Study of the induction period of the thermal decomposition of irradiated barium bromate

The influence of -irradiation upto 200 Mrad on the thermal decomposition of barium bromate has been studied in the temperature range 553–583 K. The fraction decomposed //-time /t/ characteristics for irradiated barium bromate exhibit stages, viz. initial gas and decay stages. Irradiation shortens the induction period conforming to the relation I=C₁–C₂ lg dose. All experimental data for induction period are tested against the values obtained from the theoretical calculations by making use of this induction-period dose relation. The topochemical aspect of the validity of the above relation has been considered to be due to the linear growth of nuclei during irradiation and subsequent exponential growth during the induction period.     

Rotational diffusion of dyes in micellar media from transient absorption

Solubilizer effects in dye solutions have been investigated by subnanosecond laser-pulse photometry. Different models for the transient dichroism of dye-micelle solutions are proposed. Computer fits of the experimental curves indicate that the model where dye molecules rotate within the liquid-like interior of the micelles is the most realistic one. Since the measured rotational diffusion times differ for different dyes in almost the same way as for pure highly-viscous solvents, the dye molecules do not act merely as labels for the rotation of the micelles, but rotate themselves considerably. It is shown that the rotational diffusion of dye molecules and micelles can be separated giving reasonable results for the size of the micelles. The results are compared with previous steady-state experiments.     

Rotational diffusion of dyes in solvents of low viscosity from transient-dichroism experiments

Rotational diffusion data from pulsed laser experiments are presented for dye molecules dissolved in alcohols and non-alcohols. Cresyl violet and fluorescein both exhibit strong dependence of the rotational motion upon solvent molecular structure. In complete contrast the rotational diffusion of the oblong dyes pyronine G and acridine orange do not reveal any specific solute-solvent interaction.     

Stable Tetra‐ and Penta‐Anions in the Gas Phase

The quest for stable gas‐phase anions in highly negative charge states has been a great challenge. While multiply charged anions are stabilized in solids and liquids by compensating cations and solvation cells, respectively, stable anions containing less than a hundred atoms in the gas phase and capable of carrying charge beyond ?3 is unknown. Here, we report the discovery of thermodynamically stable tetra‐ and penta‐anions, containing less than 50 and 80 atoms, respectively, in the gas phase. A universal model is developed that explains their stability in terms of the synergy between closed shell, high electron affinity, and size and predicts new highly‐charged anions by using the known charged clusters as building blocks. Synthesis of these species can open a new chapter in materials chemistry.     

Heteroatom‐Guided,Palladium‐Catalyzed,Site‐Selective CH Arylation of 4H‐Chromenes: Diastereoselective Assembly of the Core Structure of Myristinin B through Dual CH Functionalization

A highly site‐selective, heteroatom‐guided, palladium‐catalyzed direct arylation of 4H‐chromenes is reported. The C?H functionalization is driven not only by the substituents and structure of the substrate but also by the coupling partner being used. The diastereoselective assembly of the core structure of Myristinin B has been achieved by using a dual C?H functionalization strategy for regioselective direct arylation.     

Solvent‐Dependent Structure of the I3− Ion Derived from Photoelectron Spectroscopy and Ab Initio Molecular Dynamics Simulations

Ab initio molecular dynamics (MD) simulations of the solvation of LiI₃ in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I₃^? ion in relation to X‐ray photoelectron spectroscopy (XPS). Simulations show that hydrogen‐bond rearrangement in the solvation shell is coupled to intramolecular bond‐length asymmetry in the I₃^? ion. By a combination of charge analysis and I 4 d core‐level XPS measurements, the mechanism of the solvent‐induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent‐dependent structure of the I₃^? ion, and the geometric structure has been correlated with the electronic structure.     

On evolution of non-linear waves in polytropic reacting gases

In this paper we have studied the behavior of wave motion as propagating wavelets and their culmination into shock waves in polytropic reacting gases with same \(\gamma \)-law. An expansion wave resulting from the action of receding piston has been considered and the solution to this problem has been obtained. The propagation of weak waves has been considered and the flow variables in the region bounded by the piston and the characteristic wave front have been found out. The expansive action of a receding piston undergoing an abrupt change in velocity has been discussed. Central expansion fan and shock fronts have been studied and the solutions up to first order in the physical plane have been obtained. The effects of reaction mechanism on the solutions have been analyzed in each case.     

Colossal Stability of SiB11(BO)12−: An Implication as Potential Electrolyte in High-Voltage Alkali-ion Battery

High-voltage alkali metal-ion batteries (AMIBs) require a non-hazardous, low-cost, and highly stable electrolyte with a large operating potential and rapid ion conductivity. Here, we have reported a halogen-free high-voltage electrolyte based on SiB₁₁(BO)₁₂⁻. Because of the weak π-orbital interaction of −BO as well as the mixed covalent and ionic interaction between SiB₁₁-cage and −BO ligand, SiB₁₁(BO)₁₂⁻ has colossal stability. SiB₁₁(BO)₁₂⁻ possesses extremely high vertical detachment energy (9.95 eV), anodic voltage limit (∼10.05 V), and electrochemical stability window (∼9.95 V). Furthermore, SiB₁₁(BO)₁₂⁻ is thermodynamically stable at high temperatures, and its large size allows for faster cation movement. The alkali salts MSiB₁₁(BO)₁₂ (M=Li, Na, and K) are easily dissociated into ionic components. Electrolytes based on SiB₁₁(BO)₁₂⁻ greatly outperform commercial electrolytes. In short, SiB₁₁(BO)₁₂⁻-based compound is demonstrated to be a high-voltage electrolyte for AMIBs.