Cluster self-organization of silicate and germanate systems: Suprapolyhedral precursor nanoclusters and self-assembly of tetrahedral structures of the family A2T2O5 (A = Li, Na; T = Si, Ge): Li2T2O5, Li4Ge3SiO10, Li2Si2O5, and A2Si2O5

Modeling of atomic species (An clusters in the form of atoms or Kn polyhedra, where n is the number of atoms or polyhedra) corresponding to the initial stage of evolution of a chemical system has been carried out. Three series of K4 clusters built of different T tetrahedra (L and T) have been recognized. For L₂T₂ clusters, six geometrically and symmetrically different types of suprapolyhedral clusters have been discovered. The model has been used to identify precursor clusters in A₂T₂O₅ (A = Li, Na; T = Si, Ge) framework structures: A-type Li₂T₂O₅ with space group Cc, B-type Li₄Ge₃SiO₁₀ with space group Abm2, C-type Li₂Si₂O₅ with space group Ccc2, and D-type A₂Si₂O₅ with space group Pbcn. Three (of the six possible) types of suprapolyhedral precursor nanoclusters K4 in the four structures have been identified. The full 3D reconstruction of the self-assembly scenario of crystal structures is as follows: precursor nanocluster ?? primary chain ?? microlayer ?? microframework ?? ?? framework. The bifurcation of structural evolution pathways (structural branching points) at the suprapolyhedral level for type A and B structures is found to occur only when a microframework is formed of equivalent microlayers.     

A study of the electronic structure of phenylsilanes by X-ray emission spectroscopy and quantum chemical calculation methods

The electronic structure of a series of phenylsilanes Ph_4?n SiH _n (n = 0?C3) is studied by X-ray emission spectroscopy and quantum chemical calculations by the density functional theory method. Based on the calculations theoretical X-ray emission SiK??₁ spectra of phenylsilanes Ph_4?n SiH _n (n = 0?C4) are constructed and their energy structure and shape turn out to be well consistent with experiment. The distribution of the electron density of states with different symmetry of Si, C, H atoms are also constructed. An analysis of the obtained X-ray fluorescent SiK??₁ spectra and the distribution of the electron density of states in Ph₄Si and Ph₃SiH compounds shows that their energy structure is mainly determined by a system of the energy levels of phenyl ligands weakly perturbed by interactions with valence AOs of silicon. In the energy structure of MOs of the PhSiH₃ compound, energy orbitals related to t ₂ and a ₁ levels of tetrahedral SiH₄ are mainly presented.     

The variation of viscosity, refractive indices, compressibility, intermolecular free length, and excess molar volume of the acetophenone—ethyl acetate solutions at 303.15–323.15 K

Densities, viscosities, refractive indices and ultrasonic velocities of the binary mixtures of acetophenone with ethyl acetate were measured over the entire mole fractions at 303.15, 313.15, and 323.15 K. From the experimental results, excess molar volumes V ^E, viscosity deviation ??_??, refractive index deviation ??n _D , deviations in isentropic compressibility ???? _s and excess intermolecular free length ??L _f are calculated. The viscosity values were fitted to the models of Krishnan-Laddha and McAllister. The thermophysical properties under study were fit to the Jouyban-Acree model. The excess values were correlated using Redlich-Kister polynomial equation to obtain their coefficients and standard deviations. The data obtained fitted with the values correlated by the corresponding models very well. The results are interpreted in terms of molecular interactions occurring in the solution.     

Cyclopentadienyl-functionalised polyhedral silsesquioxanes as building blocks for new nanostructured materials

This work is to design new organosilicon precursors, which contain both siloxane and cyclopentadienyl functionalities and use these compounds as building blocks for new nanomaterials. Polyhedral silsesquioxanes, (RSiO_1.5)_n (n = 8 and 10) with cyclopentadienyl (R = -C₅H₅ or -(CH₂)₃-C₅H₅) functionalities have been prepared by hydrolytic condensation of the correspondent silicon organic precursors RSiCl₃ or RSi(OC₂H₅)₃. The products with cyclopentadienyl groups have been used to prepare new cross-linked 3D polymeric materials by Diels-Alder reaction. The compounds have been characterised by multinuclear (¹H and ²⁹Si) NMR, ESI MS and IR spectroscopy, UV/Vis spectrometry, gel permeation chromatography and scanning electron microscopy. The approach above seems to be very promising for the preparation of new nanostructured materials.     

Values of p(Vm, T) for n-decane up to 300 MPa and 673 K

For n-decane (p, V_m, T) has been determined from 298 to 673 K and from atmospheric pressure to 300 MPa by measuring p(T) at constant molar volumes V_m from 190 to 1050 cm³·mol^?1. The experimental results are tabulated and represented by equations. Thermal pressure coefficients have been calculated.     

Picosecond spectroscopic measurement of very fast intersystem crossing for 9,10-dioxa-anti-bimanes

Picosecond spectroscopy, following the buildup of T₁ → T_n absorption (maximum at 420 nm), shows that the T₁ state of 1,5-diazabicyclo[3,3,0]octa-3,7-diene-2,6-diones(9,10-dioxa-anti-bimanes) is formed within about 10 ps. The nature of the T₁ state was confirmed by decay rates of T₁ → T_n absorption in acetonitrile (n = 0.375 cP, k_nr = 4.5 × 10⁵ s^?1), 1,2-ethanediol (n = 26 cP, k_nr = 1.5 × 10⁴ s^?1 and glycerol (n = 1400 cP, k_nr = 1.3 × 10³ s^?1). The very fast intersystem crossing is ascribed to the proximity of a ³nπ* state to the ππ* (S₁ state produced by light absorption (El-Sayed rule).     

Silicon-29 NMR studies of polymethylhydrosiloxanes: Spin-lattice relaxation time (T1) measurements

²⁹Si NMR spectra of polymethylhydrosiloxanes, Me₃SiO[MeHSiO]_nSiMe₃ from n = 3 to 8 and 35, have been determined. Both chemical shifts and spin-lattice relaxation times (T₁) have been measured. The stereochemistry at the adjacent chiral MeHSiO unit influences the nearest neighbor ²⁹Si chemical shift. The effect of chain length and position of MeHSiO units on T₁ values for Me₃SiO[MeHSiO]_nSiMe₃ systems are discussed.     

Absorption spectra of small niobium and gold clusters measured by photodepletion of their rare gas van der Waals complexes: some preliminary experiments

The optical absorption spectra of small niobium clusters have been determined over the wavelength range 260 – 740 nm by photodetaching Krypton atoms from the corresponding neutral van der Waals, vdW, complexes, Nb_nKr_m, n=5–15, m=1–3. Cross sections for small gold clusters were determined by photodetachment experiments oncharged vdW complexes [Au_nXe_m]⁺, m=1, 2. The absorption cross sections are observed to increase monotonically with decreasing wavelength. At the long wavelength end of the range, the cross section is practically independent of the cluster nuclearity, n; whereas, at the short wavelength end of the range, the cross section increases monotonically with n.     

Phase complex of the Li,K,Ba‖F,Br quaternary reciprocal system

The partition of the Li,K,Ba??F,Br quaternary reciprocal system into simplexes was performed and confirmed by X-ray powder diffraction. Internal partitioning elements, LiF-2KBr · BaBr₂ and KBr-LiF · BaF₂, were identified; the tree of phases forms two cycles. Simplexes involving phase separation were determined. The stable partitioning triangles LiF-KBr-BaBr₂ and LiF-KBr-BaF₂ · BaBr₂ were experimentally studied by differential thermal and X-ray powder diffraction analyses. The T-x diagrams of explored sections and the liquidi of the systems were constructed. Phase separation regions within the systems under investigations were delimited. The characteristics of alloys corresponding to invariant compositions were determined.     

Multiple collisions in molecular beam scattering experiments

Due to the forward peaked differential cross section for elastic atom—atom scattering the effect of multiple collisions has to be considered in the analysis of crossed beam measurements of the total cross section and especially of the small angle differential cross section at large values of the beam attenuation. At angles θ ≈ θ₀, with θ₀ the quantum mechanical scaling angle of the elastic differential cross section, the correction for the latter case amounts to 20% at beam attenuations I/I₀ = exp(?1). Firstly, a careful analysis of the probabilities for single and multiple scattering is given, resulting in an expression for the measured beam signals which is correct for all values of the beam attenuation. The probability for multiple scattering is then calculated for an inverse power potential V(r) = ?C_sr^?s, with s = 4 through s = 7, which include both the case of ion—atom scattering (s = 4) and atom—atom scattering (s = 6). The results are given as effective differential cross sections σ_n(θ) for n-fold scattering. They are described by a single, simple analytical function with four free parameters that have been determined for n = 2, 3 and 4 by a least squares method. The σ_n(θ) are normalised to the total cross section Q.     

Effect of tetra-n-alkylammonium bromides on the volumetric properties of glycine,l-alanine and glycylglycine at T=298.15 K

The effect of tetra-n-alkylammonium bromides, R₄NBr (R=CH₃, C₂H₅, C₄H₉) on the densities, ρ, of glycine, l-alanine and glycylglycine are reported at T=298.15 K. The apparent molar volumes of amino acids in aqueous tetra-n-alkylammonium salts, φ_VAJW, and of tetra-n-alkylammonium bromides in aqueous amino acids and peptide, φ_VJAW, are calculated from the measured densities. Both φ_VAJW and φ_VJAW have been analysed accurately using a simple equation. Positive transfer volumes are observed for glycine, l-alanine and glycylglycine in the presence of R₄NBr. Tetra-n-butylammonium bromide shows almost double increase in the transfer volumes of amino acids or peptide than tetramethyl- or tetraethylammonium bromides. Negative transfer volumes for the tetra-n-alkylammonium bromide salts are noted in aqueous amino acids or peptide due to large tetra-n-alkylammonium cation undergoing hydrophobic hydration.     

Energy dependence of the cross section for alkali—methyl iodide reactions

The dependence of the reaction cross section for all the alkali—methyl iodide reactions on the translational energy in the range E_T = 0–40 kcal/mole has been discussed in an idealized collision model of hard-sphere interaction between colliding particles. In all reaction of the family, the cross section increases sharply with E_T showing an Arrhenius-like positive energy dependence for E_T just past threshold and then takes a maximum value. The maximum value is largest for the Cs reaction and decreases with the alkali mass except that it slightly increases from Rb to K, and the peak becomes broader as the mass decreases. In the post-maximum region the cross section decreases slowly with E_T.     

Mobilities of thermal cations in oxygen gas: Temperature dependence

Cation mobilities, μ, in oxygen were measured at fields E/n < 4Td, 103 ⩽ T/K ⩽ 594 and 2.53 ⩽ n / 10²⁴ molecule m^-3 ⩽ 7.94. At T < 300 K the density normalized mobility nμ agreed with previous values for O⁺₄. At T > 300 K, nμ increased with increasing T, and at > 350 K became larger than nμ for O⁺₂ in O₂ reported in the literature. The energy dependence of the momentum transfer cross section σ_m was estimated both for O⁺₄ and O⁺₂ in O₂. At ε < 0.01 eV both σ_m sets were merged into the polarization cross section σ_pol for O₂. At ε > 0.1 eV, σ_m (O⁺₂-O₂) > σ_m (O⁺₄-O₂).     

Apparent molar volumes,heat capacities,and molecular excluded volumes of methylated,hydroxy and methoxy derivatives of 1-methylcytosine in aqueous solutions at 25°C

Densities and specific heat capacities of aqueous solutions: 1-methylcytosine; 1-methyl-N⁴-hydroxycytosine; 1,5-dimethylcytosine; I,N⁴-dimethylcytosine; 1,5-dimethyl-N⁴-hydroxycytosine; 1-methyl-N⁴-methoxycytosine; 1,N⁴,N⁴-trimethylcytosine, 1,5-dimethyl-N⁴-methoxycytosine were determined using flow calorimetry and flow densimetry at 25°C. Apparent molar volumes and heat capacities were then determined. Molecular excluded volumes were evaluated. A relationship was found between the values of the increments in partial molar values and the kind of groups substituted. Four types of contributions were distinguished: substitution of hydrogen on C, N, and O (in OH group on N4) atoms by CH₃ group and replacement of hydrogen on N4 atom by OH group. The correlation between the experimental partial molar volumes and calculated molecular excluded volumes was also elaborated.     

Three-dimensional configurations of organic/inorganic hybrid nanostructural blocks (I). A quantum mechanical investigation for ladder-like structure of vinylsilsesquioxane

Silsesquioxanes (SSO) or polyhedral oligomericsilsesquioxanes (POSS) are generally prepared frommolecular precursors using the hydrolytic condensa-tion of trialkoxysilane, RSi(OR')3. They are organic/inorganic hybrid nanostructural blocks with theircomplete general formula Tn(T = RSiO1.5, n = 1,2, …), and the incomplete generic formula is Tn-(OH)x(OR')y[x, y = 0, 1, 2, …, T= RSiO1.5 ?(x+y)/2n][1,2].Each VSSO, possessing a certain structural formulaand molecular weight, may h…     

Thermochemistry of hydride and phenyl groups on the surface of amorphous silicon dioxide

The thermodynamic properties of hydride and phenyl groups on the surface of amorphous silicon dioxide are investigated in the presented work. The characteristics of the surface silane centers (SiH) are determined from the data obtained by infrared spectroscopy and caloric measurements. The conversions of hydrogen and benzene with the surface are described by thermodynamic calculations at reactions take place in the gaseous phase.To model the reaction between hydrogen and the surface the thermodynamic data for (OH)_4−nSi_n (n=0-4) in the gaseous phase are used. The surface groups and the model molecules are comparable because the thermodynamic characteristics depend only from the local environment.The thermodynamic properties of (OH)₃SiC₆H₅ in the gaseous phase are determined to describe the reaction between benzene and the surface. The predications of these calculations are confirmed by the spectroscopic results. The properties of the surface phenyl groups (SiC₆H₅) are concluded from these data.     

Heterophase synthesis of polymeric organosilanes

A new procedure was suggested for preparing polymeric organosilanes and silanosiloxanes without using a dispersion of an alkali metal in an organic solvent. The procedure allows preparation of linear organopolysilanes —(R₂Si) _n —, whereas reactions of methyl-, phenyl-, and n-hexyltrichlorosilanes with Na/NaCl yield silanosiloxane derivatives [(RSi) _x (RSiO _y ].     

On the Use of Monolithic Sol–Gel Derived Mesoporous Silica for the Calibration of Thermoporisemetry Using Various Solvents

Sol–gel derived mesoporous monolithic silica gels have been prepared to be used as standard materials for thermoporosimetry. The technique has been calibrated with n-heptane and cyclohexane and R _p = f(Δt) and W _a = f(ΔT) expressions are derived. In the specific case of cyclohexane, the solid to solid phase transition has been used. It is also shown that porous volumes can be measured by thermoporosimetry and that the correlation with N₂ gas sorption results is very good. Finally, thermoporosimetry has been applied to the study of cross linking level in polyisoprene samples containing a gradient of cross linking agent.     

Excess Molar Volumes of Oligo(Oxyethylene Glycol) Monodecyl Ethers in n-Dodecane, and Apparent Dipole Moments of {(Oligo(Oxyethylene Glycol) Monodecyl Ethers?+?n-Heptane, n-Decane or n-Dodecane} at T?=?298.15?K

Excess molar volumes and relative permittivities at a frequency of 30?kHz of oligo(oxyethylene glycol) monodecyl ethers (C₁₀E _m ) for m?=?1?C8 in n-heptane, n-decane or n-dodecane solutions were determined for the mole fraction range 0?<?x?<?0.04 at the temperature of 298.15?K. By using Frohlich??s equation the apparent dipole moments, ??, of C₁₀E _m were calculated, and the limiting values, ?? ₀, were determined by extrapolating to infinite dilution. The values of ?? ₀ increase linearly with increasing number of oxyethylene units (m) of oligo(oxyethylene glycol) monodecyl ethers in the range m?=?2?C8, while ?? ₀ of C₁₀E₁ is less than its extrapolated value. By comparing the present results with our previous ones measured in n-heptane and decane, a solvent effect on ?? ₀ was found. The excess partial molar volumes of oligo(oxyethylene glycol) monodecyl ethers at infinite dilution increase with increasing m. Those results are discussed from the viewpoint of the interactions between oligo(oxyethylene glycol) monodecyl ethers and solvent molecules.