Kinetics of decomposition of the solid electrolyte RbCu4Cl3I2

The processes of electrochemical decomposition of the solid electrolyte RbCu₄Cl₃I₂ at the vitreous carbon electrode and chemical decomposition of RbCu₄Cl₃I₂ by iodine has been investigated. The anodic decomposition of the electrolyte occurs in two steps. At first, the oxidizing electrode reaction of Cu⁺ ions up to Cu²⁺ ions takes place at potentials higher than 0.57 V and onto the electrode surface the layer of decomposition products is formed, including the compound of divalent copper RbCuCl₃. Then the oxidizing reaction of I ions occurs at potentials higher than approximately 0.67 V with deposition of the iodine layer onto the electrode surface. The deposition rate of the layers of decomposition products is controlled by instantaneous nucleation and two-dimensional growth of the deposit. It was shown that slow diffusion of the iodine in the reaction product layer is a limiting step in the chemical interaction of iodine with RbCu₄Cl₃I₂. For the compressed RbCu₄Cl₃I₂ sample investigated, iodine diffusion coefficient was calculated to be 6.2×10⁻⁷ cm² s⁻¹. Iodine loss from the glassy carbon surface is about 1.1×10⁻⁴ g cm⁻² s⁻¹ at the thickness of the RbCu₄Cl₃I₂ sample is equal to 2 mm.     

On the delay mechanism of Cl<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> diatomic anion dissociation up to the microsecond timescale

The dissociative capture of slow electrons by tetrachlorethylene (C₂Cl₄) has been investigated by resonant electron capture negative ion mass spectrometry. Metastable ions with fractional mass numbers 7.5, 17.5, and 19 corresponding to the C₂Cl₄⁻ → Cl⁻ + C₂Cl₃ and Cl₂⁻ → Cl⁻ + Cl decays occurring at the microsecond timescale have been detected. It has been revealed that Cl₂⁻ anions, which are fragment ions, can dissociate at the microsecond timescale, which is very surprising for a system with one internal degree of freedom. This process is assumingly attributed to the rotational excitation of Cl₂⁻ anions. Thus, the experimental estimate of the time of rovibronic relaxation in the Cl₂⁻ anion has been obtained.     

Interaction of chloride ions with water clusters absorbing ozone: A computer experiment

The molecular dynamics method is used to investigate the interaction of two, four, and six chloride ions with (H₂O)₅₀, clusters absorbing six ozone molecules. Chloride ions moving toward the cluster penetrate into it. The presence of ozone increases the residence time of Cl⁻ ions in the cluster. The duration of the perturbation increases with the number of Cl⁻ ions surrounding the 6O₃ + (H₂O)₅₀ system. The interaction with Cl⁻ ions enhances the positional disorder of the molecules in the system and enhances the intensity of absorption and emission of infrared radiation. These changes, however, are not monotonic function of the number of ions perturbing the system. As a result of the interaction with Cl⁻ ions, the integrated intensity of the Raman scattering on the (O₃)₆(H₂O)₅₀ cluster in the frequency range 0 ≤ ω ≤ 1100 cm⁻¹ is significantly lower and the number of peaks in the spectrum is smaller.     

On the study of ion-acoustic solitary waves and double-layers in a drift multicomponent plasma with electron-inertia

Using the pseudopotential method, theoretical investigation has been made on the firstorder Korteweg-deVries ion-acoustic solitons in a multicomponent plasma consisting of warm positive ions, negative ions and isothermal electrons. The effects of electron-inertia and drift motion of the ions on the amplitudes and widths of the solitons have been studied in a plasma having (H⁺, Cl⁻), (H⁺, O⁻), (He⁺, H⁻) and (He⁺, O⁻) ions. Ion-acoustic double-layers have also been investigated for such plasmas. It has been found that drift velocity and electron-inertia have significant contribution on the formation of double-layers in multicomponent plasma     

Temperature variation of the Debye-Waller factors of metal and halide ions in CsCl and CsBr powders by X-ray diffraction. I. Debye-Waller factors of Cs+ and Cl− ions in CsCl from room temperature to 90°K

The temperature variation of the Debye-Waller factors of Cs⁺ and Cl⁻ ions in CsCl powder has been studied using X-ray powder diffraction. A continuous flow cryostat has been used to record the diffractograms and the integrated intensities of the Bragg peaks at different temperatures have been obtained. The integrated intensities of the odd and even reflections have been analysed following the structure of the CsCl compound and the Debye-Waller factors of the Cs⁺ and Cl⁻ ions have been estimated. The results have been verified by structure factor least squares refinement. Theoretical shell model lattice dynamical calculations have been done using a 7-parameter model in the harmonic approximation and the values compared with the present X-ray measurements.     

Superparamagnetic behaviour and hyperfine interactions in ferrous hydroxide II and green rust I

The existence of a ferrous hydroxide, 2Fe(OH)₂, FeOHCl, containing Cl⁻ ions substituted for OH⁻ ions has been confirmed. The 4.4 K spectra of this hydroxide variant and green rust I obtained by oxidation are analysed in terms of a mixture of quantum states and the superparamagnetic behaviour at higher temperatures gives some informations on the particle size distribution and the mechanism of oxidation.     

Mössbauer effect evidence of chlorine environments in ferric oxyhydroxides from iron corrosion in chlorinated aqueous solution

A Mössbauer investigation of ferric oxyhydroxides obtained in chlorinated aqueous media demonstrates that Cl^– ions take a part in the corrosion process by insertion in akaganeite (FeOOH,Cl_x) and substitution in lepidocrocite (8FeOOH,FeOCl).     

Electron-stimulated desorption of negative O? ions from the oxidized O/Ru surface

This paper reports on a study of the electron-stimulated desorption of negative oxygen ions from the O/Ru surface, which represents an additional factor responsible for the destruction of the protective oxide layer of the mirrors used in ultraviolet lithography. The cross section of degradation of the O/Ru layer due to the electron-stimulated desorption of the O⁺ and O⁻ ions and the O atoms has been found to be 1.6 × 10⁻¹⁹ cm². A comparison of the dependences of the electron-stimulated desorption yield of O⁺ and O⁻ ions on the incident electron energy E with the ionization cross section of the adsorbate core level σ _O2s (E) has revealed that the ionization of the O 2s level is the main channel of the electron-stimulated desorption of O⁻ ions.     

Photophysical studies of xanthene dye in alkanols and in presence of inorganic ions

Eosin Y belongs to a xanthene group. It is an anionic fluorescent dye. The absorbance and fluorescence of Eosin Y have been investigated in a series of alkanols (methanol to propanol). When the solvents are added to the aqueous solution of Eosin Y (EY) the absorbance and fluorescence intensity are enhanced. The alkanols are found to affect the absorption and fluorescence spectra of the dye. On the basis of solvent adsorption model the binding constants of the dye with alkanols have been estimated. The interaction of solvent molecule with dye in aqueous solution is specific in nature. The fluorescence quenching of Eosin Y by the inorganic ions [Fe(CN)₆]⁻³, [Fe(CN)₆]⁻⁴ and Cl⁻ was also observed. The ions influenced the quenching process to different extents. The rate constants of quenching were calculated using the Stern-Volmer equation. The equilibrium constant of dye in presence of inorganic ions are determined by Scott equation.     

Ionic compressibilities and ionic radii - systematic trends

Ionic radii and compressibilities have been calculated for a number of monovalent and divalent ions and radicals on the basis of the compressible ion theory. In this theory, the compression energy of an ion is given as a two-parameter function of its radius,A exp (−r/p), the radius and compressibility of the ion being monotonically decreasing functions of the compressing force acting on it. Choosing a standard force reflecting the average environment in the alkali halides, univalent radii and compressibilities have been calculated. This is the first theory to estimate ionic compressibilities. The values show systematic trends among groups of related ions. Anions are found to be significantly more compressible than cations (e.g., the compressibilities of Ca⁺⁺, K⁺, Cl⁻ and S^{− −} are respectively 0.8530, 1.342, 2.952 and 5.150 × 10⁻¹² cm²/ dyne). Multivalent or ‘crystal’ radii and compressibilities have also been calculated by scaling the standard force by the square of the ionic charge. The calculated ionic radii are closer to experimental values than the classical empirical radii.     

The optimization of potential energy surface parameters for the CsCl + RbI system with the use of linear regression analysis

The influence of interaction potential parameters of likely charged ions on cross sections of various channels of a reaction of a pair of diatomic molecules with ionic bonds was studied in terms of quasi-classical trajectory simulation with the use of linear mean-square regressions. In the regression approach, the dependence of the cross section of a given reaction channel on potential parameters at each fixed collision energy is approximated by a linear function. We determined the region of softness parameters of the Cs⁺-Rb⁺ and Cl⁻-I⁻ interaction potentials. This region was optimum for the reproduction of experimental excitation functions of atomic and complex positive ions for the CsCl + RbI → products reaction.     

Multiwave electric-discharge radiator for the 175–258-nm region

The radiation spectra of plasma in the region of 130–350 nm and the intensities of the 175-nm ArCl, 193-nm ArF, and 258-nm Cl₂ bands produced in the transverse volume discharge on a mixture of Ar/CF₂Cl₂ = (1–15)/(0.008–0.150) kPa are investigated. The discharge is shown to be a multiwave source of UV-VUV radiation on transitions of ArCl, ArF, and Cl₂ molecules. The optimum content of Freon-12 molecules is 0.008–0.010 kPa and that of argon atoms 10–15 kPa. The ratio of the intensities of the ArCl (B-X) and ArF (B-X) bands is 10, which is approximately equal to the ratio of concentrations of [Cl⁻] and [F⁻] ions, which are formed in the reaction of dissociative electron attachment to CF₂Cl₂ molecules. The service life of a radiator with λ = 175 nm of ArCl on one mixture in a gas-static mode is not greater than 5·10³ pulses. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 3, pp. 407–408, May–June, 2000.     

LSP spectral changes correlating with SERS activation and quenching for R6G on immobilized Ag nanoparticles

In terms of chemical enhancement in Surface Enhanced Raman Scattering (SERS), we investigated the effect of halide and other anions to rhodamine 6G (R6G) adsorbed Ag particles that were immobilized on the substrates. The residual species on chemically prepared Ag particles such as citrate or a-carbon were thoroughly substituted by various anions, e.g., Cl⁻, Br⁻, I⁻, SCN⁻, CN⁻, or S₂O₃ ²⁻ anions, whose adsorption features are elucidated by the formation constants for AgX₂ ^(m−1)−, here X denotes the above anions. In particular, Cl⁻, Br⁻, or SCN⁻ ions activated SERS of R6G via intrinsic electronic interaction with Ag, whereas CN⁻, S₂O₃ ²⁻, or I⁻ anions quenched it due to their exclusive adsorption onto the Ag surfaces. We found that the activation process with the anions commonly yields a marked blue-shift of the coupled plasmon peak from ca. 650–700 to 500–550 nm in elastic scattering. It is rationalized by slight increase of the gap size between adjacent Ag nanoparticles by only ca. 1 nm based on theoretical simulations. This is probably caused by slight dissolution, oxidative etching, of the particles according to large formation constants of the complexes. Consequently, partly remaining negative charges on the Ag surface, and a slight increase in the gap size, providing huge electric field, facilitated R6G cations to adsorb on the nanoparticles, especially at the junction.     

Luminescence properties of calcium-iodide crystals

The effect of the conditions of preparation, temperature, and the action of x rays on the luminescence properties of calcium-iodide scintillation crystals is investigated. On the basis of the results of a study of the spectral characteristics of CaI₂ and CaI₂:H₂ crystals for optical and x-ray excitation in the temperature range 90–400 K, also taking into account the results of a study of the luminescence properties of CaI₂ crystals activated by Cl⁻, Br⁻, OH⁻, and Ca²⁺ impurities, it is suggested that the 236-nm band observed in the excitation spectra of crystals of calcium iodide may be caused by an uncontrollable hydrogen impurity. The luminescence of these crystals with maximum at 395 nm is ascribed to radiative recombination of excitons trapped at H⁻ ions. Zh. Tekh. Fiz. 69, 135–136 (January 1999)     

Analysis of a qualitative criterion for forecasting off-centre displacement of impurity ions in ionic crystals

Summary With the aid of the Sanderson model for nonmolecular structure a qualitative criterion is derived for forecasting off-centre configurations of monovalent impurity ions (Li⁺, F⁻, Cl⁻, Na⁺, Ag⁺, Cu⁺) in alkali halide crystals. The same criterion is checked for Mn²⁺ impurity ions in some oxides. We also present a critical review of the criteria introduced in the past, as well as of the experimental results up to now known in the literature. Due to the relevance of its scientific content, this paper has been given priority by the Journal Direction. Work jointly supported by the Ministero della Pubblica Istruzione and by Consiglio Nazionale delle Ricerche, Gruppo Nazionale di Struttura della Materia.     

X-ray diffraction studies of silicon implanted with high-energy erbium ions

Silicon crystals after implantation of erbium ions with energies in the range 0.8–2.0 MeV and doses in the range 1×10¹²–1×10¹⁴ cm⁻² have been studied by two-and three-crystal x-ray diffraction. Three types of two-crystal reflection curves are observed. They correspond to different structural states of the implanted layers. At moderate doses (1×10¹²–1×10¹³ cm⁻²) a positive strain is observed, due to the formation of secondary radiation defects of interstitial type. An increase of the implantation dose is accompanied by the formation of an amorphous layer separating the bulk layer and a thin monocrystalline surface layer. At an implantation dose of 1×10¹⁴ cm⁻² the monocrystalline surface layer is completely amorphized. Parameters of the implantation layers are determined. A model of the transformation of structural damage is discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 853–857 (May 1997)     

Self-assembly of boehmite nanopetals to form 3D high surface area nanoarchitectures

A flower-like boehmite nanostructure was prepared through a template-free chemical route by the self-assembly process of nanosize petals 800–1000 nm long, 200–250 nm wide, 20–50 nm thick and having an average crystallite size of about 2.21 nm. X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), DTA/TGA analyses and Brunauer–Emmet–Teller (BET-N₂) analyses were used in order to characterize the product obtained. XRD results exhibited that the obtained nanostructures composed of pure orthorhombic AlOOH phase. The effects of Cl⁻ ions and TEA on the growth of boehmite three-dimensional nanoarchitectures in the presence of NO₃^-\mathrm{NO}_{3}^{-} ions were investigated. BET analyses of as-prepared material demonstrate that this nanostructure material has a high specific surface area, as high as 123 m² g⁻¹.     

Rheological behaviour of worm-like micelles: Effect of electrostatic interactions

Summary Both linear and non-linear viscoelasticity experiments have been performed in semi-dilute micellar aqueous solutions of ethanediyl-α,ω-bis (dodecylmethylammonium bromide) as a function of solution chloride (NaCl) concentration. The results suggest that both linear and non-linear properties are affected by the electrostatic interactions. In particular, the plateau modulusG′_∞ and the ratioσ _m/G′_∞, whereσ _m represents the plateau value in a stress-shear rate experiment, are enhanced as the electrostatic interactions are screened by addition of salt. The zero-shear viscosity is lowered upon addition of NaCl, due likely to an exchange of the Cl⁻ ions with the Br⁻ counterions. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Counterion condensation in ionic micelles as studied by a combined use of SANS and SAXS

We report a combined use of small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) to the study of counterion condensation in ionic micelles. Small-angle neutron and X-ray scattering measurements have been carried out on two surfactants cetyltrimethylammonium bromide (CTABr) and cetyltrimethylammonium chloride (CTACl), which are similar but having different counterions. SANS measurements show that CTABr surfactant forms much larger micelles than CTACl. This is explained in terms of higher condensation of Br⁻ counterions than Cl⁻ counterions. SAXS data on these systems suggest that the Br⁻ counterions are condensed around the micelles over smaller thickness than those of Cl⁻ counterions.