The Zintl ion As-7](2-): an example of an electron-deficient As-x radical anion

K(2,2,2-crypt)](2)As-7]center dot THF, 1 (2,2,2-crypt = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo8.8.8]hexacosane) is the first well characterized seven-atom radical anion of group 15. UV-Vis spectroscopy confirms the presence and electronic structure of As-7](2-). Cyclic voltammetry in DMF solution shows the As-7(3) /As-7(2) redox couple as a one-electron reversible process. Theoretical investigations explore the bonding and properties of compound 1.

Bi2W1–xCuxO6–x(0.7[less-than-or-eq]x[less-than-or-eq]0.8): a new oxide-ion conductor

Anion-deficient Aurivillius phases of the general formula, Bi2Wi-xCuxO6-2x, possessing orthorhombic/tetragonal Bi2WO6-like structures, have been synthesized by quenching the oxide melts. The tetragonal phase stabilized for the compositions 0.7 less-than-or-equal-to x less-than-or-equal-to 0.8 is a good oxide-ion conductor in the temperature range 500-900 K, the x = 0.7 composition exhibiting the highest conductivity in the series.

Dielectric Relaxation Spectroscopy for Evaluation of the Influence of Solvent Dynamics on Ion Transport in Succinonitrile-Salt Plastic Crystalline Electrolytes

Influence of succinonitrile (SN) dynamics on ion transport in SN-lithium perchlorate (LiClO4) electrolytes is discussed here via dielectric relaxation spectroscopy. Dielectric relaxation spectroscopy (similar to 2 x 10(-3) Hz to 3 MHz) of SN and SN-LiClO4 was studied as a function of salt content (up to 7 mol % or 1 M) and temperature (-20 to +60 degrees C). Analyses of real and imaginary parts of permittivity convincingly reveal the influence Of trans gauche isomerism and solvent-salt association (solvation) effects on ion transport. The relaxation processes are highly dependent on the salt concentration and temperature. While pristine SN display only intrinsic dynamics (i.e., trans-gauche isomerism) which enhances with an increase in temperature, SN-LiClO4 electrolytes especially at high salt concentrations (similar to 0.04-1 M) show salt-induced relaxation processes. In the concentrated electrolytes, the intrinsic dynamics was observed to be a function of salt content, becoming faster with an increase in salt concentration. Deconvolution of the imaginary part of the permittivity spectra using Havriliak-Negami (HN) function show a relaxation process corresponding to the above phenomena. The permittivity data analyzed using HN and Kohlrausch-Williams-Watta (KWW) functions show non-Debye relaxation processes and enhancement in the trans phase (enhanced solvent dynamics) as a function of salt concentration and temperature.

Effect of Li+-ion on enhancement of photoluminescence in Gd2O3:Eu3+ nanophosphors prepared by combustion technique

Gd2O3:Eu3+ (4 mol%) nanophosphor co-doped with Li+ ions have been synthesized by low-temperature solution combustion technique in a short time. Powder X-ray diffractometer (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), UV-VIS and photoluminescence (PL) techniques have been employed to characterize the synthesized nanoparticles. It is found that the lattice of Gd2O3:Eu3+ phosphor transforms from monoclinic to cubic as the Li+-ions are doped. Upon 254 nm excitation, the phosphor showed characteristic luminescence D-5(0) -> F-7(J) (J= 0-4) of the Eu3+ ions. The electronic transition located at 626 nm (D-5(0) -> F-7(2)) of Eu3+ ions was stronger than the magnetic dipole transition located at 595 nm (D-5(0) -> F-7(1)). Furthermore, the effects of the Li+ co-doping as well as calcinations temperature on the PL properties have been studied. The results show that incorporation of Li+ ions in Gd2O3:Eu3+ lattice could induce a remarkable improvement of their PL intensity. The emission intensity was observed to be enhanced four times than that of with out Li+-doped Gd2O3:Eu3+. (C) 2010 Elsevier B.V. All rights reserved,

Solvation dynamics, energy distribution and trapping of a light solute ion

In the theoretical treatments of the dynamics of solvation of a newly created ion in a dipolar solvent, the self-motion of the solute is usually ignored. Recently, it has been shown that for a light ion the translational motion of the ion can significantly enhance its own rate of solvation. Therefore, solvation itself may not be the rate determining step in the equilibration. Instead, the rate determining step is the search of the low energy configuration which serves to localize the light ion. In this article a microscopic calculation of the probability distribution of the interaction energy of the nascent charge with the dipolar solvent molecules is presented in order to address this problem of solute trapping. It is found that to a good approximation, this distribution is Gaussian and the second moment of this distribution is exactly equal to the half of its own solvation energy. It is shown that this is in excellent agreement with the simulation results that are available for the model Brownian dipolar lattice and for liquid acetonitrile. If the distortion of the solvent by the ion is negligible then the same relation gives the energy distribution for the solvated ion, with the average centered at the final equilibrium solvation energy. These results are expected to be useful in understanding various chemical processes in dipolar liquids. Another interesting outcome of the present study is a simple dynamic argument that supports Onsager's ''inverse snow-ball'' conjecture of solvation of a light ion. A simple derivation of the semi-phenomenological relation between the solvation time correlation function and the single particle orientation, reported recently by Maroncelli et al. (J. Phys. Chem. 97 (1993) 13), is also presented.

ChemInform Abstract: Synthesis of Anion-Deficient Layered Perovskites, ACa2Nb3-xMxO10-x (A: Rb, Cs; M: Al, Fe), Exhibiting Ion-Exchange and Intercalation. Evidence for the Formation of Layered Brownmillerites, ACa2Nb2AlO9 (A: Cs, H)

Anion-deficient layered perovskite oxides of the formula, ACa2Nb3-xMxO10-x (A = Rb, Cs; M = Al, Fe) for 0 < x less-than-or-equal-to 1.0, possessing tetragonal structures similar to the parent ACa2Nb3O10, have been synthesized. The interlayer A cations in these materials are readily exchanged with protons in aqueous HNO3 to give the protonated derivatives, HCa2Nb3-xMxO10-x; the latter are solid Bronsted acids intercalating a number of organic amines including aniline (pK(a) = 4.63). The distribution of acid sites in the interlayer region of HCa2Nb2MO9 inferred from n-alkylamine intercalation suggests that oxygen vacancies and Nb/M atoms are disordered in the ACa2Nb2MO9 samples prepared at 1100-1200-degrees-C. Annealing a disordered sample of CsCa2Nb2AlO9 for a long time at lower temperatures tends to order the Nb/Al atoms and oxygen vacancies to produce octahedral (NbO6/2)-tetrahedral (AlO4/2)-octahedral (NbO6/2) layer sequence reminiscent of the brownmillerite structure.

Ionic conductivity, mechanical strength and Li-ion battery performance of mono-functional and bi-functional (''Janus'') ``soggy sand'' electrolytes

Influence of dispersion of uniformly sized mono-functional and bi-functional (''Janus'') particles on ionic conductivity of novel ``soggy sand'' electrolytes and its implications on mechanical strength and lithium-ion battery performance are discussed here.

AM(1-x)Al(x)O(3-x) (A=Na or K; M=Nb or Ta): New anion-deficient Perovskite oxides exhibiting oxide ion conduction

Anion-deficient perovskite oxides of the formula AM(1-x)Al(x)O(3-x) (A = Na or K; M = Nb or Ta) have been prepared for 0 < x less than or equal to 0.5. Diffraction experiments reveal that while the potassium compounds adopt orthorhombic/cubic perovskite structures similar to the parent KNbO3/KTaO3, the sodium compound, NaNb0.5Al0.5O2.5, possesses a brownmillerite/LaSr-CuAlO5-like superstructure. Al-27 NMR spectra show an exclusive tetrahedral oxygen coordination for AI(III) in Na-Nb0.5Al0.5O2.5 (I) and both tetrahedral and octahedral coordination for Al(III) in KNb0.5Al0.5O2.5 (II). The results suggest a long-range and short-range ordering of oxide ion vacancies in I and II respectively. Electrical conductivity measurements show a significant oxide ion conduction for KNb1-xAlxO3-x, with the conductivity increasing with x up to x = 0.5. The differences in the Arrhenius plots of the ionic conductivity of I and II have been rationalized in terms of the long-range and short-range ordering of oxide ion vacancies in the anion-deficient perovskite oxides.

Modulation of vesicular properties by variation of shapes of bolaform counter ions in hybrid-ion paired surfactants

Four new vesicle-forming bolaphile/amphiphile ion pairs are synthesized; the bolaphile shapes in such hybrid systems strongly control their vesicular properties.

Non-linear optical response of rutile-related oxides, LiM(V)M(VI)O(6), and their derivatives obtained by ion-exchange and intercalation

Polycrystalline samples of oxides of the general formula LiM(V)M(VI)O(6) (M(V) = Nb, Ta; M(VI) = Mo, W), crystallizing in a non-centrosymmetric (space group P (4) over bar 2(1)m) trirutile structure, exhibit second harmonic generation (SHG) of 1064 nm radiation with efficiencies 15-45 times that of alpha-quartz; interestingly, the SHG response is retained by the protonated derivatives HM(V)M(VI)O(6) . xH(2)O, and their n-alkylamine intercalates as well.

Non-Marcus energy gap dependence of electron transfer rate in contact ion pairs. Novel interplay between relaxation and reaction in solution

Electron transfer reactions between donor-acceptor pairs in solution and in organized media exhibit diverse behaviour. Recent experiments have indicated an interesting breakdown of the Marcus parabolic energy gap dependence in the normal regime for back electron transfer from contact ion pairs. A novel explanation of this breakdown has recently been proposed (M. Tachiya and S. Murata, J. Am. Chem. Sec., 116(1994) 2434) which attributes the breakdown to the interplay between the relaxation in the reactant well and the reaction. A particularly interesting aspect of the model is that it envisages the electron transfer in the normal regime to take place from a completely non-equilibrium condition. In this article a time dependent solution of the model is presented for the first time, after generalizing it to include a realistic initial population distribution. The decay of the contact ion pair population is completely non-exponential. This can be used to check the validity of the Tachiya-Murata model. The dynamics of electron transfer from the solvent separated ion pair, which seem to obey the Marcus relation, is exponential.

Solid Oxide-Ion Electrolytes

Solid oxide-ion electrolytes find application in oxygen sensors, oxygen pumps and in high-temperature electrolyser-fuel-cell hybrid systems. All the solid electrolytes known so Qr, however, exhibit: tow oxide-ion conductivities below 973 K. Therefore, there is a need for fast oxide-ion conductors operative at temperatures around 673 K, Recently, efforts have been directed towards developing such materials. This article summarizes various type of oxide-ton electrolytes reported in literature and outlines a strategy for the identificatiom/synthesis of improved materials.

Influence of carbide particles on the dynamic recrystallization of as-cast 304 stainless steel: a study using secondary ion mass spectrometric (SIMS) analysis

The domain of dynamic recrystallization (DRX) in as-cast 304 stainless steel material occurs at higher temperatures (1250 degrees C) and lower strain rates (0.001 s(-1)) than in wrought 304 stainless steel (1100 degrees C and 0.01 s(-1)). The above result has been explained earlier on the basis of a simple theoretical DRX model involving the rate of nucleation versus rate of grain boundary migration. The present investigation is aimed at examining experimentally the influence of carbide particles on the DRX of ascast 304 using secondary ion mass spectrometric (SIMS) analysis. Isothermal compression tests at a constant true strain rate have been performed on wrought 304 and as-cast 304 materials in the temperature and strain rate ranges of 1000 to 1250 degrees C and 0.001 to 1 s(-1) respectively. The SIMS analysis carried out on the deformed samples revealed that the large carbides present in the as-cast 304 material strongly influence the DRX process. In as-cast 304 material, the presence of large carbide particles in the microstructure shifts the DRX domain to higher temperature and lower strain rate in comparison with wrought 304 material.