An ab initio potential energy surface for the υ4 vibrational mode of hydrogen peroxide

In this paper, the levels and the torsional microstates of hydrogen peroxide are determined from fully optimized ab initio calculations using a nuclear model in one dimension. Calculations have been performed at the MP2 level with the 6-311 G(2df,2pd), 6-31 1+G(2df,2pd), cc-pVTZ and AUG-cc-pVTZ basis sets including polarization orbitals and diffuse functions. The most stable conformation, calculated with the MP2/AUG-cc-pVTZ approach, is a trans–gauche conformer lying at 67.5° from the trans structure. By using the same level of calculations, the heights of the trans and cis barriers have been determined to be 386.5 and 2643.8 cm⁻¹ in a good agreement with the experimental data. The variational torsional levels split into four components by the tunnelling effect of the barriers. The splitting of the fundamental level caused by the trans barrier has been found to be 11.8683 cm⁻¹, whereas the splitting caused by the cis barrier is insignificant under n=2. Current ab initio energies confirm the experimental assignments and verify the separability of the torsion from the rest of the vibrations. However, the experimental relation of dependence on the torsion of the rotational constants cannot be reproduced in one-dimension and depends on several additional vibrational effects.     

Spectroscopic and structural analysis of Ca substituted La orthoferrite

Samples of orthoferrites La_1−xCa_xFeO₃ (0.15≤x≤0.45) were synthesized by double sintering ceramic technique. X-ray diffraction and infrared spectroscopy experiments were carried out and discussed for the investigated samples. The data showed the formation of single-phase orthorhombic structure of space group Pbnm. The FTIR spectra were performed in the region (1200–200 cm⁻¹). Four main absorption bands were present with some side bands and shoulders in the range (1200–400 cm⁻¹). Another four bands were appeared in the range (400–200 cm⁻¹). The positions, intensities and values of the absorptions bands vary depending on the Ca content in the samples. The first absorption band appeared at about 920 cm⁻¹ was assigned to the La–O stretching vibration.     

A new electrolytic dissolution of aluminum alloys and determination of some constituents by inductively coupled plasma optical emission spectrometry

The new electrolytic dissolution in batch of aluminum alloys samples as grains or turns and the determination of Fe, Cu, Mn, Mg, Cr, Ni, Zn, Pb and Ti by ICP OES was investigated. In on-line electrodissolution procedures described in the literature, samples were restricted to be in the form of solid blocks or plates with one polished flat face. Here, the sample was loaded in the barrel of a modified disposable syringe (the anodic semi-cell) and pressed with a modified plunger fitted with a platinum disk to establish electrical contact with the analyte. This arrangement was introduced in a beaker containing the electrolyte (1 mol L⁻¹ HNO₃) and a platinum wire as the cathode. The resulting solution from electrodissolution (0.6 A) was used for the ICP OES determinations. The influence of the aluminum concentration increase on the determination of the elements was evaluated. Electrodissolution of certified reference materials and commercial samples revealed relative errors lower than 10% for the elements Fe, Cu, Mg, Ni, Cr, Zn and Ti (when their content is above 0.1%). Higher inaccuracies (>10%) were observed for Mn and for Fe in B.C.S. 268/1 reference material certified. The proposed method presented a relative standard deviations (R.S.D.) lower or circa 10% to all of the elements (except Pb). In comparison with traditional acid dissolution, the proposed electrodissolution method is relatively fast (about 30 min), it is clean (there is no projection of solution) and simple (heating and fumes exhaust system were not necessaries).     

Structural investigation of dibromobis(benzimidazole)Zn(II) complex

The molecular structure of the title complex [ZnBr₂(C₇H₆N₂)₂] was investigated by X-ray diffraction and IR spectroscopy methods. Molecules of zinc(II) complex crystallize in the triclinic crystal system with cell constants a=7.526(2) Å, b=7.8971(8) Å, c=13.431(1) Å, Z=2 and V=791.3(2) Å³. In the molecular structure, the Zn atom is coordinated tetrahedrally by two Br⁻ anions and two benzimidazole ligands. Intramolecular steric repulsions between Br⁻ anions and benzimidazole groups have been caused to cis configuration around the central metal atom.     

4,4′-Dipyridyl and 2,2′-dipyridyl complexes of rare-earth perchlorates

4,4-Dipyridyl and 2,2-dipyridyl complexes of rare-earth perchlorates of the formulaLn(4-dipy)₈(ClO₄)₃HClO₄ · 4H₂O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 4-dipy=4,4-dipyridyl) andLn(2-dipy)₃(ClO₄)₃ · 6H₂O (Ln=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 2-dipy = 2,2-dipyridyl) have been synthesized. The IR spectra of these compounds and other physical properties are discussed.

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4,4-Dipyridyl- und 2,2-Dipyridylkomplexe von Seltenerdmetallperchloraten

Zusammenfassung Es wurden 4,4-Dipyridylkomplexe des TypsLn(4-dipy)₈(ClO₄)₃HClO₄ · · 4 H₂O mitLn=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y und 2,2-Dipyridylkomplexe des TypsLn(2-dipy)₃(ClO₄)₃ · 6 H₂O mitLn=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu und Y dargestellt. Die IR-Spektren und andere physikalische Eigenschaften werden diskutiert.

     

The ν(OH/OD) band shape of strong hydrogen bonded dimers of phosphinic acids. Phenomenology and formation models

The infrared spectra of phosphinic acid R₂POOH dimers (R=CH₃, CH₂Cl, C₆H₅) have been studied in CCl₄ and CH₂Cl₂ solutions (T=300 K). The infrared spectra of deuterated R₂POOD dimers (R=CH₃, CH₂Cl) were also studied in the gas phase (T=400–550 K) and solid state (T=100–300 K). They are compared with previously studied spectra of the light (non-deuterated) dimers in the gas phase, in the solid state and in low-temperature argon matrices (T=12–30 K) in the 4000–400 cm⁻¹ spectral region. It is found that the strong and broad ν(OH) dimer bands have similar shapes, nearly equal values of bandwidth and low-frequency shift, and possess the Hadzi ABC structure irrespective of the type of acid, significant differences of dimerization enthalpies, influence of solvent, the type of H-bonded complexes (cyclic dimers in the gas phase, in solutions, and in inert matrices, and infinite chains in the solid state), and temperature in the range 12–600 K. Isotopic ratio of the first moments of light and deuterated acid bands has been measured. Analysis of the ν(OH/OD) band of hydrogen bonded dimers of phosphinic acids shows that the interaction between the two intermolecular bonds O–HOP in a cyclic complex plays virtually no role in the mechanism of the ν(OH/OD) band formation; the shape of ν(OH/OD) band is controlled mainly by the POOH(D)O fragment; and the band shape of strong hydrogen bonded complexes is formed by a number of vibrational transitions from the ground state to different combination levels in the region 3500–1500 cm⁻¹.     

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.     

Comparison of zinc and cadmium plasma parameters produced by laser-ablation

We report the measurement of the zinc and cadmium plasma parameters produced by the fundamental, second, and third harmonics of the neodymium-doped yttrium aluminium garnet laser. The excitation temperature has been determined from the Boltzmann plot method, whereas the electron number density is estimated from the Stark broadened profile of several spectral lines. The temporal evolution of the plasma has also been investigated. Besides, we present experimental relative transition probabilities of the Zn (4s5s ³S₁ → 4s4p ³P_0,1,2) and Cd (5s6s ³S₁ → 5s5p ³P_0,1,2) triplets and compare our data with that listed in the National Institute of Standards and Technology database. The experiments have been performed in air but also in He, Ne and Ar atmosphere to study the effects of ambient gas environment on the emission intensity of the atomic and ionic lines and on the plasma parameters.