Photolysis of alkaline-earth nitrates

Peroxynitrite and nitrite ions are the diamagnetic products of photolysis (with light at a wavelength of 253.7 nm) of alkaline-earth nitrates; the paramagnetic products and hydrogen peroxide were not found. The structural water in alkaline-earth nitrate crystals did not affect the qualitative composition of the photodecomposition products. The quantum yield of nitrite ions was 0.0012, 0.0038, 0.0078, and 0.0091 quanta^?1 and that of peroxynitrite ions was 0.0070, 0.0107, 0.0286, and 0.0407 quanta^?1 for Sr(NO₃)₂, Ba(NO₃)₂, Ca(NO₃)₂ · 4H₂O, and Mg(NO₃)₂ · 6H₂O, respectively.     

Blue photoluminescence in Ti-doped alkaline-earth stannates

Blue photoluminescence properties of Ti-doped alkaline-earth stannates, A₂(Sn_1−xTi_x)O₄ (A=Ca, Sr, Ba) (x=0.005-0.15), were examined at room temperature. These stannates showed intense broad emission bands peaking at 445 nm for Ca₂SnO₄, at 410 nm for Sr₂SnO₄, and at 425 nm for Ba₂SnO₄ under UV excitation. Emission intensities were relatively insensitive to Ti concentration and no sharp concentration quenching was observed. Mixing alkaline-earth ions in the crystal structures did not increase the emission intensities in the A₂(Sn_1−xTi_x)O₄ system. The excitation spectra of these stannates exhibited broad bands just below the fundamental absorption edges, implying that luminescence centers do not consist of the component elements in the host materials. It was suggested that the isolated TiO₆ complexes are possible luminescence centers in these materials, as previously proposed in other Ti-doped stannates such as Mg₂SnO₄ and Y₂Sn₂O₇.     

Improvement of thermoelectric properties of alkaline-earth hexaborides

Thermoelectric (TE) and transport properties of alkaline-earth hexaborides were examined to investigate the possibility of improvement in their TE performance. As carrier concentration increased, electrical conductivity increased and the absolute value of the Seebeck coefficient decreased monotonically, while carrier mobility was almost unchanged. These results suggest that the electrical properties of the hexaboride depend largely on carrier concentration. Thermal conductivity of the hexaboride was higher than 10 W/m K even at 1073 K, which is relatively high among TE materials. Alloys of CaB₆ and SrB₆ were prepared in order to reduce lattice thermal conductivity. Whereas the Seebeck coefficient and electrical conductivity of the alloys were intermediate between those of CaB₆ and SrB₆ single phases, the thermal conductivities of the alloys were lower than those of both single phases. The highest TE performance was obtained in the vicinity of Ca_0.5Sr_0.5B₆, indicating that alloying is effective in improving the performance.     

Metal–metal bonded alkaline-earth distannyls

The first families of alkaline-earth stannylides [Ae(SnPh₃)₂·(thf)_x] (Ae = Ca, x = 3, 1; Sr, x = 3, 2; Ba, x = 4, 3) and [Ae{Sn(SiMe₃)₃}₂·(thf)_x] (Ae = Ca, x = 4, 4; Sr, x = 4, 5; Ba, x = 4, 6), where Ae is a large alkaline earth with direct Ae–Sn bonds, are presented. All complexes have been characterised by high-resolution solution NMR spectroscopy, including ¹¹⁹Sn NMR, and by X-ray diffraction crystallography. The molecular structures of [Ca(SnPh₃)₂·(thf)₄] (1′), [Sr(SnPh₃)₂·(thf)₄] (2′), [Ba(SnPh₃)₂·(thf)₅] (3′), 4, 5 and [Ba{Sn(SiMe₃)₃}₂·(thf)₅] (6′), most of which crystallised as higher thf solvates than their parents 1–6, were established by XRD analysis; the experimentally determined Sn–Ae–Sn′ angles lie in the range 158.10(3)–179.33(4)°. In a given series, the ¹¹⁹Sn NMR chemical shifts are slightly deshielded upon descending group 2 from Ca to Ba, while the silyl-substituted stannyls are much more shielded than the phenyl ones (δ¹¹⁹Sn/ppm: 1′, −133.4; 2′, −123.6; 3′, −95.5; 4, −856.8; 5, −848.2; 6′, −792.7). The bonding and electronic properties of these complexes were also analysed by DFT calculations. The combined spectroscopic, crystallographic and computational analysis of these complexes provide some insight into the main features of these unique families of homoleptic complexes. A comprehensive DFT study (Wiberg bond index, QTAIM and energy decomposition analysis) points at a primarily ionic Ae–Sn bonding, with a small covalent contribution, in these series of complexes; the Sn–Ae–Sn′ angle is associated with a flat energy potential surface around its minimum, consistent with the broad range of values determined by experimental and computational methods.

The complete series of heterobimetallic alkaline-earth distannyls [Ae{SnR₃}₂·(thf)_x] (Ae = Ca, Sr, Ba) have been prepared for R = Ph and SiMe₃, and their bonding and electronic properties have been comprehensively investigated.     

Electrophysical properties of titanates of alkaline-earth metals

Results on oxygen-ion, electron, and proton conduction and oxygen penetrability of titanates of alkaline-earth metals doped with acceptor admixtures are briefly reviewed. The applicability of these materials in electrochemical devices, in particular, as oxygen-penetrable membranes, is considered. The focus is on the studies carried out at the Institute of High-Temperature Electrochemistry, Ural Branch, Russian Academy of Sciences.     

Synthesis of first representatives of alkaline-earth metal diselenophosphinates

A three-component reaction between secondary phosphines, elemental selenium, and calcium or barium hydroxides in a molar ratio of 1: 2: 0.5 proceeds under mild conditions (70?C75 °C, 10 min, aqueous ethanol) to give previously unknown Ca and Ba diselenophosphinates (78?C89%).     

High-voltage electroconduction in molten chlorides of alkaline-earth metals

Effects of high-voltage pulses on electroconduction of molten chlorides of alkaline-earth metals and their mixtures with potassium chloride are studied experimentally. It is established that the electroconductivity of the melts subjected to the pulses increases proportionally to the voltage amplitude and the number of activating pulses in a pulse series. Oscillatory relaxation of nonequilibrium melts is discovered.     

Valence p functions for alkali and alkaline-earth atoms

Contracted Gaussian-type function (CGTF) basis sets are reported for valence p orbitals of the six alkali and alkaline-earth atoms Li, Be, Na, Mg, K, and Ca for molecular applications. These sets are constructed by Roothaan–Hartree–Fock calculations for the ns → np excited states of atoms, in which both linear and nonlinear parameters of CGTFs are variationally optimized. The present CGTF sets reproduce well the numerical Hartree–Fock ns → np excitation energies: the largest error is 0.0009 hartrees for Li. New CGTFs are tested with diatomic Li₂, Na₂, K₂, and MH molecules, where M = Li, Be, Na, Mg, K, and Ca, by self-consistent-field (SCF) and multiconfiguration SCF calculations. The resultant spectroscopic constants compare well with those of more elaborate calculations and are sufficiently close to experimental values, supporting the efficiency of the present set for the valence p orbitals. Received: 9 July 1998 / Accepted: 17 September 1998 / Published online: 1 February 1999     

Mixed-ligand complexes of alkaline-earth metal trifluoroacetates with monoethanolamine

The mixed-ligand complexes of the formula [M(CF₃COO)₂(MEA) _n ] (MEA is monoethanolamine; M = Ca (I) and Sr (II), n = 1.5; M = Ba (III), (n = 1) were obtained from appropriate salts M(CF₃COO)₂ · nH₂O and MEA in ethanol. Complexes I–III were characterized by elemental analysis data and IR spectra. Slow crystallization of a solution of complex III in air gave a single crystal of the formula [Ba(CF₃COO)₂(MEA)(H₂O)], which is a coordination polymer with C.N.(Ba) 9 (X-ray diffraction data). Thermal analysis showed that complexes I–III decompose under argon and in air to the corresponding fluorides at T < 400°C.     

Gas-phase formation of large neutral alkaline-earth metal tryptophan complexes

We report on the first observation of isolated large neutral metal amino acid complexes such as Trp(n)Me(k), with Me=Ca, Ba, Sr, cluster combinations covering n=1...33, k=0..2 and masses beyond 6500 u. The cluster beam is generated using UV laser desorption from a mixed powder of alkaline-earth metal salts and tryptophan inside a cluster mixing channel. The particles are detected using VUV photoionization followed by time-of-flight mass spectroscopy. The enhanced stability of metal amino acid clusters over pure amino acid clusters is substantiated in molecular dynamics simulations by determining the gain in binding energy related to the inclusion of the metal atoms.     

Optical properties of alkaline-earth metal oxides from first principles

This study reports the results of an ab initio electronic and optical calculation of alkaline-earth metal oxides (MgO, CaO, SrO and BaO) in the NaCl crystal structure using the full potential linearized augmented plane wave (FP-LAPW) method within the density functional theory. The exchange-correlation potential is treated by the generalized gradient approximation within the Perdew et al scheme. Moreover, the Engel–Vosko GGA formalism is applied so as to optimize the corresponding potential for band structure calculations. The real and imaginary parts of the dielectric function ?(ω), the optical absorption coefficient I(ω), the reflectivity R(ω) and the energy loss function are calculated by random phase approximation (RPA). The calculated results show a qualitative agreement with the available experimental results in the sense that we can recognize some peaks qualitatively, those due to single particle transitions. Furthermore the interband transitions responsible for the structures in the spectra are specified. It is shown that the oxygen 2p states and metal d states play the major role in optical transitions as initial and final states respectively. The effect of the spin–orbit coupling on the optical properties is also investigated and found to be quite small, especially in the low energy region. The dielectric constants are calculated and compared with the available theoretical and experimental results.     

79Br nuclear quadrupole resonance in some alkaline-earth bromides

Theoretical and Experimental Chemistry -     

Thermal decomposition of alkaline-earth carbonate samples of extreme thickness

Forward and reverse reactions were studied of the type MCO₃ = MO+CO₂, (M = Mg, Ca, Sr and Ba). The samples were of three types: (1) thick (some mm) crystals; (2) powders; (3) thin layers (about 10 nm).Pressure—temperature data of the reactions are reported from the point of view of reversibility and equilibrium. The effect of repeated isothermal reaction cycles resulted in decreasing conversion of CO₂ uptake.Isothermal and non-isothermal thermal measurements were completed with studies on an electron microprobe analyzer to explain the results.