Comparison of reactivity on step and terrace sites of Pd (3 3 2) surface for the dissociative adsorption of hydrogen: A quantum chemical molecular dynamics study

The notion of “active sites” is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface.     

Ab-initio calculations of structural,electronic,and optical properties of Zn_3(VO_4)_2

The structural, electronic, and optical properties of Zn_3(VO_4)_2 are investigated using full potential linearized augmented plane wave(FP-LAPW) method within the framework of density functional theory(DFT). Various approaches are adopted to treat the exchange and correlation potential energy such as generalized gradient approximation(GGA),GGA+U, and the Tran–Blaha modified Becke–Johnson(TB-mBJ) potential. The calculated band gap of 3.424 eV by TB-mBJ is found to be close to the experimental result(3.3 eV). The optical anisotropy is analyzed through optical constants,such as dielectric function and absorption coefficient along parallel and perpendicular crystal orientations. The absorption coefficient reveals high absorption(1.5 × 10~(6) cm~(-1)) of photons in the ultraviolet region.     

The master equation for a two-level atom in a laser field with squeezing-like terms

In this paper, we derive the time dependent solution of the effective master equation for the reduced density matrix operator of a two-level atom driven by a strong classical field and damped into a “modelled” reservoir with non-flat density of modes. The effects of different parameters on the atomic inversion, the von Neumann entropy and the entropy squeezing are discussed.     

The role of F A1:Ag+ defects in laser light generation and coadsorption of CO and halogen atoms at the KCl and KBr surface sites. First principles calculations

F _A1:Ag⁺ color center at the low coordination (100) and (110) surface sites of KCl and KBr thin films play an important role in providing tunable laser oscillation and adsorbatesubstrate interactions. Double-well potentials at this site are investigated using ab initio molecular electronic structure calculations. The calculated Stokes shifted (optical transition bands), opticaloptical conversion efficiencies, the probability of orientational destruction, exciton (energy) transfer and Glasner-Tompkins empirical rule suggest that laser light generation is sensitive to (i) the lattice anion, (ii) the coordination number of surface ions, and (iii) the choice of the basis set centered on the anion vacancy. The adsorbate-substrate interactions were found to be dependent on the electronegativity of the adatom and on the lattice anion. Optimised geometries and the coadsorption of CO and (F, Cl, Br, I) on KCl and KBr (100) crystals are presented. Calculated chemisorption energies for CO on the (halogen atom/defect free sites of KCl and KBr (100) crystals) showed that the coadsorption of halogen atom tends to block other adsorbate-substrate interactions at the nearest neighbour sites. Thus if halogen atom coverage increases, the CO prefers to be adsorbed on the K⁺ site of the KCl and KBr (100) surfaces and on KBr relative to KCl.      

Control of spontaneous emission in a five-level system

We study the control of spontaneous emission in a five-level atomic system driven by four fields. We show that with the variation of dynamical variables, namely, Rabi frequencies and carrier phases of driven fields, a wide variety of the spectral behavior can be obtained, including extreme spectral narrowing. Our system can be found easily in real atoms.     

Competing ferromagnetism and superconductivity on FeAs layers in EuFe2(As0.73P0.27)2

We have measured the spin-polarized electron momentum density distributions of EuFe2(As0.73P0.27)2 by magnetic Compton scattering (MCS) measurements. For the first time, we show direct evidence of competing ferromagnetism and superconductivity (SC) on FeAs layers in this iron pnictide system. The MCS orbitalwise decomposition of the density distributions reveals that between 16 and 19 K, the spin-polarized Fe-3d character is enhanced (as the ferromagnetic character supersedes superconducting character), where the resistivity shows a maximum, reentrant SC-like peak, at 18 K. The spin polarization of the Fe-3d orbital, enhanced by ferromagnetic Eu ions, suppresses the SC around 18 K, while at other temperatures the system indeed exhibits SC where the Fe-3d spin polarization is suppressed or collapses.     

D3→FJ emission of Tb doped sol–gel silica

Amorphous silica samples doped with 0.1 and 1 mol% of terbium (Tb) were synthesized by the sol–gel method. In addition to the green light associated with ⁵D₄→⁷F_J transitions of Tb³⁺, the sample containing 0.1 mol% also emitted blue light as a result of ⁵D₃→⁷F_J transitions during photoluminescence (PL) measurements. As a result of concentration quenching this blue emission was not observed for the samples doped with the higher concentration (1 mol%). However the blue ⁵D₃ →⁷F_J emission was observed in the 1 mol% doped samples during cathodoluminescence (CL) measurements. Since a rough calculation indicated that the excitation rate in the CL system where the blue emission is observed may be similar to a laser PL system under conditions where the blue emission is not observed, the difference is attributed to the nature of the excitation sources. It is suggested that during the CL excitation incident electrons can reduce non-luminescent Tb⁴⁺ ions in the silica, substituting for Si⁴⁺ ions, to the excited (Tb³⁺)? state and that these are responsible for the blue emission, which does not occur during PL excitation.     

Dual-channel spectral subtraction algorithms based speech enhancement dedicated to a bilateral cochlear implant

In this paper, two speech enhancement algorithms (SEAs) based on spectral subtraction (SS) principle have been evaluated for bilateral cochlear implant (BCI) users. Specifically, dual-channel noise power spectral estimation algorithm using power spectral densities (PSD) and cross power spectral density (CPSD) of the observed signals was studied. The enhanced speech signals were obtained using either Dual Channel Non Linear Spectral Subtraction ‘DC-NLSS’ or Dual-Channel Multi-Band Spectral Subtraction ‘DC-MBSS’ algorithms. For performance evaluation, some objective speech assessment tests relying on Perceptual Evaluation of Speech Quality (PESQ) score and speech Itakura-Saito (IS) distortion measurement were performed to fix the optimal number of frequency band needed in DC-MBSS algorithm. In order to evaluate the speech intelligibility, subjective listening tests were assessed with 50 normal hearing listeners using a specific BCI simulator and with three deafened BCI patients. Experimental results, obtained using French Lafon database corrupted by an additive babble noise at different Signal-to-Noise Ratios (SNR), showed that DC-MBSS algorithm improves speech understanding better than DC-NLSS algorithm for single and multiple interfering noise sources.     

On Quantum Team Games

Recently Liu and Simaan (2004) convex static multi-team classical games have been introduced. Here they are generalized to both nonconvex, dynamic and quantum games. Puu's incomplete information dynamical systems are modified and applied to Cournot team game. The replicator dynamics of the quantum prisoner's dilemma game is also studied.