Absolute infrared intensities of hydrocarbons

Dipole-moment derivatives, calculated by both the CNDO/2 method with different parameterizations and the INDO method, are compared to the experimental values determined from absolute infrared intensity measurements for the IR active modes of methane, ethane, ethylene and acetylene. A parameter refinement procedure is introduced in which the CNDO/2 molecular orbital parameters are adjusted through a damped least-squares treatment to give best agreement with the observed dipole-moment derivatives. It is found that the refinement does not substantially improve the agreement obtained with the original CNDO/2 parameterization. The INDO method gives somewhat poorer agreement than the CNDO/2 calculations. As an example of the applicability of the molecular orbital methods toward reproducing relative infrared intensities, the spectrum of cyclopropane in the gasphase is examined.

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Zusammenfassung Die Ableitungen des Dipol-Moments, die nach der CNDO/2-Methode mit verschiedenen Parametrisierungen sowie der INDO-Methode berechnet wurden, werden mit den experimentellen Ergebnissen aus Messungen der absoluten Infrarot-Intensitäten für die IR-aktiven Schwingungen von Methan, Äthan, Äthylen und Azetylen verglichen. Die CNDO/2-Parameter werden mit einer Methode der kleinsten Quadrate den beobachteten Dipol-Moment-Ableitungen angepaßt. Die Ergebnisse sind jedoch nicht wesentlich von denen der ursprünglichen CNDO/2-Methode verschieden. Die INDO-Ergebnisse sind nicht so gut wie die CNDO/2-Ergebnisse. Als Beispiel der Anwendbarkeit der MO-Methoden zur Berechnung von relativen IR-Intensitäten wird das Spektrum des Cyclopropans in der Gasphase untersucht.

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Résumé Les dérivées du moment dipolaire, calculées par la méthode CNDO/2 avec différentes paramétrisations et par la méthode INDO, sont comparées aux valeurs expérimentales déterminées à partir de mesures d'intensité absolue pour les modes actifs dans l'infra-rouge dans le méthane, l'éthane, l'éthylène et l'acétylène. Les paramètres sont ajustés de manière à donner le meilleur accord avec les dérivées du moment dipolaire. Cet ajustement n'améliore pas sensiblement l'accord obtenu avec la paramétrisation CNDO/2 originale. La méthode INDO donne des résultats moins bons que les calculs CNDO/2. Le spectre du cyclopropane en phase gazeuse est étudié comme exemple de l'applicabilité de la méthode des orbitales moléculaires au calcul des intensités relatives infra-rouge.

     

Electron tunneling into ion implanted PbMn and SnMn alloys

Tunnel junctions ofPb-I-Al andSn-I-Al were implanted at low temperatures with Mn ions in the ppm region. The tunnel characteristicdI/dV was measured on the pure sample and on the alloy with different concentrations. A bound state is found in both systems at an energy 0.7 ₀. Comparison with theory confirms, that the Kondo effect is not necessary for the existence of a bound state.     

Exploration of the Crystal Structure and Thermal and Spectroscopic Properties of Monoclinic Praseodymium Sulfate Pr2(SO4)3

Praseodymium sulfate was obtained by the precipitation method and the crystal structure was determined by Rietveld analysis. Pr₂(SO₄)₃ is crystallized in the monoclinic structure, space group C2/c, with cell parameters a = 21.6052 (4), b = 6.7237 (1) and c = 6.9777 (1) Å, β = 107.9148 (7)°, Z = 4, V = 964.48 (3) ų (T = 150 °C). The thermal expansion of Pr₂(SO₄)₃ is strongly anisotropic. As was obtained by XRD measurements, all cell parameters are increased on heating. However, due to a strong increase of the monoclinic angle β, there is a direction of negative thermal expansion. In the argon atmosphere, Pr₂(SO₄)₃ is stable in the temperature range of T = 30–870 °C. The kinetics of the thermal decomposition process of praseodymium sulfate octahydrate Pr₂(SO₄)₃·8H₂O was studied as well. The vibrational properties of Pr₂(SO₄)₃ were examined by Raman and Fourier-transform infrared absorption spectroscopy methods. The band gap structure of Pr₂(SO₄)₃ was evaluated by ab initio calculations, and it was found that the valence band top is dominated by the p electrons of oxygen ions, while the conduction band bottom is formed by the d electrons of Pr³⁺ ions. The exact position of ZPL is determined via PL and PLE spectra at 77 K to be at 481 nm, and that enabled a correct assignment of luminescent bands. The maximum luminescent band in Pr₂(SO₄)₃ belongs to the ³P₀ → ³F₂ transition at 640 nm.     

From Chaos to Ordering: New Studies in the Shannon Entropy of 2D Patterns

Properties of the Voronoi tessellations arising from random 2D distribution points are reported. We applied an iterative procedure to the Voronoi diagrams generated by a set of points randomly placed on the plane. The procedure implied dividing the edges of Voronoi cells into equal or random parts. The dividing points were then used to construct the following Voronoi diagram. Repeating this procedure led to a surprising effect of the positional ordering of Voronoi cells, reminiscent of the formation of lamellae and spherulites in linear semi-crystalline polymers and metallic glasses. Thus, we can conclude that by applying even a simple set of rules to a random set of seeds, we can introduce order into an initially disordered system. At the same time, the Shannon (Voronoi) entropy showed a tendency to attain values that are typical for completely random patterns; thus, the Shannon (Voronoi) entropy does not distinguish the short-range ordering. The Shannon entropy and the continuous measure of symmetry of the patterns demonstrated the distinct asymptotic behavior, while approaching the close saturation values with the increase in the number of iteration steps. The Shannon entropy grew with the number of iterations, whereas the continuous measure of symmetry of the same patterns demonstrated the opposite asymptotic behavior. The Shannon (Voronoi) entropy is not an unambiguous measure of order in the 2D patterns. The more symmetrical patterns may demonstrate the higher values of the Shannon entropy.     

The spectral maximum of synchrotron radiation

A three-level system is considered as a simplest example where a possibility of solving the spectral problem is observed. We thoroughly analyze the relation between the amount of radiation emitted by the particle during the transitions to the first excited state and to the ground state. Generalizing basic expressions we can follow the evolution of spectral maximum. It turns out there is a condition for radiation maximum to stay at highest harmonic.     

Synthesis of Phosphonoindoprofen

Two synthetic routes to phosphonic analogues of indoprofen, a nonsteroidal anti-inflammatory drug, were developed by the cyclization of aniline 2 (method A) and by the Arbuzov reaction of corresponding alkylchloride 3 with triethylphosphite (method B).     

Synthesis of high-purity lower silicon alcoholates for new technology

Purification of a number of silicon derivatives (chloride, lower alcoholates) formed in processing of high-purity silicon for electronic and electrical industries was considered. It was found that high-purity substances suitable for use in electronics and optics can be produced from industrial wastes.     

Spatial condensation of trapped polaritons in graphene and semiconductor structures

The theoretical and experimental status of the Bose–Einstein Condensation (BEC) of trapped quantum well (QW) polaritons in a microcavity is presented. The results of recent experiments that have shown the possibility to create an in-plane harmonic potential trap for a two-dimensional (2D) exciton polaritons in a cavity are discussed. We report the theory of BEC and of the trapped QW exciton polaritons in a microcavity. In addition, we study the BEC of trapped magnetoexciton polaritons in a graphene layer (GL) embedded in an optical microcavity in high magnetic field. In both cases the polaritons are considered to be in a harmonic potential trap. We compare the theoretical results with the existing experiments and discuss the experimental observation of predicted phenomena.