Examining the redox and formate mechanisms for water–gas shift reaction on Au/CeO2 using density functional theory

We perform DFT calculations to investigate the redox and formate mechanisms of water–gas-shift (WGS) reaction on Au/CeO₂ catalysts. In the redox mechanism, we analyze all the key elementary steps and find that the OH cleavage is the key step. Three possible pathways of OH cleavage are calculated: (1) OH_ad^″+*^′→H_ad^′+O_ad^″; (2) H_ad^′+OH_ad^″→H₂(g)+O_ad^″+*^′; and (3) OH_ad^″+OH_ad^″→2O_ad^″+H₂(g) (*′: the free adsorption sites on the oxides; ad′: adsorption on the metal; ad″: adsorption on the oxide, respectively). In the formate mechanism, we identify all the possible pathways for the formation and decomposition of surface formates in the WGS reaction. It is found that there is a shortcoming in the redox and formate mechanisms which is related to surface oxygen reproduction. Four possible pathways for producing surface oxygen are studied, and all the barriers of the four pathways are more than 1 eV. Our results suggest that the processes to reproduce surface oxygen in the reaction circle are not kinetically easy.     

Fourier spectrometry: Rovibrational analysis of an infrared Π → Σ system of yttrium monoiodide

The infrared spectrum of yttrium monoiodide has been excited in an electrodeless microwave discharge and explored between 2500 and 12 000cm⁻¹ with a high-resolution Fourier transform spectrometer. A unique system is observed (ν₀₀ = 9905.520 cm⁻¹), which we attribute to a ¹Π → ¹Σ transition and an extensive analysis is made. Rovibrational constants are obtained for both states mainly from a simultaneous multiband fitting. This procedure is applied to the whole set of 2231 observed line wavenumbers in the 1-0, 0-0, and 0–1 bands, yielding a final weighted standard deviation of 0.0038 cm⁻¹. Furthermore, a partial analysis of the 2-0 and 3-1 bands is performed. The following equilibrium constants are derived (cm⁻¹): ω′_e=192.210 ω′_ex′_e=0.463B′_e=0.0399133 α′_e=0.0001150ω″_e=215.815 ω″_ex″_e=0.514B″_e=0.0422163 α″_e=0.0001125 High-order constants D_v and H_v are also calculated for the various vibrational levels (v′ = 0, 1, 2, 3; v″ = 0, 1).     

On the profile of temperature dependent electrical and dielectric properties of Au/SiO2/n-GaAs (MOS) structures at various frequencies

The temperature (T) dependence of electrical and dielectric characteristics such as series resistance (R_s), dielectric constant (ε′), dielectric loss (ε″), dielectric loss tangent (tan δ), and real and imaginary part of electrical modulus (M′ and M″) of the Au/SiO2/n-GaAs (MOS) structures have been investigated in the temperature range of 80–350 K at various frequencies by using experimental capacitance (C) and conductance (G/w) measurements. Experimental results show that both C and G/w characteristics were quite sensitive to frequency and temperature at especially high temperatures and low frequencies due to a continuous density distribution of interface states and their relaxation time, and thermal restructuring and reordering of the interface. Series resistance values of this device obtained from Nicollian method decrease with increasing frequency and temperature. The ε′, ε″, tan δ, and M′ and M″ were found a strong function of frequency and temperature. While the values of ε′, ε″, and tan δ decrease, M′ and M″ increase with increasing frequency. Also, while ε′ and ε″ increase, M′ and M″ decrease with increasing temperature. The tan δ and M′ values are almost independent temperature especially at high frequencies (f≥500 kHz).     

The emission spectrum of the diatomic radical, phosphorus selenide

The emission spectrum of the PSe radical is reported for the first time. Seventy-eight reddegraded bands in the region 4000–6500 Å have been measured and assigned to the A²Π-X²Π transition of PSe. Isotope shifts observed for some bandheads have been utilized in deriving the vibrational numbering. The molecular constants have been determined as (in units of cm⁻¹): ω′ = 406.9, ω′_eχ′_e = 1.3, ω″ = 556.9, ω″_eχ″_e = 1.3, and T_e = 19477.3 for the ²Π_1/2 states; and ω′_e = 402.4, ω′_eχ′_e = 1.5, ω″_e = 556.8, ω″_eχ″_e = 1.6, and T_e = 19178.0 for the ²Π_3/2 states.     

System-parameter dependence of the metallic phase of the non-doped 2D Hubbard model

Naito et al. reported that some non-doped T′-214-type compounds drive high-T_c superconductivity. The compounds are considered to be metallic since on-site Coulomb energy U is moderate and the Fermi surface is much deformed in these compounds. In order to confirm this picture and extract electronic structure information, we have examined the phase diagram of the metallic state of the 2D Hubbard model as a function of U and t′ (with t″ we fixed at − t′/2 here; t′ and t″ are the second- and third-neighbor transfer energies, respectively) by means of the variational Monte–Carlo method. We employed a Jastrow-type Gutzwiller trial wave function. In the studied range of U = 2–12, the boundary value for |t′| at which SDW disappears increases almost linearly with U. Jump-wise transition to the Mott insulator state was not observed. Using the boundary curve and experimental band parameter values, we estimate U  5 for T′-214 compounds. Preceding works are discussed in the last part.     

On the spectroscopy in ee annihilation

The properties of the radial excitations of the , ω and mesons are discussed. In particular it is proposed to identify the recently observed states at √s 1.5, 1.82 and 2.13 GeV in e⁺e⁻ annihilation with the _D ≡ ³D₁(λλ), ″ and ′″ mesons respectively. The ′ meson is suggested to lie in the vicinity of 1.5 GeV and strongly coupled to the _D. The ″(1.6) width is also suggested to be smaller than previously reported.     

Dielectric properties of nano Si/C/N composite powder and nano SiC powder at high frequencies

The dielectric properties of nano Si/C/N composite powder and nano SiC powder at high frequencies have been studied. The nano Si/C/N composite powder and nano SiC powder were synthesized from hexamethyldisilazane ((Me₃Si)₂NH) (Me:CH₃) and SiH₄–C₂H₂, respectively, by a laser-induced gas-phase reaction. The complex permittivities of the nano Si/C/N composite powder and nano SiC powder were measured at a frequency range of 8.2–12.4 GHz. The real part (′) and imaginary part (″) of the complex permittivity, and dissipation factor (tg δ=″/′) of nano Si/C/N composite powder are much higher than those of nano SiC powder and bulk SiC, Si₃N₄, SiO₂, and Si, especially the tg δ. The promising features of nano Si/C/N composite powder would be due to more complicated Si, C, and N atomic chemical environment than in a mixture of pure SiC and Si₃N₄ phase. The charged defects and quasi-free electrons moved in response to the electric field, diffusion or polarization current resulted from the field propagation. Because there exists graphite in the nano Si/C/N composite powder, some charge carries are related to the sp³ dangling bonds (of silicon and carbon) and unsaturated sp² carbons. The high ″ and tg δ of nano Si/C/N composite powder were due to the dielectric relaxation. The nano Si/C/N composite powder would be a good candidate for electromagnetic interface shielding material.     

The study of distribution and forms of uranium occurrences in Lake Baikal sediments by the SSNTD method

Sediments of Lake Baikal drill cores VER-96-1 St8 TW2 (5332^′15^″E; 10756^′25^″N), (interval 181.8–235 cm from the sediment surface) were studied by means of SSNTD with the aim of defining uranium occurrence in the sediments and the uranium concentration. The neutron-fission ((n,f)-autoradiographic) method allowed a detailed study of uranium distribution of these Lake Baikal sediments within the Academicheskiy Ridge. Layered accumulations of uranium-bearing grained phosphorite, uranium-bearing particles of organic material, and abnormal uranium concentration in diatomite of unknown origin were discovered.     

Analysis of the 2ν3 band of CD3F at 5.06 μm recorded under high resolution

The 2ν₃(A₁) band of ¹²CD₃F near 5.06 μm has been recorded with a resolution of 20–24 × 10⁻³ cm⁻¹. The value of the parameter (α^B − α^A) for this band was found to be very small and, therefore, the K structure of the R(J) and P(J) manifolds was unresolved for J < 15 and only partially resolved for larger J values. The band was analyzed using standard techniques and values for the following constants determined: ν₀ = 1977.178(3) cm⁻¹, B″ = 0.68216(9) cm⁻¹, D″_J = 1.10(30) × 10⁻⁶ cm⁻¹, α^B = (B″ − B′) = 3.086(7) × 10⁻³ cm⁻¹, and β^J = (D″_J − D′_J) = −3.24(11) × 10⁻⁷ cm⁻¹. A value of α^A = (A″ − A′) = 2.90(5) × 10⁻³ cm⁻¹ has been obtained through band contour simulations of the R(J) and P(J) multiplets.     

A vibronic analysis of the electronic transition in thiophosgene

The ultraviolet absorption spectrum assigned to the electronic transition has been photographed under conditions of moderately high resolution. The spectrum proved to be very complicated and only 30% of the observed bands could be assigned. Three progressions were located in the spectrum and were assigned to ν″₄, ν′₄, and ν′₁. Inversion doubling splittings were obtained for a number of cold bands from an analysis of the hot bands in ν″₄. The inversion doubling splittings were sensitive to ν₁ and ν₄. An estimate was made for the barrier to inversion along each of these directions.     

Correlation between P chemical shift tensor and local structure in lithium cyclohexaphosphates Li6P6O18·3H2O and Li6P6O18

To understand the surprising behavior between the variations of the P′–P–P″ angles and the correlated variations of the O′–P–O″ ones, two lithium cyclohexaphosphate compounds Li₆P₆O₁₈·3H₂O and Li₆P₆O₁₈ are studied by solid state nuclear magnetic resonance (NMR) spectroscopy. The two compounds exhibit the same [P₆O₁₈]⁶⁻ ring anions but with 3m or internal symmetry, respectively. Such symmetries induce local distortions that are exhibited by NMR spectroscopy. One-dimensional (1D) NMR gives information on structural sites of ⁷Li and ³¹P ions and the crystallographic non-equivalencies are observed. Nevertheless, in the anhydrous compound, X-ray diffraction and NMR results do not completely agree and some discrepancy exists between the number of sites observed with the first technique and the number of lines exhibited in the NMR spectra either for ⁷Li or ³¹P nuclei. This problem is elucidated by using 2D double quantum NMR spectroscopy coupled with theoretical considerations. We find that the ³¹P chemical shift tensor is dependent on the deviations of the O–P–O angles from those in the regular tetrahedron. Within the same empirical model, we suggest that the surprising behavior between the variations of the P′–P–P″ and the ones of the O′–P–O″ is related to the overall charge on the PO₄ group. We also find the positions of the isotropic lines for ⁷Li essentially depend on the site co-ordination of this nuclei.     

The Electronic Spectrum of Tellurium Dioxide

The electronic spectrum of gas-phase tellurium dioxide has been recorded between 345 and 406 nm using the technique of laser-induced fluorescence spectroscopy. The TeO₂ sample was prepared by direct heating of the solid and by seeding it in a continuous free-jet expansion in argon. Twenty-seven cold bands and thirty-two hot bands were assigned. The wavenumbers of the band origin and symmetric stretching and bending vibrational modes for the upper and lower states were determined in a simple least-squares fit: ν₀ = 25526 cm⁻¹, ω₁^′ = 679 cm⁻¹, ω₂^′ = 220 cm⁻¹, ω₁^″ = 823 cm⁻¹, ω₂^″ = 282 cm⁻¹.     

Magnetic and structural properties of nitrified FINEMET powder using mechanical milling method

The magnetic and structural properties of FINEMET [Fe_73.5Si_13.5B₉Nb₃Cu₁ wt%] amorphous powder were investigated after nitrification and mechanical milling. Fe-based amorphous powder were nitrified and crystallized simultaneously at 550 °C using by ammonia (NH₃) gas. Nitrified powder exhibited iron nitride phase such as γ′-Fe₄N, Fe₃N, and α″-Fe₁₆N₂. Nitrified particles were more brittle than raw particles. As a result, nanometer-sized nitride powder was fabricated by high-energy ball milling method. The saturation magnetization (M_s) and coercivity (H_c) of nitrified powder were increased due to nitride phase.     

ηη′ threshold enhancement in p annihilations into πηη′ at rest

We report on the observation of an ηη′ threshold enhancement produced in p annihilations at rest into π⁰ηη′, which we identify with the recently discovered ƒ₀(1500).     

Argon matrix absorption spectra of ClO, BrO, and IO and emission spectra of IO

Absorption spectra of ClO, BrO, and IO and the emission spectrum of IO have been observed from argon matrix samples prepared by microwave discharging the reagent mixture before condensation. Vibronic progressions were observed for each system. The spectroscopic scopic constants T_e, ω′_e, ω_ex′_e, ω″_e, and ω_ex″_e were evaluated from the absorption and emission data for comparison with gas-phase constants. Very good agreement is found for ClO. The argon matrix observations dictate a revision of the gas-phase vibronic assignments for BrO. The ground-state vibrational fundamental and T_e for argon matrix isolated IO are similar to the gas-phase values, but a lower excited-state spacing is found in the matrix.     

Isoscalar quadrupole strength in Ca from the (p,p′α0) reaction at Ep = 100 MeV

The ⁴⁰Ca(p,p′ α) reaction has been studied at an incident proton energy E_p = 99.5 MeV for proton laboratory scattering angles Θ_p^lab = 17°, 23° and 27°. Emission of α particles coincident with the scattered proton has been measured for an angular range Θ_α 0° − 180° relative to the recoil axis. A multipole decomposition for the α₀-decay channel to the ³⁶Ar ground state has been performed from the angular-correlation functions. The energy distribution of the dominating E2 strength deduced in the excitation energy range E_x = 11–21 MeV agrees reasonably well with the results from electron and α-induced α₀-decay investigations. The exhaustion of the E2 energy-weighted sum rule in this channel up to an energy of 17 MeV is 16.1(4.0)%, in accord with the study of the (α, α′ α₀) reaction. However, this value is twice what is found in the (e,e′ α₀) experiment in the same energy region. Thus, the puzzling discrepancy in the E2 strengths derived from electromagnetic and hadronic probes remains unsolved.     

The electronic spectrum of bismuth monofluoride: A reinvestigation of the A0-X10 system

A reinvestigation of the A0⁺-X₁0⁺ band system, the most electronic transitions reported for bismuth monofluoride, is presented. Approximately 65 bands were photographed in emission between 4220 and 5417 Å, of which 33 were rotationally analyzed. Inconsistencies in earlier vibrational analyses were resolved. Rotational constants for 0 ≤ ν′ ≤ 12 and 0 ≤ ν″ ≤ 18 were determined from direct least-squares fitting to the measured line positions of each band. “Merging” of the overdetermined constants was performed to obtain the best single estimate of each parameter. The resulting minimum-variance linear unbiased estimates were used to calculate RKR potential curves. Franck-Condon factors and r centroids were subsequently obtained and are presented. Evidence is given for predissociation in the upper state; perturbations involving levels above the crossing point are correlated with those previously reported in the B0⁺ state. The upper limit of the ground-state dissociation energy (3.14 eV) is in accord with extrapolated values as given in earlier investigations. The nature of a postulated third interacting state is also discussed.     

Photoluminescence studies of confined states in AlGaAs/GaAs asymmetric quantum well

In the recombination spectra of AlGaAs/GaAs heterostructures, a peculiar and asymmetric photoluminescence (PL) band F has previously been reported [Aloulou et al., Mater. Sci. Eng. B 96 (2002) 14] to be due to recombinations of confined electrons from the two-dimensional electron gas (2DEG) formed at AlGaAs/GaAs interface in asymmetric quantum well (AQW). Detailed experiments are reported here on GaAs/Al_0.31Ga_0.69As/GaAs:δSi/Al_0.31Ga_0.69As/GaAs samples with different spacer layer thicknesses. We show that the band F is the superposition of two PL bands F′ and F″ associated, respectively, to AQW and a symmetric quantum well (SQW). In the low excitation regime, the F′ band present a blue shift (4.4 meV) followed by important red shift (16.5 meV) when increasing optical excitation intensity. The blue shift in energy is interpreted in terms of optical control of the 2DEG density in the AQW while the red shift is due to the narrowing of the band gaps caused by the local heating of the sample and band bending modification for relatively high-optical excitation intensity. Calculation performed using self-consistent resolution of the coupled Schrödinger–Poisson equations are included to support the interpretation of the experimental data.     

Resonance excitation process for Ni-like gold

A detailed and large-scale calculation on the resonant excitation rate coefficients from the ground state to the 106 fine-structure levels belonging to 3l¹⁷4l^′(l=0,1,2;l^′=0,1,2,3) configurations of Ni-like gold have been performed using the relativistic distorted-wave approximation. The contributions through all possible Cu-like doubly excited states 3l¹⁷4l^′n^″l^″and 3l¹⁷5l^′n^″l^″(n^″≤15,l^″≤8) are calculated explicitly. The radiative damping effects on resonant excitation rates are studied. Significant effects arising from decays to autoionizing levels are also investigated. The n⁻³scaling law is investigated and is used to obtain the contributions from high-n configurations. Contributions from resonant excitation are found to be as important as direct excitation processes for most transitions. In some cases, resonant excitation can enhance the excitation rate coefficients by an order of magnitude. In addition, the total dielectronic recombination rate coefficients of Ni-like gold are also presented and compared with other works.     

A theoretical study of “structure-induced” surface plasmon polariton modes on metals and semiconductors using ATR

The possibility is theoretically examined, of the observation of “structure-induce” surface plasmon polariton modes on semi-finite free electron metals and semiconductors, using the Otto ATR configuration. This is achieved by introducing spatial dispersion into a model double step-function surface density profile. For both metals and semiconductors it is shown that well-defined minima in the reflectivity plots are associated with structure-induced modes. Furthermore, these modes occur quite strongly below the critical angle, which suggests that they are best developed in their radiative form.