1,2-Shift in the anodic oxidation of aromatic compounds

The 1,2-shift observed during oxidation of organic substrates can arise by involvement of cation radicals.     

Effects of disorder on ferromagnetism in diluted magnetic semiconductors

We present results of a numerical mean-field treatment of interacting spins and carriers in doped diluted magnetic semiconductors, which takes into account the positional disorder present in these alloy systems. Within our mean-field approximation, disorder enhances the ferromagnetic transition temperature for metallic densities not too far from the metal-insulator transition. Concurrently, the ferromagnetic phase is found to have very unusual temperature dependence of the magnetization as well as specific heat as a result of disorder. Unusual spin and charge transport is implied.     

Clouding Behavior and Thermodynamic Study of Nonionic Surfactants in Presence of Additives

The present study investigates the effect of different additives on the cloud point (CP) of nonionic surfactants Triton X-100 (TX-100) and Triton X-114 (TX-114) in aqueous solutions. The thermodynamic parameters of these mixtures were calculated at different additive concentrations. The cloud point of nonionic surfactants TX-100 and TX-114 decreased with the increment of electrolyte concentrations and increased with alcohol concentrations. The standard Gibbs free energy was found to be positive for both the surfactants, whereas the enthalpy and the entropy of the clouding phenomenon were found to be positive with alcohols and negative with electrolytes. The overall clouding process was endothermic for alcohols and exothermic for electrolytes.     

Realizing universal edge properties in graphene fractional quantum Hall liquids

Universal chiral Luttinger liquid behavior has been predicted for fractional quantum Hall edge states, but so far has not been observed experimentally in semiconductor-based two-dimensional electron gases. One likely cause of this absence of universality is the generic occurrence of edge reconstruction in such systems, which is the result of a competition between confinement potential and Coulomb repulsion. We show that due to a completely different mechanism of confinement, edge reconstruction can be avoided in graphene, which allows for the observation of the predicted universality.     

Tuning the electrocrystallization parameters of semiconducting Co[TCNQ]2-based materials to yield either single nanowires or crystalline thin films

Electrocrystallization of single nanowires and/or crystalline thin films of the semiconducting and magnetic Co[TCNQ]2(H2O)2 (TCNQ=tetracyanoquinodimethane) charge-transfer complex onto glassy carbon, indium tin oxide, or metallic electrodes occurs when TCNQ is reduced in acetonitrile (0.1 M [NBu4][ClO4]) in the presence of hydrated cobalt(II) salts. The morphology of the deposited solid is potential dependent. Other factors influencing the electrocrystallization process include deposition time, concentration, and identity of the Co2+(MeCN) counteranion. Mechanistic details have been elucidated by use of cyclic voltammetry, chronoamperometry, electrochemical quartz crystal microbalance, and galvanostatic methods together with spectroscopic and microscopic techniques. The results provide direct evidence that electrocrystallization takes place through two distinctly different, potential-dependent mechanisms, with progressive nucleation and 3-D growth being controlled by the generation of [TCNQ]*- at the electrode and the diffusion of Co2+(MeCN) from the bulk solution. Images obtained by scanning electron microscopy reveal that electrocrystallization of Co[TCNQ]2(H2O)2 at potentials in the range of 0.1-0 V vs Ag/AgCl, corresponding to the [TCNQ]0/*- diffusion-controlled regime, gives rise to arrays of well-separated, needle-shaped nanowires via the overall reaction 2[TCNQ]*-(MeCN)+Co2+(MeCN)+2H2O right harpoon over left harpoon {Co[TCNQ]2(H2O)2}(s). In this potential region, nucleation and growth occur at randomly separated defect sites on the electrode surface. In contrast, at more negative potentials, a compact film of densely packed, uniformly oriented, hexagonal-shaped nanorods is formed. This is achieved at a substantially increased number of nucleation sites created by direct reduction of a thin film of what is proposed to be cobalt-stabilized {(Co2+)([TCNQ2]*-)2} dimeric anion. Despite the potential-dependent morphology of the electrocrystallized Co[TCNQ]2(H2O)2 and the markedly different nucleation-growth mechanisms, IR, Raman, elemental, and thermogravimetric analyses, together with X-ray diffraction, all confirmed the formation of a highly pure and crystalline phase of Co[TCNQ]2(H2O)2 on the electrode surface. Thus, differences in the electrodeposited material are confined to morphology and not to phase or composition differences. This study highlights the importance of the electrocrystallization approach in constructing and precisely controlling the morphology and stoichiometry of Co[TCNQ]2-based materials.     

Aspects of tautomerism. Part 16. Influence of the y-keto function on the reactions of sulphonic acids

Reaction of sodium 2-formylbenzenesulphonate (1) with thionyl chloride or phosphorous pentachloride gives a mixture of pseudo (2) and normal (3) sulphonyl chlorides. Whereas ammonium 2-carboxybenzenesulphonate (6) gives only the normal sulphonyl chloride (7) on reaction with thionyl chloride, a mixture of normal (7) and pseudo (8) isomers are formed on reaction with phosphorous pentachloride. Sodium 2-benzoylbenzenesulphonate (15), on the other hand, gives the corresponding normal sulphonyl chloride (16) on reaction with both of the reagents mentioned above. Based on these observations it is concluded that γ-keto sulphonic acids are amenable to the influence of γ-carbonyl group as in the case of γ-keto carboxylic acids but to a lesser extent.     

Automated sampling assessment for molecular simulations using the effective sample size

To quantify the progress in the development of algorithms and forcefields used in molecular simulations, a general method for the assessment of the sampling quality is needed. Statistical mechanics principles suggest the populations of physical states characterize equilibrium sampling in a fundamental way. We therefore develop an approach for analyzing the variances in state populations, which quantifies the degree of sampling in terms of the effective sample size (ESS). The ESS estimates the number of statistically independent configurations contained in a simulated ensemble. The method is applicable to both traditional dynamics simulations as well as more modern (e.g., multi-canonical) approaches. Our procedure is tested in a variety of systems from toy models to atomistic protein simulations. We also introduce a simple automated procedure to obtain approximate physical states from dynamic trajectories: this allows sample-size estimation in systems for which physical states are not known in advance.     

Thorium free antireflection coating in MWIR region on Silicon optics

Most infrared transmitting optics have high refractive indices which in turn have high per surface reflection loss. So antireflection coating has very important role in increasing the transmission in the desired wavelength region. In this paper a study has been carried out on the design and fabrication of Thorium free antireflection coating effective for Silicon substrate in MWIR (3.6–4.9 μm) region. The wave band 3.6–4.9 μm is chosen for the reported work because the detected system used in MWIR region has a band selection filter effective in the same wavelength region. Comprehensive search method was used to design the multilayer stack on Silicon substrate. The coating materials used in the design were Germanium (Ge) and Silicon dioxide (SiO₂). The fabrication of coating was made in a coating plant fitted with Cryo pump system and Residual Gas Analyzer. The evaporation was carried out at high vacuum (2–6 × 10–6 mbar) using Electron Beam Gun and layer thicknesses were measured with crystal monitor. The result achieved for the antireflection coating was 96% average transmission in 3.6–4.9 μm band which withstood MIL-F-48616 environmental testing. This work provides an alternate antireflection coating on Silicon by replacing radioactive Thorium Fluoride, used as a coating material in most IR antireflection coating designs.     

All-inorganic solid-state electrochromic devices: a review

Electrochromic devices (ECDs) are currently attracting much interest in academic and industry for both research and their commercial applications because of their controllable transmission, absorption, and/or reflectance. This paper reviews the progress that has taken place from 1969 until the year 2015 with regard to all-solid-state inorganic ECD fabrication. The main aim of this review article is to provide an easy entrance to literature of all-inorganic solid-state ECD.