Ab-initio molecular dynamics and vibrational Raman spectroscopy investigations of quartz polymorph at high temperature

Quartz has found a wide range of applications over the past years. In the present work, the temperature dependence of microcrystalline quartz is investigated with Raman spectroscopy and DFT-based molecular dynamics simulations. We aimed to determine the structure at short and medium range distances as a function of the increasing temperature. The dynamics and the structural changes are analysed in terms of time-dependent properties, and the vibrational analysis obtained from calculated dipole trajectory and vibrational density of states (VDOS). The computed data is compared to Raman and infrared spectroscopic measurements. The approach is of a particularly great interest when we focus on the structural behaviour, and the dynamical disorder observed and characterised through geometric and thermodynamic data. The calculations confirm that the infrared and Raman signature as a function of temperature provide a sensitive analysis of the structural behaviour of quartz.     

Electrosynthesis of biologically active dicycloalkyl di- and trisulfides involving an H<Subscript>2</Subscript>S—S<Subscript>8</Subscript> redox system

Biologically active dicycloalkyl di- and trisulfides were prepared by the reactions of cycloalkanes C₅—C₇ with H₂S and S₈ under the anodic (cathodic) activation of hydrogen sulfide. In dichloromethane, the electrochemical activation of H₂S in the presence of sulfur can generate sulfur-centered radical intermediates that react with cycloalkanes at room temperature. The current yield of di- and trisulfides depends on the method of redox activation of hydrogen sulfide, the concentration of sulfur, and the time of electrosynthesis. The anodic activation of hydrogen sulfide in the synthesis of dicycloalkyl di- and trisulfides in an excess S8 is more efficient than the cathodic activation. In the series of cycloalkanes C₅—C₇, the highest yield of sulfur-containing products is observed for cycloheptane.     

Effilement minimal en une singularité isolée de l'équation de Schrödinger et application au principe de Picard

In this paper, the generalized Schrödinger equation (–)u=0 on the punctured unit disk of ² is investigated. If is rotation free and satisfies the Picard principle at the origin, it is shown that if a setE is minimal thin relatively to an extremal harmonic functionh with zero boundary values at {|x|=1}, there exists a sequence (r _n ) converging to zero such that B(O,r _n ) C E. Lete be the -unit. It is proved that if a measure satisfies _\E e h d<, for a minimal thin, relatively toh , setE then the Picard principle is valid for the measure + .

     

Chromium(III) and indium(III) 3,6-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-<Emphasis Type="Italic">o</Emphasis>-semiquinolate complexes as redox mediators of hydrogen sulfide oxidation in reactions with cycloalkanes

The electrochemical oxidation of the chromium(III) and indium(III) complexes with 3,6-di-tert-butyl-o-semiquinolate leading to the formation of active monocationic species is studied by cyclic voltammetry. The reactions of the latter with hydrogen sulfide generate the radical cation of H₂S, whose fragmentation affords the proton and thiyl radical. These complexes are proposed for the first time as redox mediators for the one-pot thiolation of inert cycloalkanes C₆–C₈, which decreases the activation energy of hydrogen sulfide compared to that for direct electrochemical oxidation. The major products of cycloalkane functionalization involving H₂S are thiols and organic di- and trisulfides. The yield of the synthesized compounds depends on the type of the mediator: the chromium(III) complex exhibits the highest efficiency in the electrocatalytic transformations.     

Lattice Boltzmann Simulation of Mixed Convection Heat Transfer in a Driven Cavity with Non-uniform Heating of the Bottom Wall

The goal of this article is to study numerically the mixed convection in a differentially heated lid-driven cavity with non-uniform heating of the bottom wall. The velocity field is solved by a hybrid scheme with multiple relaxation time Lattice Boltzmann(MRT-LBM) model, while the temperature field is obtained by resolution of the energy balance equation using the finite difference method(FDM). First, the model is checked and validated using data from the literature. Validation of the present results with those available in the literature shows a good agreement.A good efficiency in time simulation is confirmed. Thereafter, the model has been applied to mixed convection in a driven cavity with non-uniform heating wall at the fixed Grashof number Gr = 106. It is found that, the heat transfer is weakened as the Richardson number is augmented. For Gr = 106, we note the appearance of secondary vortices at different positions of the cavity corners.     

Nature of the eigenstates in the miniband of random dimer-barrier superlattices

The dc conductance, the universal quantum fluctuations and the resistance distribution are numerically investigated in dimer semiconductor superlattices by means of the transfer matrix formalism. We are interested in the GaAs/Al_x Ga _1 − xAs layers, having identical thickness, where the aluminium concentration x takes, at random, two different values, with the constraint that one of them appears only in pairs, i.e. the random dimer barrier (RDB). These systems exhibit a miniband of extended states, around a critical energy, lying to the typical structure of the dimer cell. The states close to this resonant energy consist of weakly localized states, while in band tails i.e. for negligible conductance, the states are strongly localized. This is evidence of the suppression of localization in the RDB superlattices. The nature of the transition between these two regimes is quantitatively investigated through relevant physical quantities. The model is, hence, clearly and statistically examined.