Study of the phase composition of AgI microcrystals by exciton spectroscopy and differential scanning calorimetry

Differential absorption spectra of RbAg₄I₅ have been measured in the exciton absorption region of AgI within the temperature range 27–250 °C. In the same temperature range, the temperature behavior of the heat capacity of RbAg₄I₅, Rb₂AgI₃, and KAg₄I₅ have been obtained by differential scanning calorimetry. An analysis of the results suggests that, in AgI microcrystals less than r _cr in size, the upper boundary for stability of the low-temperature β modification is higher by several tens of degrees. Fiz. Tverd. Tela (St. Petersburg) 40, 852–854 (May 1998)     

Characterization and Photocatalytic Performance of Rb+-Doped TiO2 Photocatalysts

ABSTRACT

Rb⁺-doped TiO₂ nanoparticles with higher photocatalytic activity were prepared by sol–gel method. The prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive analysis of X-rays (EDAX), and surface area (BET) measurements. The photocatalytic activity for the degradation of rhodamine B (RhB) was evaluated. The effects of calcination temperature, Rb⁺-doping amount, and the dosage of catalyst in the reaction liquid were investigated. The results showed that Rb⁺ doping can inhibit phase transformation from anatase to rutile, increase surface area of TiO₂ crystals, and reduce crystallite size. TiO₂ doped with 1% Rb⁺ and calcined at 650°C shows much higher photoactivity than the others when the doping level of Rb⁺ and calcination temperature are 0–5% and 350–850°C, respectively. The kinetics of the degradation of RhB was also analyzed. The kinetics of this reaction fits the pseudo first-order kinetics model well, and the reaction rate constants for pure TiO₂ and Rb1-650 are 0.086 min^?1 and 0.226 min^?1 respectively. Doping with Rb⁺ improves the photocatalytic activity of TiO₂ significantly.     

Point defects in alkali halide mixed crystals

Measurements of self diffusion coefficients of ⁴²K, ⁸⁵Rb and ¹²⁵I and measurements of ionic conductivity were carried out on single crystals of the (Rb₂K_1-Z)I solid solutions (z varying from 0 to 1). The self-diffusion coefficient measurements (T=875 K) indicate that two types of cation have the same mobility and that this mobility is about twice that of the anion. All these mobilities are higher for the solid solutions than for the pure components, KI and RbI. The ionic conductivity was analysed using the Schottky defect model. Interactions between defects were taken into account in this analysis. Thus, enthalpies and entropies of formation and migration of vacancies were determined. Examining the variations of these parameters as functions of composition z at a given temperature shows that the density of vacant sites is significantly higher in the case of solid solutions than in the case of pure components (for example, this density is about twice as large for (Rbo.sK_0.5)I as for KI or RbI).     

Optical excitation of the Rb+ 4p-level in rubidium halides at 8 K

In the 15–19 eV range new spectral features have been resolved in the reflection spectra of RbCl, RbBr, and RbI single crystals. They are not entirely consistent with results of a recently proposed ligand field model for the Rb⁺4p- excitons.     

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.      

Compound synthesis in TiO2 implanted with Rubidium

Rubidium ions, with energy in the range 0.1 MeV, 2.0 MeV have been implanted in TiO₂ single crystals at RT and LNT.

Defects induced by implantation have been studied by optical spectroscopy, X-ray diffraction, RBS, TEM and electrical conductivity.

During implantation, the implanted samples are blue colored after irradiation. This coloration is due to an optical absorption band localized at 900 nm which corresponds to optical transition of intrinsic defects identified as Ti³⁺. These defects are induced by a chemical reaction between the implanted ions and the oxygen of the lattice as in the case of D⁺, H⁺, Li⁺, Na⁺ and K⁺ implanted in rutile.^1-3

The synthesis of a new phase in heavily implanted rutile is exhibited by using a thermal treatment and by combining techniques such as RBS, TEM and X-ray diffraction at glancing angle in the temperature range 300°C-700°C.

This compound does not correspond to metallic precipitates of rubidium which are observed in MgO implanted with Rb ions.

Planar defects have been observed in the implanted area. A correlation is exhibited between these defects and the precipitates of the new phase. From X-ray diffraction measurements and TEM observations, the composition of the synthetized compound is likely Rb₂TiO₃.     

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.     

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.     

The structure and lattice dynamics of RbBr(1 0 0) and RbI(1 0 0) single crystal surfaces: A tensor low energy electron diffraction analysis

The structure and lattice dynamics of RbBr(1 0 0) and RbI(1 0 0) single crystal surfaces cleaved under UHV conditions were investigated by means of low energy electron diffraction (LEED) at temperatures of 156 K and 183 K, respectively. Since RbBr and RbI are insulators the experiments were carried out with a microchannel plate LEED system at very low primary currents (5 nA). For both materials four different diffraction orders could be observed. Diffraction patterns were recorded over an energy range from 30 eV to 220 eV in increments of 2 eV and I(V) curves for each spot were extracted. The I(V) curves were analyzed using the tensor LEED approach. For both alkali halide substrates surface structures of (1 × 1) periodicity close to the truncated bulk structure were found. For RbBr, the first interlayer distance is reduced by about 2.2%, where the Rb⁺ cations in the topmost layer are shifted inwards by 0.06(3) Å, and the anions also exhibit an inward shift which is however smaller (0.04(3) Å). The root mean square vibrational amplitudes are enlarged by a factor of 1.3 for Rb⁺ and 1.25 for Br⁻, respectively. For RbI(1 0 0) the cations of the topmost layer are shifted inwards by 0.07(3) Å and the anions outwards by 0.02(1) Å. The vibrational amplitudes of the ions are not enlarged as for RbBr but close to the corresponding bulk values.     

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.     

Decoupling of the order-disorder and displacive contributions to the phase transition in NH4H(ClH2CCOO)2

The effects of hydrostatic pressure and substitution of Rb⁺for the ammonium cations on the ferroelectric phase transition temperature in NH₄H(ClH₂CCOO)₂ have been studied by electric permittivity measurements. The transition temperature (T_c) decreases with increasing pressure up to 800 MPa and the pressure coefficient dT_c/dp=−1.4×10⁻² [K/MPa] has been experimentally determined. The substitution of Rb⁺ for the ammonium cations has been shown to considerably lower the ferroelectric phase transition temperature T_c. In mixed crystals, additional electric permittivity anomaly has been clearly evidenced. The results are discussed assuming a model, which combines polarizability effects, related to the heavy ion units, with the pseudo-spin tunnelling.     

UV laser induced desorption of CsI and RbI ion clusters

Experimental results of laser sputtering of cesium and rubidium iodide secondary ions are presented. A TOF mass spectrometer, operating in linear mode, continuous extraction for positive or negative ions, was used for the analysis of (CsI)_nCs⁺, (CsI)_nI⁻, (RbI)_nRb⁺ and (RbI)_nI⁻ ion emission as a function of the laser irradiance. Experimental data show that the cluster ion emission yields decrease exponentially with n, for all the laser irradiances applied. Theoretical analysis of the clusters structure was performed using density functional theory at the B3LYP/LACV3P level, for the positive and negative cluster series. A quasi-equilibrium evolution of the clusters is proposed to extract a parameter characteristic of the cluster recombination process: the effective temperature. The hypothesis of the atomic species’ recombination (during the expansion of a high density highly ionized cloud) leading to cluster formation is confirmed to some extent in a second set of experiments: the UV laser ablation of a mixed and non-mixed cesium iodide and potassium bromide targets. These experiments show that the emission yields contain contributions from both the recombination process and from the sample stoichiometry, even for high laser irradiances.     

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.     

Structure of low-lying levels in91Rb and93Rb

Life-times of low-lying levels in ₃₇ ⁹¹ Rb₅₄ and ₃₇ ⁹³ Rb₅₆ have been determined fromβ ^??γ coincidence measurements at the fission-product separator JOSEF. Values oft _1/2=17.0(8) ns and 2.0(2) ns have been obtained for the levels at 1,134 keV in⁹¹Rb and 267 keV in⁹³Rb, respectively, and upper limits could be deduced for several other states. Calculations in the frame of IBFM/PTQM have been performed for⁹¹Rb, the results of which allow an interpretation of the low-lying levels of this nucleus. For the 1,134 keV level the configuration [πg _9/2?2⁺] 7/2⁺ is suggested which lies close to or even below the 9/2 ₁ ⁺ level. The calculated half-life of 14 ns for the 1,134 keV level reproduces well the experimental value. The half-life of the 267 keV level in⁹³Rb favours the assignment ofI ^π=1/2^? to this state over the alternative 3/2^?.     

Beta decay and nuclear structure: Rb86

It was aimed to gain information on the nuclear structure of Rb⁸⁶ by investigation of the 2^?→2⁺ β transition. For this purpose the energy dependence of theβγ angular correlation and the angle dependence of theβγ circular polarization correlation have been measured. A novel experimental set-up has been used for the angular correlation measurement allowing a simultaneous determination of the anisotropy coefficientsA ₂ andA ₄ under considerable reduction of systematical and statistical errors. For the polarization correlation measurement an unusual experimental arrangement has been applied providing the possibility of simultaneous observation under four different angles. Employing additional data on shape factor measurements and energy dependent circular polarization correlations from other authors the nuclear structure of the 2^? state in Rb⁸⁶ and the 2⁺ first excited state in Sr⁸⁶ have been evaluated. For the latter purpose the unified model with weak coupling has been chosen.     

Etude des transitions de phases des composes Rb2KMO3F3, Cs2KMO3F3 et Cs2RbMO3F3 (M = Mo,W)

Crystallographic, micro-D.T.A., dielectric and pyroelectric measurements have been performed for the Rb₂KMO₃F₃, Cs₂KMO₃F₃ and Cs₂RbMO₃F₃ (M = Mo, W) compounds. Two types of transitions have been detected : the first one, for Rb₂KMoO₃F₃ at low temperature, is due to the disappearance of the superstructure detected for Rb₃MoO₃F₃α, the second one is of ferroelectric - paraelectric type (Rb₂KMO₃F₃ and Cs₂RbMO₃F₃ ; M = Mo, W). The transition temperatures have been compared vs the size of the alcaline ions and the nature of the M-O bonds. The increase of the transition temperatures from the A₂A'MO₃F₃ to the A₃MO₃F₃ compounds is likely due to the simultaneous presence of the A⁺ cations in the former ones in 6 and 12 coordination sites.     

Thermochemistry of the reactions between CN+ and H2O in the gas phase

The [H₂, C, N, 0]⁺ potential energy surface (PES) has been explored by means of high-level ab initio calculations, carried out in the framework of the G2 theory. From this survey we concluded that the predominant products of the CN⁺ + H₂O reaction are the result of the dissociation of HNCOH⁺ species and to a much lesser extent of the CNHOH⁺ cation to yield CNH⁺ + OH. According to our results HCN⁺ should not be a product of this reaction because all pathways leading to its formation are unfavourable with regards to other competitive processes. Other reactive channels lead to the formation of the H₂ONC⁺ structure which dissociates into CN + H₂O⁺. The loss of NH(3σ) and O(³P) seems to take place following spin-forbidden reaction paths through an intersystem crossing between the singlet and the triplet PESs. The global minimum of the PES, H₂NCO⁺ is easily accessible and should lead to the loss of carbon monoxide which has not been experimentally observed in CN⁺ + H₂O reactions. We cannot offer a clear explanation for this disagreement between theory and experiment.     

Preparation of amorphous films of superionic conducting glasses in systems AgIAg2MoO4 and AgIAg2OB2O3

Thermal evaporation, flash evaporation and rf-sputtering techniques were applied to the preparation of amorphous films of superionic conducting glasses in the systems AgIAg₂MoO₄ and AgIAg₂OB₂O₃. The flash-evaporated films were amorphous and showed very high conductivities, about 2 × 10^?2S/cm for the AgIAg₂MoO₄ and about 5 × 10^?3S/cm for the AgIAg₂OB₂O₃ at room temperature, and gave a Ag⁺ transport number of unity. The thermal evaporation method produced crystalline-phase included films. The rf-sputtered films were amorphous by X-ray diffraction and the transport number of Ag⁺ ions was smaller than unity (about 0.9). Thus flash evaporation was concluded to be the most suitable method for preparing amorphous films of superionic conducting glasses.     

Crystal structure features of RbFeO<Subscript>2</Subscript> polymorphs and their correlation with ionic conductivity

Analysis of correlation between structural features and rubidium ion conductivity is performed for RbFeO₂ polymorphs in a wide temperature range of 296–843 K. To explore the migration maps of Rb⁺ cations, we used neutron diffraction data for low- and high-temperature RbFeO₂ polymorphs and natural tiling concept implemented in the TOPOS software. Five independent elementary channels for the Rb⁺ cation migration have been revealed whose cross- sections were found to be essentially different in the low-temperature form, indicating a high anisotropy of the cation conductivity. During the transition to the cubic high-temperature phase all five channels become equivalent with sharply increased cross-sections, which accounts for the increase of cations mobility and gives rise to the three-dimensional character of conductivity.     

Chemical effects on x‐ray fluorescence yield of Ag+ compounds

X‐ray fluorescence measurements were carried out for silver metal and a number of silver compounds containing Ag⁺ ions such as Ag₂CO₃, Ag₂SO₄, AgNO₃, AgCl, AgBr and AgI using 59.6 keV γ‐rays, emitted from ²⁴¹Am, as the excitation source, to evaluate the value of Kβ/Kα x‐ray intensity ratio. For silver metal the value of this parameter is found to be 0.206 ± 0.003 and wide variations, 0.190 ≤ Kβ/Kα≤ 0.207, were observed for these compounds. The results are explained in terms of the charge transfer occurring between Ag⁺ and the coordinating anions. Copyright © 2005 John Wiley & Sons, Ltd.