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The status of theory and experiment for the determination of the CO vibrational frequencies in binary unsaturated transition metal carbonyl cations, neutrals and anions is reviewed.
Until 1989, ion chromatography (IC) was the baseline technology selected for the Specific Ion Analyzer, an in-flight inorganic water quality monitor being designed for Space Station Freedom. Recent developments in capillary electrophoresis (CE) may offer significant savings of consumables, power consumption, and weight/volume allocation, relative to IC technology. A thorough evaluation of CE's analytical capability, however, is necessary before one of the two techniques is chosen. Unfortunately, analytical methods currently available for inorganic CE are unproven for NASA's target list of anions and cations. Thus, CE electrolyte chemistry and methods to measure the target contaminants must be first identified and optimized. This paper reports the status of a study to evaluate CE's capability with regard to inorganic and carboxylate anions, alkali and alkaline earth cations, and transition metal cations. Preliminary results indicate that CE has an impressive selectivity and trace sensitivity, although considerable methods development remains to be performed.
Understanding of chemical properties of monovalent transition metal cations in aqueous solutions was obtained by a study of kinetics of reduction of different inorganic substrates by zinc, cadmium, and nickel.
The optimization of the geometry and calculation of zero-point energies are carried out at the B3LYP level of theory. The bond energies are determined at this level, as well as at the CCSD(T) level using very large basis sets. The successive OH bond energies to the first row transition metal cations are reported. For most systems there has been an experimental determination of the first OH. In general, the CCSD(T) values are in good agreement with experiment. The bonding changes from mostly covalent for the early metals to mostly electrostatic for the late transition metal systems.
The geometries of the molecules formed by the interaction of the first- and second-row transition-metal cations with methylene are optimized at the modified coupled-pair functional (MCPF) level of theory using large Gaussian basis sets, and their dissociation energies are computed employing both the MCPF and internally contracted averaged coupled-pair functional (ICACPF) methods. The computed binding energies are generally in good agreement with the available experimental results, although the calculations indicate that the experimental values for ScCH2(+), TiCH2(+), and NbCH2(+) are probably too large. The nature of the bonding in each case and trends in the bonding patterns across the transition-metal rows are discussed.
Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.
Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.
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The electrical conductivity sigma of MgO single crystals shows a sharp increase at 500-800 C, in particular of sigma surface, generally attributed to surface contamination. Charge Distribution Analysis (CDA), a new technique providing information on fundamental properties that was previously unavailable, allows for the determination of surface charges, their sign and associated internal electric field. Data on 99.99% purity, arc-fusion grown MgO crystals show that mobile charge carriers start to appear in the bulk of the MgO crystals between 200 and 400 C when sigma (measured by conventional techniques) is in t he 10(exp -14) to 10(exp -16) /omega/cm range. Above 500 C, as sigma increases to 10(exp -6) to 10(exp -7)/omega/cm, more charges appear giving rise to a strong positive surface charge supported by a strong internal field. This indicates that charges are generated in the bulk and diffuse to the surface by an internally controlled process. On the basis of their positive sign they are identified as holes (defect electrons). Because of the low cation content of these very pure MgO crystals, theses holes cannnot be associated with transition metal impurties. Instead, they are associated with the O(2-) sublattice, e.g. consist of O(-) states or positive holes. This conclusion is supported by magnetic susceptibility data showing the appearance of 1000 +/- 500 ppm paramagnetic species between 200-500 C. The magnetic data are consistent with strongly coupled, diamagnetic O(-) pairs below 200-500 C, chemically equivalent to peroxy anions, O2(2-), and probably associated with cation vacancies in the MgO matrix. The formation of O2(2-) in arc-fusion grown MgO crystals is very unexpected because of the highly reducing growth conditions. Their presence implies an internal redox reaction involving dissolved 'water' by which OH(-) pairs convert to O2(2-) plus H2 molecules. This redox conversion is supported by mass spectroscopic measurements of the H2 release from highly OH(-)-doped, finely divided MgO and by wet-chemical analysis of its oxidant concentration.
The atom superposition and electron delocalization molecular orbital theory and large cluster models have been employed to study cation vacancy diffusion in alpha-Al2O3 and the bonding of alpha-Al2O3 to nickel, aluminum, and yttrium surfaces. Al(3+) diffusion barriers in alpha-Al2O3 by the vacancy mechanism are in reasonable agreement with experiment. The barrier to Y(3+) diffusion is predicted to be much higher. Since addition of yttrium to transition metal alloys is known to reduce the growth rate and stress convolutions in protective alumina scales, this result suggests the rate-limiting step in scale growth is cation vacancy diffusion. This may partially explain the beneficial effect of yttrium dopants on scale adhesion. The theory also predicts a very strong bonding between alumina and yttrium at the surface of the alloy. This may also be important to the adhesion phenomenon. It is also found that aluminum and yttrium atoms bond very strongly to nickel because of charge transfer from their higher lying valence orbitals to the lower lying nickel s-d band.
The present invention includes compositions, surface and bulk modifications, and methods of making of (1-x)Li[Li.sub.1/3Mn.sub.2/3]O.sub.2.xLi[Mn.sub.0.5-yNi.sub.0.5-yCo.sub.2- y]O.sub.2 cathode materials having an O3 crystal structure with a x value between 0 and 1 and y value between 0 and 0.5, reducing the irreversible capacity loss in the first cycle by surface modification with oxides and bulk modification with cationic and anionic substitutions, and increasing the reversible capacity to close to the theoretical value of insertion/extraction of one lithium per transition metal ion (250-300 mAh/g).
Prominent bands in the spectral profiles of Fe-Ti phases in lunar samples have been attributed to charge-transfer transitions between Fe and Ti cations, and a model is presented for calculating charge transfer energies from energy levels computed by the SCF-X(alpha) scattered wave molecular orbital method for isolated MO6 octahedral coordination clusters containing Fe(2+), Fe(3+), Ti(3+), and Ti(4+) cations. The calculated charge transfer energy for the Fe(2+) to Ti(4+) transition correlates well with a measured spectral feature around 0.6 micron in ilmenite, and, since ilmenite is a major constituent of mare basalts and dark-mantling material, the observed darkness and blueness of the regolith in lunar black spots is attributed primarily to this transition. The Ti(3+) to Ti(4+) transition is thought to contribute to some phases.
Ion-exchange membrane metallic composites (IPMC), which were first reported in 1992, are one of the electroactive materials (EAP) with potential applications as artificial muscle actuators. The recent introduction of perfluorocarboxylate-gold composite with tetra-n-butylammonium and Lithium cations instead of sodium made the most significant improvement of the material electroactivity. Under less than 3 volts, IPMC with the new constituents is capable of bending beyond a complete loop. Taking into account the fact that IMPC materials do not induce a significant force, the authors are extensively seeking applications for these bending EAP. Some of the applications that were demonstrated include dust-wiper, catheter guide, miniature motor, robotic-gripper, micro-manipulator, etc. Generally, space applications are the most demanding in terms of operating conditions, robustness and durability, and the co-authors of this paper are jointly addressing the associated challenges. Specifically, a dust-wiper is being developed for the Nanorover's infrared camera window of the MUSES-CN mission. This joint NASA and the Japanese space agency mission, is scheduled to be launch from Kagoshima, Japan, in January 2002, to explore the surface of a small near-Earth asteroid. Several issues that are critical to the operation of IPMC are addressed including the operation in vacuum, low temperatures, and the effect of the electromechanical characteristic of the IPMC on its actuation capability. Highly efficient IPMC materials, mechanical modeling, unique elements and protective coating were introduced by the authors and are making a high probability the success of the IPMC actuated dust-wiper.
The characteristics of cation vacancies and site occupancies of natural hibonites in meteors are discussed. Note is taken of the effect of the specific locations of the hibonites in the matrices on the crystal chemistry, electronic stabilities, and spectral features of the metal ions which replace the Al(3+). Hibonites form beta-alumina hexagonal cells with 26 cation sites. Fe cations are found in octahedral, tetrahedral, and five-fold coordinates. Fe(2+) is found in face-shared Al(3) octahedra, a siting explained in terms of ionic radius and crystal field stabilization energy criteria. Spectral colors are attributed to V(3+) and Ti(3+) field transitions at 400 and 700 nm, respectively, although the 700 nm line may arise from transitions of Ti(3+) to Ti(4+) or Fe(2+) to Fe(3+) during heating. Excesses of Mg-26 can be traced to decay of nebular Al-26.
The characteristics of cation vacancies and site occupancies of natural hibonites in meteors are discussed. Note is taken of the effect of the specific locations of the hibonites in the matrices on the crystal chemistry, electronic stabilities, and spectral features of the metal ions which replace the Al(3+). Hibonites form beta-alumina hexagonal cells with 26 cation sites. Fe cations are found in octahedral, tetrahedral, and five-fold coordinations. Fe(2+) is found in face-shared Al(3) octahedra, a siting explained in terms of ionic radius and crystal field stabilization energy criteria. Spectral colors are attributed to V(3+) and Ti(3+) field transitions at 400 and 700 nm, respectively, although the 700 nm line may arise from transitions of Ti(3+) to Ti(4+) or Fe(2+) to Fe(3+) during heating. Excesses of Mg-26 can be traced to decay of nebular Al-26.
The role of divalent cations in the mechanism of pyrophosphate-activated, template-directed oligoribonucleotide ligation has been investigated. The dependence of the reaction rate on Mg2+ concentration suggests a kinetic scheme in which a Mg2+ ion must bind before ligation can proceed. Mn2+, Ca2+, Sr2+, and Ba2+ can also catalyze the reaction. Although Pb2+ and Zn2+ do not catalyze the reaction in the absence of other divalent ions, they significantly modulate the reaction rate when added in the presence of Mg2+, with Pb2+ stimulating the reaction (up to 65-fold) and Zn2+ inhibiting the reaction. The logarithm of the ligation rate increases linearly, with slope of 0.95, as a function of pH, indicating that the reaction involves a single critical deprotonation step. The ligation rates observed with the different divalent metal ion catalysts (Mn2+ > Mg2+ > Ca2+ > Sr2+ = Ba2+) vary inversely with the pKa values of their bound water molecules. The pH profile and these relative ligation rates suggest a mechanism in which a metal-bound hydroxide ion located near the ligation junction promotes catalysis, most likely by deprotonation of the hydroxl nucleophile. The effects of changing either the leaving group or the attacking hydroxyl, together with the large delta S(++) value for oligonucleotide ligation (about -20 eu), are consistent with an associative transition state.
The electrical, magnetic, and optical properties of charge-transfer salts containing tetrathiafulvalene (TTF) and the pseudohalides, thiocyanate (SCN) and selenocyanate (SeCN), have been investigated. These salts are quasi-one-dimensional compounds containing cation radicals only, in contrast to a cation-radical-anion-radical system, such as tetrathiafulvalene tetracyanoquinodimethane (TTF) (TCNQ). Measurements of electrical conductivity, thermoelectric power, and optical reflectivity of single crystals of the nonstoichiometric salts (TTF)12(SCN)7 and (TTF)12(SeCN)7 show metal-like characteristics above 200 K (high-temperature region). The conductivities at room temperature are approximately 750 mho/cm comparable to those found in (TTF) (TCNQ), and increase with decreasing temperature down to approximately 200 K. The thermoelectric power at room temperature is small and positive (approximately 9 microvolts/deg K), and decreases linearly with decreasing temperature in this region (as expected for metal-like hole conduction along the TTF chains). The ESR intensity, however, decreases with decreasing temperature above 200 K. At 170 K a metal-nonmetal transition occurs, and the transport and magnetic properties below this temperature are characteristic of a semiconducting state.