipole-forbidden electronic transitions in the O₃ spectrum are calculated to occur at 1.20, 1.44, 1.59, and 1.72 eV, respectively, while the corresponding low-energy-allowed species known as the Chappuis, Huggins, and Hartley bands are predicted to possess vertical excitation energies of 1.95, 3.60, and 4.97 eV, respectively. These results all appear to fit in quite well with the observed location of the pertinent spectral features, with respect to both energy and intensity. The 5- to 8-eV region of the ozone spectrum is found to be characterized by a series of double-excitation transitions out of the highest three occupied orbitals to the lowest unoccupied 2b₁(π^*) species. The strong features observed at 9.3 and 10.2 eV are thereupon calculated to result primarily from transitions into the 7a₁ (σ^*) MO (calculated 9.29 and 10.05 eV) and in the former case also from the 3s members of the various O₃ Rydberg series (calculated 9.21 and 9.38 eV). Finally the order of the first three ip's is found to be 6a₁, 4b₂, and 1a₂, while the feature in the neighborhood of 16 eV is attributed to a shake-up state of ²B₁ symmetry.     

Tuning the bottleneck effect in Ag metallic host doped with magnetic Gd and non-magnetic Sb ions

The Ag metallic host doped with Gd and Sb is an excellent model system to study the bottleneck effect associated to the conduction-electron (c-e) spin-flip scattering mechanism. Electron spin resonance of Gd³⁺ in both, Ag-(Gd doped)- and Ag-(Gd and Sb doped)-systems, reveal the presence of bottleneck which can be tuned by the amount of Gd and Sb impurities. The increase of the Gd concentration leads to a c-e spin-flip relaxation rate to the magnetic Gd³⁺ ions larger than that to the lattice, favoring the bottleneck regime. Whereas the effect of the non-magnetic impurities (Sb ions) is to increase, via spin–orbit scattering, the spin-flip relaxation rate of the c-e to the lattice, weakening the bottleneck regime.     

Muonium formation in xenon and argon up to 60 atmospheres

Results of muon polarization studies in xenon and argon up to 60 atm are reported. In argon for pressures up to 10 atm, the muon polarization is best explained by an epithermalcharge exchange model. Above this pressure, the decrease inP _D and increase inP _L are ascribed to charge neutralization and spin exchange reactions, respectively, in the radiolysis track. Measurements with Xe/He mixtures with a xenon pressure of 1 atm indicate that the lost polarization in the pure xenon at this pressure is due to inefficient moderation of the muon. As the pressure in pure xenon is increased above 10 atm, we find thatP _L remains roughly constant andP _D begins to increase. The lost fraction may be due to the formation of a XeMu Van der Waals type complex, whileP _D is ascribed to XeMu⁺ formation. This suggests that spur processes appear to be less important in xenon than in argon.     

Multi-component T1 relaxation and magnetisation transfer in peripheral nerve

We report here a study of longitudinal relaxation (T₁) and magnetisation transfer (MT) in peripheral nerve. Amphibian sciatic nerve was maintained in vitro and studied at a magnetic field strength of 3 T. A CPMG pulse sequence was modified to include either a saturation pulse to measure T₁ relaxation or an off-resonance RF irradiation pulse to measure MT. The resulting transverse relaxation (T₂) spectra yielded four components corresponding to three nerve compartments, taken to result from myelinic, axonal, and inter-axonal water, and a fourth corresponding to the buffer solution water in which the nerve sample was bathed. Each nerve component was analysed for T₁ relaxation and MT. All three nerve T₂ components exhibited unique T₁ relaxation and MT characteristics, providing further support for the assignment of the components to unique physical compartments of water. Numerical investigation of T_1sat measurements of each of the three nerve T₂ components indicates that while the two shorter-lived exhibit similar steady-state magnetisation transfer ratios (MTRs), their respective MT properties are quite different. Simulations demonstrate that mobile water exchange between these two components is not necessary to explain their similar steady-state MTR. In the context of the assignment of these two components to signal from myelinic and axonal water, this is to say that these two microanatomical regions of nerve may exhibit similar steady-state MTR characteristics despite possessing widely different MT exchange rates. Therefore, interpreting changes in MTR solely to reflect a change in degree of myelination could lead to erroneous conclusions.     

Using the natural 15N abundance to assess the main nitrogen inputs into the sand dune area of the North-Western Negev desert (ISRAEL)

The variation of the natural ¹⁵N abundance is often used to evaluate the origin of nitrogen or the pathways of N input into ecosystems. We tried to use this approach to assess the main input pathways of nitrogen into the sand dune area of the north-western Negev Desert (Israel). The following two pathways are the main sources for nitrogen input into the system:

1. Biological fixation of atmospheric nitrogen by cyanobacteria present in biological crusts and by N₂-fixing vascular plants (e.g. the shrub Retama raetam);

2. Atmospheric input of nitrogen by wet deposition with rainfall, dry deposition of dust containing N compounds, and gaseous deposition.

Samples were taken from selected environmental compartments such as biological crusts, sand underneath these crusts (down to a depth of 90?cm), N₂-fixing and non-N₂-fixing plants, atmospheric bulk deposition as well as soil from arable land north of the sandy area in three field campaigns in March 1998, 1999 and 2000. The δ¹⁵N values measured were in the following ranges: grass ?2.5‰ to +1.5‰; R. reatam: +0.5‰ to +4.5‰; non-N₂-fixing shrubs +1‰ to +7‰; sand beneath the biological crusts +4‰ to +20‰ (soil depth 2–90?cm); and arable land to the north up to 10‰. Thus, the natural ¹⁵N abundance of the different N pools varies significantly. Accordingly, it should be feasible to assess different input pathways from the various ¹⁵N abundances of nitrogen. For example, the biological N fixation rates of the Fabaceae shrub R. reatam from the ¹⁵N abundances measured were calculated to be 46–86% of biomass N derived from the atmosphere. The biological crusts themselves generally show slight negative ¹⁵N values (?3‰ to ?0.5‰), which can be explained by biological N fixation. However, areas with a high share of lichens, which are unable to fix atmospheric nitrogen, show very negative values down to ?10‰. The atmospheric N bulk deposition, which amounts to 1.9–3.8?kg?N/ha?yr, has a ¹⁵N abundance between 4.4‰ and 11.6‰ and is likely to be caused by dust from the arable land to the north. Thus, it cannot be responsible for the very negative values of lichens measured either. There must be an additional N input from the atmosphere with negative δ¹⁵N values, e.g. gaseous N forms (NO _x , NH₃). To explain these conflicting findings, detailed information is still needed on the wet, particulate and gaseous atmospheric deposition of nitrogen.     

Magnetoresistance and thermopower of tellurium at high pressures up to 30 GPa

Measurements are reported of the transverse magnetoresistance MR and of the thermopower S, carried out at high pressures P on Te single crystals in synthetic-diamond chambers. The MR is found to increase with decreasing gas width under a pressure up to 4 GPa as one approaches the semiconductor-metal phase-transition point, to fall off subsequently in the high-pressure metallic phase. The behavior of S(P) correlates with the pressure dependences of the measured MR. A negative MR at T=77 K was found within a narrow interval P=1.5–2 GPa, where the valence band of Te is assumed to undergo rearrangement. Above the point of the phase transition to the β-Po structure, MR is established to increase with pressure for P>12 GPa. The MR data are used to estimate the hole mobility μ for various Te phases. A comparison is made of the mobilities in Te, Se, and high-pressure phases of mercury chalcogenides, which are their structural and electronic analogs, for pressures of up to 30 GPa.     

Magnetic properties of cobalt substituted M-type barium hexaferrite prepared by co-precipitation

The co-precipitation and solid state methods were used in the synthesis of barium hexaferrite (BaM). Phase pure BaM was obtained with 1, 2, 3, 5, 10, 15, 20 and 30 wt% cobalt oxide (Co₃O₄). The addition of Co^2+/3+ ions to the BaM increased the permeability and magnetic loss tangent to a value of 3.5 at 5% and reduced to 1 at 30% doping. With increased Co doping, M_s was reduced from 87-58 emu/g, M_r increased from 11 to 40 emu/g with 3–5 wt% Co and 9 emu/g for 30% doping. H_c sharply increased from 540 to 2200 Oe with a reduction to 280 Oe at 10 K with increasing temperature to 300 K. T_c increased from 740 to 750 K for 30% Co doping. DTA–TGA studies of green body showed decarboxilation to occur at around 825 °C and the transformation of residual Co₃O₄ to Co₂O₃ at around 577 °C. The XRD data confirmed the Co ions substituting into Fe sites until a 10–15% doping level where the structure altered to W-type hexaferrite. The densities of the compounds varied with doping to a maximum of 4.45 g/cm³.     

The physical role of gravitational and gauge degrees of freedom in general relativity — I: Dynamical synchronization and generalized inertial effects

This is the first of a couple of papers in which the peculiar capabilities of the Hamiltonian approach to general relativity are exploited to get both new results concerning specific technical issues, and new insights about old foundational problems of the theory. The first paper includes: (1) a critical analysis of the various concepts of symmetry related to the Einstein-Hilbert Lagrangian viewpoint on the one hand, and to the Hamiltonian viewpoint, on the other. This analysis leads, in particular, to a re-interpretation of active diffeomorphisms as passive and metric-dependent dynamical symmetries of Einstein's equations, a re-interpretation which enables to disclose the (not widely known)) connection of a subgroup of them to Hamiltonian gauge transformations on-shell; (2) a re-visitation of the canonical reduction of the ADM formulation of general relativity, with particular emphasis on the geometro-dynamical effects of the gauge-fixing procedure, which amounts to the definition of a global non-inertial, space-time laboratory. This analysis discloses the peculiar dynamical nature that the traditional definition of distant simultaneity and clock-synchronization assume in general relativity, as well as the gauge relatedness of the “conventions” which generalize the classical Einstein's convention. (3) a clarification of the physical role of Dirac and gauge variables, as their being related to tidal-like and generalized inertial effects, respectively. This clarification is mainly due to the fact that, unlike the standard formulations of the equivalence principle, the Hamiltonian formalism allows to define a generalized notion of “force” in general relativity in a natural way.     

Surface oxidation of NiCo alloy: A comparative X-ray photoelectron spectroscopy study in a wide pressure range

Oxidation of NiCo alloy has been studied under two pressure regimes, 5 × 10⁻¹⁰ and 5 × 10⁻¹ bar, by X-ray photoelectron spectroscopy (XPS). The aim of this work is to investigate the synergetic effect between the two alloy components during the initial stages of oxidation. The results showed that at low oxygen pressure, segregation and preferential oxidation of cobalt takes place, while oxidation of nickel is largely suppressed. The species dominating the surface is CoO but small amount of metallic cobalt still remains even after prolonged oxidation at 670 K. At 0.5 bar O₂ pressure, alloy oxidation was found to be temperature depended. From 420 K to 520 K, cobalt is completely transformed to CoO and the Ni:Co atomic ratio at the surface approaches a minimum, similar to the observations at low pressure regime. However, at higher temperatures (from 520 K to 720 K), nickel is re-segregated on the surface, in the expense of cobalt, while CoO is further oxidized to Co₃O₄. At this temperature range formation of mixed Ni-Co-O spinel-like oxides is probable as supported by the characteristic modifications of the Ni 2p_3/2 photoelectron peak and the increase of the Ni:Co atomic ratio.     

Color tuning of up-conversion emission in ytterbium,erbium, aluminum tri-doped zinc oxide crystal by adjusting aluminum concentration

Ytterbium, erbium, aluminum tri-doped zinc oxide crystal was synthesized, which can turn color from red to green up-conversion luminescence through adjusting aluminum content. When the aluminum concentration reached 4?mol%, the color of up-conversion emission first turn from red to green. Meanwhile, the ratio of red to green emission reduced from 25.32 to 0.26, and the coordinates of chromaticity coordinate calculation changes from (0.5749, 0.3378) to (0.2190, 0.7169) with aluminum concentration range from 0 to 4?mol%. The up-conversion emission peaks at 521, 542, and 660?nm of sample originate from the transitions of ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, and ⁴F_9/2 → ⁴I_15/2 of erbium ions, respectively. X-ray diffraction patterns perform the better crystallization degree with increasing aluminum concentration. The scanning electron microscopy images show the porous and lamellar structures with different aluminum concentrations. A convenient but effective design to obtain ytterbium, erbium, aluminum tri-doped zinc oxide up-conversion luminescence is reported, which can turn color from red to green.     

The two-dimensional t-t'-U model as a minimal model for cuprate materials

The addition to the Hubbard Hamiltonian of a t' diagonal hopping term, which is considered to be material dependent for high-T _c cuprate superconductors, is generally suggested to obtain a model capable to describe the physics of high-T _c cuprate materials. In this line of thinking, the two-dimensional t-t'-U model has been studied by means of the Composite Operator Method, which allows to determine the dynamics in a fully self-consistent way by use of symmetry requirements, as the ones coming from the Pauli principle. At first, some local quantities have been calculated to be compared with quantum Monte Carlo data. Then, the structure of the energy bands, the shape of the Fermi surface and the position of the van Hove singularity have been computed as functions of the model parameters and studied by the light of the available experimental data. The results of our study show that there exists two sets of parameters that allows the model to describe the relevant features of the 1-layer compounds Nd_2-xCe_xCuO₄ and La_2-xSr_xCuO₄. On the other hand, for the 2-layer compound YBa₂Cu₃O _{7 - δ} is not possible to find a reasonable set of parameters which could reproduce the position of the van Hove singularity as predicted by ARPES experiments. Hence, it results questionable the existence of an unique model that could properly describe the variety of cuprate superconductors, as the two-dimensional t-t'-U model was thought to be. Received 29 March 2000 and Received in final form 10 August 2000     

Electrochemical promotion of Pd for the hydrogenation of C2H2

The effect of Non-Faradaic Electrochemical Modification of Catalytic Activity, orin-situ controlled promotion, was investigated during Acetylene selective hydrogenation on Pd films deposited on β″ - Al₂O₃, a Na⁺ conductor, at temperatures from 60 to 100 °C and GHSVs from 10³ to 10⁴ h-⁻¹, i.e., under conditions similar to those used in industrial processes. It was found that both acetylene conversion and hydrogenation selectivity can be affected by means of externally applied potentials, i.e., by supplying or removing sodium ions to or from the catalyst surface. Electrochemical sodium supply to the Pd catalyst surfaċe was found to supress both the rate of acetylene hydrogenation and, to a larger extent the rate of ethylene hydrogenation to ethane. Consequently electrochemical sodium supply was found to enhance the selectivity to ethylene. Thus, β″ - Al₂O₃ can act as an active catalyst support causing enhanced performance of the Pd catalyst. Acetylene conversion and hydrogenation selectivity values up to 90 % and 95 %, respectively, were obtained. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.