Synthesis, crystal structure and mono-dimensional thallium ion conduction of TlFe0.22Al0.78As2O7

A new solid solution TlFe_0.22Al_0.78As₂O₇ has been synthesized by a solid-state reaction. The structure of the title compound has been determined from a single-crystal X-ray diffraction and refined to final values of the reliability factors: R(F²)=0.030 and wR(F²)=0.081 for 1343 independent reflections with I>2σ(I). It crystallizes in the triclinic space group P-1, with a=6.296(2) Å, b=6.397(2) Å, c=8.242(2) Å, α=96.74(2)°, β=103.78(2)°, γ=102.99(3)°, V=309.0(2) Å³ and Z=2. The structure can be described as a three-dimensional framework containing (Fe/Al)O₆ octahedra connected through As₂O₇ groups. The metallic units and diarsenate groups share oxygen corners to form a three-dimensional framework with interconnected tunnels parallel to the a, b and c directions, where Tl⁺ cations are located. The ionic conductivity measurements are performed on pellets of the polycrystalline powder. At 683 K, The conductivity value is 5.23×10⁻⁶ S cm⁻¹ and the ionic jump activation energy is 0.656 eV. The bond valence analysis reveals that the ionic conductivity is ensured by Tl⁺ along the [001] direction.     

Vibrational frequencies and structural determination of phosphirane

The normal mode frequencies and corresponding vibrational assignments of phosphirane in are examined theoretically using the GAUSSIAN 98 set of quantum chemistry codes. All normal modes were successfully assigned to one of nine types of motion (C–C stretch, P–C stretch C–H stretch, P–H stretch, CH₂ scissors, CH₂ wag, CH₂ rock, CH₂ twist, and P–H wag) predicted by a group theoretical analysis. Comparing the vibrational frequencies with IR and Raman spectra available in the literature, a set of scaling factors are derived. Predicted infrared and Raman intensities are reported.     

Cis- and trans-3-hexene: infrared spectrum in liquid argon solution, ab initio calculations of equilibrium geometry, normal coordinate analysis, and vibrational assignments

The infrared spectra of cis-3-hexene and trans-3-hexene dissolved in liquid argon have been obtained at temperatures from 93 to 120 K. The absorptions were observed with a low-temperature cell and a Fourier transform infrared spectrophotometer. Ab initio molecular orbital calculations were performed to obtain the equilibrium geometry, vibrational frequencies, force fields, and infrared intensities. The calculations were done at the Hartree-Fock level using 6-31G basis set. The Cartesian force fields from ab initio calculations have been converted to the force field in symmetry coordinates. The scale factors of ab initio calculated force fields were determined. Normal coordinate calculations were performed using a scaled quantum mechanical (SQM) force field. Vibrational normal modes calculated for the lowest energy rotamers of cis- and trans-3-hexene have been assigned to infrared absorption bands observed in liquid argon solution. The assignments were based on calculated frequencies and potential energy distributions. The equilibrium geometries of the two lowest energy rotamers (symmetry C₂ and C_s) of cis-3-hexene and of the three lowest energy rotamers (symmetry C_i, C₂, and C₁) of trans-3-hexene were calculated. Variable temperature studies of the infrared spectrum of cis- and trans-3-hexenes dissolved in liquid argon were done to obtain the ΔH of conversion between the rotamers C₂ and C_s of cis-3-hexene and between the rotamers C_i, C₂, and C₁ of trans-3-hexene.     

The MPE/UCB far-infrared imaging Fabry-Perot interferometer (FIFI)

FIFI is an imaging spectrometer with two or three Fabry-Perot interferometers (FPI) in series for airborne astronomical observations in the far-infrared range (=40...200m). It employs 5×5 arrays of photoconducting detectors and offers spectral resolutions as small as 2km/s. Resolution and bandwidth can be set over a wide range to match a variety of astronomical sources. Cryogenic optics minimizes thermal background radiation and provides for in-flight step tunable spatial resolution. At 158 m wavelength the background-limited NEP is 3 × 10^-15W/Hz at 40 km/s resolution and with two FPI's; with three FPI's the expected NEP is 10^-15WHz at 5 km/s resolution.The frequency-chopping mode of the high-resolution Fabry-Perot allows for line detection in extended objects. Absolute internal flux calibration ensures adequate flat fielding of the array elements.     

Photoinduced rotational isomerization mechanism of 2-chlorobenzaldehyde in low-temperature rare-gas matrices by vibrational and electronic spectroscopies

Rotational isomerization of 2-chlorobenzaldehyde in low-temperature rare-gas matrices has been investigated by vibrational and electronic spectroscopies with aids of the density functional theory (DFT) and configuration interaction single (CIS) calculations. Infrared spectrum of the less stable O-cis isomer, produced from the more stable O-trans isomer upon UV irradiation, is measured with an FT-IR spectrophotometer. The enthalpy difference between the O-cis and O-trans isomers is estimated to be 9.7±0.2 kJ mol⁻¹ from the temperature dependence of the infrared band intensities. Analyses of the infrared and electronic absorption spectral changes after UV irradiation and the phosphorescence spectra measured at various excitation wavelengths suggest that the rotational isomerization occurs via the intersystem crossing from S₁ to T₁.     

Efficient synthesis of magnetic nanoparticle-Musa acuminata peel composite for the adsorption of anionic dye

The impregnation of magnetite (Mt) nanoparticle (NPs) onto Musa acuminata peel (MApe), to form a novel magnetic combo (MApe-Mt) for the adsorption of anionic bromophenol blue (BPB) was studied. The SEM, EDX, BET, XRD, FTIR and TGA were used to characterize the adsorbents. The FTIR showed that the OH and CO groups were the major sites for BPB uptake onto the adsorbent materials. The average Mt crystalline size on MApe-Mt was 21.13 nm. SEM analysis revealed that Mt NPs were agglomerated on the surface of the MApe biosorbent, with an average Mt diameter of 25.97 nm. After Mt impregnation, a decrease in BET surface area (14.89 to 3.80 m²/g) and an increase in pore diameter (2.25–3.11 nm), pore volume (0.0052–0.01418 cm³/g) and pH point of zero charge (6.4–7.2) was obtained. The presence of Pb(II) ions in solution significantly decreased the uptake of BPB onto both MApe (66.1–43.8%) and MApe-Mt (80.3–59.1%), compared to other competing ions (Zn(II), Cd(II), Ni(II)) in the solution. Isotherm modeling showed that the Freundlich model best fitted the adsorption data (R² > 0.994 and SSE < 0.0013). In addition, maximum monolayer uptake was enhanced from 6.04 to 8.12 mg/g after Mt impregnation. Kinetics were well described by the pseudo-first order and liquid film diffusion models. Thermodynamics revealed a physical, endothermic adsorption of BPB onto the adsorbents, with ΔH^o values of 15.87–16.49 kJ/mol, corroborated by high desorption (over 90%) of BPB from the loaded materials. The viability of the prepared adsorbents was also revealed in its reusability for BPB uptake.     

Infrared spectra of two sexithiophenes in neutral and doped states: a theoretical and spectroscopic study

The FT-infrared spectra of two sexithiophenes having their end ,′-positions substituted by n-hexyl or -thiohexyl groups, in neutral and doped states, are studied with the main aim of deriving information about the π-electrons delocalization and about the electronic structure of the charged defects created upon doping with iodine. The analysis of the experimental data is aided by Density Functional Theory calculations. The modifications in the electronic structure of the sexithiophene backbone induced by the n-thiohexyl encapsulation are discussed from the point of view of single molecule interactions in thiol-terminated π-conjugated oligomers bound to metallic or cluster electrodes.     

由季戊四醇合成季戊四硫醇的新方法

以季戊四醇为原料,先合成四对甲苯磺酸季戊四醇酯,然后四对甲苯磺酸季戊四醇酯与硫氰酸钾在N,N-二甲基甲酰胺中加热反应,生成了2,3,7,8-四硫螺[4,4]壬烷,2,3,7,8-四硫螺[4,4]壬烷经四氢化铝锂还原、酸化,得到季戊四硫醇.产物结构经熔点、红外光谱、质子核磁共振谱、拉曼光谱鉴定.     

Optical constants of silver and copper indium ternary sulfides from infrared reflectivity measurements

Infrared reflection spectra are obtained in the frequency range of 50–2000 cm⁻¹ for AgIn₅S₈ and CuIn₅S₈ single crystals grown by Bridgman method. All four infrared-active modes are detected, which are in full agreement with the prediction of group-theoretical analysis. Spectral dependence of optical parameters; real and imaginary parts of the dielectric function, the function of energy losses, refractive index, absorption index and absorption coefficient were calculated from reflectivity experiments. The frequencies of transverse and longitudinal optical modes and oscillator strengths were also determined. The bands detected in IR spectra of studied crystals were assigned to various vibration types (valence and valence-deformation) on the basis of the symmetrized displacements of atoms obtained employing the Melvin projection operators.     

Local structure of core/shell nanocrystalline particles produced by surfactant-assisted ball milling of Fe powder in paraffin

Surfactant-assisted ball milling of the Fe powder in paraffin has been used for fabrication of core–shell nanocrystalline particles. The local atomic structure of the bulk and surface layers of the mechanically milled particles has been studied using X-ray absorption spectroscopic techniques with synchrotron radiation from the DORIS storage ring at DESY, Hamburg. Regardless of milling environment composition, the as-prepared powders were shown to be characterized by a significant drop in the EXAFS signal intensity and coordination numbers of the Fe–Fe pairs due to the formation of nanocrystalline state in the particles. It has been shown that an addition of perfluorononanoic acid as a surfactant has a more prominent effect on the structure of the shell layers. The effect is revealed as an appearance of light element atoms (O, F, C) in the local atomic environment of the Fe atoms due to formation of oxide, carbide and adsorbed structures of different types in the particle shell.