Influence of divalent cationic impurities on plasticity of AgCl

The hardening effect of Mg²⁺, Ca²⁺, Sr²⁺, Cd²⁺ and Ba²⁺ impurities in polycrystalline AgCl was investigated. With exception of Mg²⁺ the hardening effect of the impurities decreases with increasing atomic number (atomic weight). The hardening effects of Mg²⁺ and Ca²⁺ are expressively stronger than those of the three remaining impurities. Approximately linear dependence of the stress at the beginning of plastic deformation on the impurity concentration was found. Possible causes of the different hardening effects of the divalent impurities are discussed.     

Far-infrared absorption due to impurities in CsBr crystals

The far-infrared absorption in the phonon band of CsBr due to Na⁺, K⁺, Rb⁺, In⁺, and Tl⁺ impurities has been measured and compared with the calculated density of phonon states of the host lattice.     

Gap modes due to impurity pairs in ki

The pair modes due to Cl^?, Br^?, Na⁺W and Rb^v impurities in KI have been investigated using the Greens function technique. Group theory is used to put the final results as solutions of (2 × 2) determinants which could be tried by a hand calculator. Even a mass defect approximation reproduced the gap modes due to chlorine pairs, but in all cases a small change in the force constant, deduced from fitting single impurity gap modes, was used. The Raman active modes in all these cases were also computed.     

Anisotropie dipole polarizabilities and quadrupole moments of open-shell atoms and ions: O,F, S,Cl, Se,Br and isoelectronic systems

Quadrupole moment and dipole polarizability tensor components are calculated at the correlated complete-active-space self-consistent-field (CASSCF) and complete-active-space perturbation-theory (CASPT) levels for ²P states of O^?, F, Ne⁺, Na²⁺, S^?, Cl, Ar⁺, 98, K²⁺ , Se^?, Br, Kr⁺, Rb²⁺ and ³P, ¹D, ¹S states of O^?, F⁺, Ne²⁺, Na³⁺, S, Cl⁺, Ar²⁺, K³⁺, Se, Br⁺, Kr²⁺, Rb³⁺. Relativistic corrections are included perturbatively for the 34- and 35-electron systems.     

Evidence of mobile correlation between conduction layers in β-alumina

The ordering of the mobile ions in the conducting layers to form an $\text{a}\text{√3 ×}\text{a}\text{√3}$ superlattice has been investigated in K⁺, Ag⁺ and Rb⁺ β-aluminas by electron diffraction. In addition to the correlation of mobile ions within the conduction layer, the correlation between conduction layers has also been detected in Rb⁺ β-alumina with periods of 68.4 Å and 22.8 Å, or three and one multiple of the $\text{c}$ dimension. A possible mechanism for such long distance correlation through spinel blocks is discussed.     

Hofmeister series and ionic effects of alkali metal ions on DNA conformation transition in normal and less polarised water solvent

Normal and less polarised water models are used as the solvent to investigate Hofmeister effects and alkali metal ionic effects on dodecamer d(CGCGAATTCGCG) B-DNA with atomic dynamics simulations. As normal water solvent is replaced by less polarised water, the Hofmeister series of alkali metal ions is changed from Li⁺ > Na⁺ ? K⁺ ? Cs⁺ ? Rb⁺ to Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺. In less polarised water, DNA experiences the B→A conformational transition for the lighter alkali metal counterions (Li⁺, Na⁺ and K⁺). However, it keeps B form for the heavier ions (Rb⁺ and Cs⁺). We find that the underlying cause of the conformation transition for these alkali metal ions except K⁺ is the competition between water molecules and counterions coupling to the free oxygen atoms of the phosphate groups. For K⁺ ions, the ‘economics’ of phosphate hydration and ‘spine of hydration’ are both concerned with the DNA helixes changing.     

离子与通道相互作用对NaK 通道通透特性影响的研究

以NaK 通道的三维精细结构为基础,从理论上阐述了NaK 通道对钠离子、钾离子、铷离子以及钙离子的通透机理,钡离子可以作为NaK 通道阻断剂的微观机理,我们的研究结果表明,通道与离子的相互作用是决定通道对不同离子选择性的基础, 反映通道与离子相互作用的位能曲线是通道对不同离子通透性的外在表现. 关键词： NaK 通道 密度泛函 布朗动力学 通透性     

Pseudo potential calculations for Na+2, K+2, Rb+2 and Cs+2

A Hellmann type pseudopotential, is used to calculate the six lowest Σ potential energy curves of Na⁺₂, K⁺₂, Rb⁺₂ and Cs⁺₂ molecular ions.     

Solid state reactions and transport properties in the quasibinary system AgI/RbI

The reactions between AgI and Rb₂AgI₃, RbI and RbAg₄I₅ and AgI and RbI have been investigated by measurements of reaction layer thickness and by experiments with inert markers. A theoretical derivation of the growth kinetics for reactions with double layers is given. The Rb⁺-diffusion coefficients, which are needed to apply these relations to the reaction between AgI and RbI, have been obtained from an investigation of the other two reactions which form only a single product layer. The diffusion coefficient of Ag⁺in Rb₂AgI₃ was also determined from conductivity measurements on Rb₂AgI₃.     

Hydrothermal reactions of simple molecules by real-time infrared spectroscopy

Abstract

The relative roles of the materials of construction of the reactor (stainless steel or titanium) and the effects of Group 1 cations are discussed in terms of their effect on the rate of decarboxylation of acetic acid derivatives, RCO₂H. Past work indicates that the reaction container composition has a very large effect when R is CH3—. A smaller but significant effect is seen when R is electron neutral (i.e., R=H). When R is electron Withdrawing the rate depends less on the reactor type than the nature of R. The effect of the counter ion M on the rate of decarboxylation of monovalent malonate salts, HC&CHzC02M, is discussed for M=Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺. The rate generally increases with the ionic radius except that the Rb⁺ salt exhibits the fastest rate. Preliminary explanations are given.     

Parametres thermodynamiques des defauts ponctuels dans le chlorure de strontium pur ou dope par des cations monovalents ou trivalents

The electrical conductivity of a great number of SrCl₂ crystals, either purified or doped with Na⁺, K⁺, Rb⁺, Gd³⁺ and Ce³⁺, has been studied. The microscopic models used for the interpretation of the results have been justified by dielectric loss measurements, ITC and EPR (for Gd³⁺). The thermodynamic parameters of point defects have been derived, over the temperature range 420–860 K, from the fitting of experimental data to the equations of the Lidiard-Debye-Hückel theory. The values of the enthalpies of Cl vacancy mobility (0.30 eV) and Cl interstitial mobility (0.76eV), association of Cl vacancy with Na⁺ (0.53 eV), K⁺ (0.42 eV), Rb⁺ (0.40 eV) and ionic Frenkel defects formation (2.20 ± 0.11 eV) have been used in the interpretation of the experimental results over a large concentration range. The solubility enthalpy of Na ⁺ is 1.2 ± 0.1 eV; the solubility of the rare earths is very small at low temperature. The thennodynamic parameters which have been found have been compared with other known experimental values and with theoretical results.     

Kinetics of Rb<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> and Rb<Superscript>+</Superscript> formation in laser-excited rubidium vapor

We have studied the formation of the molecular ion Rb₂⁺ and the atomic ion Rb⁺. These are created in laser excited rubidium vapor at the first resonance, 5s–5p and 5p-nl transitions. A theoretical model is applied to this interaction to explain the time evolution and the laser-power dependence of the population density of Rb⁺ and Rb₂⁺. A set of rate equations which describe: the temporal variation of the population density of the excited states; the atomic ion density; and the electron density, were solved numerically under the experimental conditions of Barbier and Cheret. In their experiment the Rb concentration was 1×10¹³cm⁻³ and the laser power was taken to be 50–500 mW at vapor temperature = 450 K. The results showed that the main processes for producing Rb₂⁺ are associative ionization and Hornbeck-Molnar ionization. The calculations have also showed that, the atomic ions Rb⁺ are formed through the Penning Ionization (PI) and photoionization processes. Moreover, a reasonable agreement between the experimental results and our calculations for the ion currents of the Rb⁺ and Rb₂⁺ is obtained.      

Stationary inverted Lyman populations and free-free and bound-free emission of lower-energy state hydride ion formed by an exothermic catalytic reaction of atomic hydrogen and certain group I catalysts

Rb⁺ to Rb²⁺ and 2K⁺ to K + K²⁺ each provide a reaction with a net enthalpy equal to the potential energy of atomic hydrogen. The presence of these gaseous ions with thermally dissociated hydrogen formed a plasma having strong VUV emission with a stationary inverted Lyman population. Significant Balmer α line broadening of 18 and 9 eV was observed from a rt-plasma of hydrogen with KNO₃, and RbNO₃, respectively, compared to 3 eV from a hydrogen microwave plasma. The reaction was exothermic since excess power of about 20 mW/cc was measured by Calvet calorimetry. We propose an energetic catalytic reaction involving a resonance energy transfer between hydrogen atoms and Rb⁺ or 2K⁺ to form a very stable novel hydride ion. Its predicted binding energy of 3.0471 eV with the fine structure was observed at 4071 Å, and its predicted bound-free hyperfine structure lines matched those observed for about 40 lines to within.01 percent. Characteristic emission from each catalyst was observed. This catalytic reaction may pump a CW HI laser.     

Alkali metal ion-poly (ethylene oxide) complexes. II. Effect of cation on conductivity

Complexes of alkali metal salts with various polymers have for some time been recognized as fast ionic conductors. Polymer electrolyte fast ion conductors are currently under consideration for use in high energy density electrochemical cells. In order to aid in our understanding of the mechanism of ionic conductivity we have examined systematically complexes of poly(ethylene oxide) (PEO) with the alkali metal salt series of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ with both tetraflouroborate (BF₄^-) and trifluoromethanesulfonate (CF₃SO₄^-) anions. The ratio of monomer to salt was 10:1 in all cases. Complex impedance measurements were made on all samples in the temperature range 40°–125°C. With CF₃SO₄^- as the anion a definite trend was apparent with the smallest cation Li⁺ being the worst conductor and Cs⁺, the largest cation, being the best. When BF₄^- salts are used, the Na⁺ complex is found to be the best conductor and Rb⁺ the worst. This study, in connection with our earlier studies, has shown that synergy between cation and anion in the polymer matrix is an important consideration in determining the ionic conductivity.     

Synthesis and Spectral Study of Several Solid M3[Eu(2,6-Pyridinedicarboxylate)3] Salts (M=Li+, Na+, K+, Rb+, Cs+, NH4 +, and Pyridinium+)

Abstract

Salts of the [Eu(2,6-pyridinedicarboxylate)₃]^3- complex anion and various monovalent inorganic and organic counterions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, and pyridinium⁺) have been synthesized and studied by emission spectroscopy. The Eu³⁺ ion emission spectra exhibited by these salts have been observed with high resolution (less than 1.0 cm^?1) and at low temperature (77 K). The emission spectra of these compounds indicate that changing the attached counterion does not affect the site symmetry observed by the europium ion beyond slight distortions indicated by small shifts in the energies of the Eu³⁺ electronic levels.     

Study of ethylene adsorption on zeolite NaY modified with group I metal ions

The adsorption of ethylene by zeolite NaY and zeolite NaY modified by cation exchange with potassium, rubidium, and cesium ions was studied. Cation exchanges were carried out using KNO₃, RbNO₃, and CsNO₃ in the concentration ranges of 0.2-10 mM. XRD patterns and specific surface areas illustrated that modification of NaY zeolite by very dilute solutions containing K⁺, Rb⁺ and Cs⁺ did not lead to significant changes in the crystallinity. Analysis of metals content (ICP-OES) showed that Cs⁺ can replace Na⁺ better than Rb⁺ and K⁺. Particle analysis indicated slight decreases in surface area but pore volumes and pore diameters remained unchanged. Ethylene adsorption isotherms indicated that Na-Y zeolite which was modified by 5.0 mM KNO₃, 0.5 mM RbNO₃ and 1.0 mM CsNO₃ could adsorb ethylene better than zeolite Na-Y. K-NaY zeolite adsorbed up to 102.45 cm³/g ethylene, while Rb-NaY and Cs-NaY zeolites adsorbed up to 98.50 cm³/g and 90.15 cm³/g ethylene, respectively. Ethylene adsorption capacities depended on number of adsorption sites and surface interactions.     

Zur Adsorptionskinetik von Tracermengen 22Na+, 42K+ und 86Rb+ aus gemischten Lösungsmitteln an Aktivkohle

Die Adsorption von Tracermengen der Alkaliionen (²²Na⁺, ⁴²K⁺, ⁸⁶Rb⁺) aus gemischten Lösungsmitteln (z. B. Wasser-Methanol, Äthanol, -Aceton, -Dioxan) an Aktivkohle (KO) steigt mit zunehmender Konzentration an organischem Lösungsmittel ab einem bestimmten Gehalt exponentiell an. Dabei nehmen die adsorbierten Ionenmengen zu, desgleichen die Geschwindigkeit der Adsorption. Bei vergleichbarer spezifischer Aktivität hängt die Adsorption von der Art und Zusammensetzung des Lösungsmittelgemisches ab. Werden die maximal adsorbierten relativen Ionenmengen bei konstanter spezifischer Aktivität gegen die reziproke Dielektrizitälskonstante des entsprechenden Lösungsmittelgemisches aufgetragen, so erhält man für bestimmte Konzentrationsbereiche an organischem Lösungsmittel charakteristische Geraden, deren Steigungen in der Reihenfolge ²²Na⁺, ⁴²K⁺, ⁸⁶Rb⁺ abnehmen.

Auβer der Zusammensetzung des Lösungsmittelgemisches sind für die Adsorption der Alkaliionen auch spezielle Wechselwirkungen zwischen Kationen und Solvatmolekühn von Einfluβ.     

The Hd-center interaction with a Rb+ ion during irradiation and thermal annealing in kBr

The role of Rb⁺ ions on defect formation in KBr has been studied. The impurity suppresses colorability due to X-raying at 6 K, but does not result in the formation of any centers characteristic to Rb⁺ ions at this temperature. A new optical absorption band peaked at 3.19 eV is produced only by thermal annealing of irradiated KBr:Rb. This band is annealed in parallel to the annealing of the F band in a stage at 55 K, obeying second-order rate equation with an activation energy of 0.102 eV. This band is ascribed to the H_A(Rb⁺)-center. Calculation is made on the elastic interaction energy between the H-center and a Rb⁺ ion, to show that the interaction along 〈110〉 is repulsive, whereas that along 〈001〉 is attractive. Based on this result of calculation, the structure and the formation mechanism of the H_A(Rb⁺) center, and origin of suppression of colorability at 6 K are discussed. The difference in the interaction of the interstitial atom with Rb⁺ during its dynamical motion and thermal motion is emphasized.     

Density functional theory study of the bis‐3‐benzo‐crown ethers and their complexes with alkali metal cations Na+, K+, Rb+ and Cs+

The binding interactions of bis‐3‐benzo‐15‐crown‐5 ethers and bis‐3‐benzo‐18‐crown‐6 ethers (neutral hosts) with a series of alkali metal cations Na⁺, K⁺, Rb⁺ and Cs⁺ (charged guests) were investigated using quantum chemical density functional theory. Different optimized structures, binding energies and various thermodynamic parameters of free crown ethers and their metal cation complexes were obtained based on the Becke, three‐parameter, Lee–Yang–Parr functional using mixed basis set (C, H, O, Na⁺ and K⁺ using 6‐31 g, and the heavier cation Rb⁺ and Cs⁺ using effective core potentials). Natural bond orbital analysis is conducted on the optimized geometric structures. The main types of driving force host–guest interactions are investigated. The electron donating O offers a lone pair of electrons to the contacting LP* (1‐center valence antibond lone pair) orbitals of metal cations. The bis‐3‐benzocrown ethers are assumed to have sandwich‐like conformations, considering the binding energies to gauge the exact interactions with alkali cations. It is found that there are two different types of complexes: one is a tight ion pair and the other is a separated ion pair. Copyright © 2011 John Wiley & Sons, Ltd.     

Structural phase transitions in KCdF3 and K0.5Rb0.5CdF3

Successive structural transitions of KCdF₃ and K_0.5Rb_0.5CdF₃ have been studied by means of thermal diffusivity, polarized light scattering and X-ray diffraction. It is found that transitions occur at about 460 K and 475 K in KCdF₃, and at 222 K, 232 K, 250 K, 258 K and 268 K in K_0.5Rb_0.5CdF₃. The partial exchange between K⁺ and Rb⁺ ions gives rise to simultaneous condensation of the M^z ₃ and R^x ₂₅ soft phonons.