Spectroscopic and theoretical study of the molecular and electronic structures of a terthiophene-based quinodimethane.

The UV/Vis, infrared absorption, and Raman scattering spectra of 3',4'-dibutyl-5,5"-bis(dicyanomethylene)-5,5"-dihydro-2,2':5',2"-terthiophene have been analyzed with the aid of density functional theory calculations. The compound exhibits a quinoid structure in its ground electronic state and presents an intramolecular charge transfer from the terthiophene moiety to the C(CN)2 groups. The molecular system therefore consists of an electron-deficient terthiophene backbone end-capped with electron-rich C(CN)2 groups. The molecule is characterized by a strong absorption in the red, due to the HOMO-->LUMO pi-pi* electronic transition of the terthiophene backbone that shifts hypsochromically on passing from the solid state to solution and with the polarity of the solvent. The analysis of the vibrational spectra confirms the structural conclusions and supports the existence of an intramolecular charge transfer. Vibrational spectra in several solvents and as a function of temperature have also been studied. Significant frequency upshifts of the vibrations involved in the pi-electron-conjugated pathway have been noticed upon solution in polar solvents and with the lowering of the temperature. Finally, we propose a quinoid molecule as a reliable structural and electronic model for dication species in doped oligothiophenes or for bipolaron charged defects in doped polythiophene.     

Organoplatinum(II) complexes containing chelating or bridging bis(N-heterocyclic carbene) ligands: formation of a platinum(II) carbonate complex by aerial CO2 fixation

The preparation of two new bis(N-heterocyclic carbene) platinum(II) complexes, in which NHC rings are joined by a CH(2) linker group, is described. While, the chelate complex [PtMe(2)(bis-NHC1)], 1, was formed with large tert-butyl wingtips, the iso-propyl N-substituent analogue favors formation of the cluster complex [Pt(2)Me(4)(μ-SMe(2))(μ-bis-NHC2)](2)(μ-Ag(2)Br(2)), 2, in which two binuclear platinum(II) complexes are linked together by an Ag(2)Br(2) unit. The chelating platinum complex 1 undergoes aerial CO(2) fixation and forms platinum(II) carbonate complex [Pt(CO(3))(bis-NHC1)], 3.     

Controlled Growth of Hybrid Halide Perovskites by Crown Ether Complexation for Perovskite Solar Cells

Host-guest complexation has demonstrated potential for controlling hybrid organic-inorganic metal halide perovskite materials. In particular, crown ethers have been used due to their capacity to interact with metal cations (e. g., Pb²⁺) and small organic cations (e. g., methylammonium (MA)), which can affect hybrid perovskite materials and their solar cells. However, this strategy has been underexploited in perovskite photovoltaics, and the underlying mechanisms are not well understood. In this study, we investigate the influence of 15-crown-5 ( 15C5 ) and its benzannulated derivative (benzo-15-crown-5, B15C5 ), as well as amino-functionalized analogues (15-crown-5)-2-methylamine, 2A-15C5 , and 4′-aminobenzo-15-crown-5, 4A-B15C5 , on MAPbI₃ perovskite crystallization and inverted solar cell performance. We demonstrate the propensity of crown ether modulators to interact with Pb²⁺ cations at the perovskite interface by density functional theory calculations. This has been shown to facilitate oriented crystal growth and homogeneous film formation, as revealed by X-ray diffraction analysis complemented by scanning electron microscopy. As a result, we demonstrate an increase in the power conversion efficiency of the solar cells of interest to advancing hybrid photovoltaics.     

Differences in coating mechanism of structurally different aluminosilicates observed through the thermal analysis

Systematic modification of three structurally different minerals (zeolite, mica, and vermiculite) was carried out with the aim of determining the modification mechanism and exposing the hydrophobic surface that can be used as a sorbent for many organic compounds. Mechanism of modification with cationic surfactant depends strongly on the mineral type. In order to identify the influence of aluminosilicates structural differences on the modification process, adsorption experiments with organic matter and water vapor, supplemented with the DTA/TG analysis, were performed. The cation exchange capacity (CEC) value was 1454?>?560?>?28 meq kg^?1 for zeolite (clinoptilolite), vermiculite, and mica (muscovite), respectively. Despite its CEC value, vermiculite adsorbed three times the amount of organic matter than did clinoptilolite due to the porous structure of zeolite, which acted to limit the adsorption only on the external exchangeable cations. If the loading amount is equal to the CEC or the external cation exchange capacity for clinoptilolite (ECEC?≈?10% CEC), the monolayer will form while mineral surface will have hydrophobic character. Only one active center exists at the surface of the clinoptilolite that was identified by DTA curves with a sharp and defined peak around 300 °C and by the mass loss at the TG diagrams. Two significant and equal active centers were observed in vermiculite, one for the exchange of the surface cations and the other for the interlayer cations and H₂O molecules. Muscovite CEC is negligible, and due to the absence of any other functional groups, the modification of this mineral was impossible.     

Untersuchungen der Hydroxylammonium-Aluminate

Summary Two microcristalline phases have been isolated from aqueous solutions: (NH₃OH)₂AlF₅(A) and (NH₃OH)AlF₄·H₂O(B). They crystallize in the orthorhombic system with cell parameters for A:a=6.475 (3) Å,b=7.295 (3) Å,c=10.827 (5) Å, and for B:a=7.003 (3) Å,b=8.489 (4) Å,c=10.745 (5) Å. The Hydroxylammonium-aluminates were characterized by vibrational spectroscopy and their thermal decomposition studied by DSC and TG analysis.

     

A simplified quantum energy-transport model for semiconductors

The existence of global-in-time weak solutions to a quantum energy-transport model for semiconductors is proved. The equations are formally derived from the quantum hydrodynamic model in the large-time and small-velocity regime. They consist of a nonlinear parabolic fourth-order equation for the electron density, including temperature gradients; an elliptic nonlinear heat equation for the electron temperature; and the Poisson equation for the electric potential. The equations are solved in a bounded domain with periodic boundary conditions. The existence proof is based on an entropy-type estimate, exponential variable transformations, and a fixed-point argument. Furthermore, we discretize the equations by central finite differences and present some numerical simulations of a one-dimensional ballistic diode.     

Femtosecond pulse compression in a hollow-core photonic bandgap fiber by tuning its cross section

We present a numerical study of soliton pulse compression in a seven-cell hollow-core photonic bandgap fiber. We analyze the enhancement of both the compression factor and the pulse shape quality of 360 nJ femtosecond pulses at the wavelength of 800 nm by tuning the cross section size of the fiber. We use the generalized non-linear Schrödinger equation in order to modeled the propagation of light pulses along the fiber. Our numerical results show that output compressed pulses can be obtained, in a propagation length of 31 cm, with a compression factor of 5.7 and pulse shape quality of 77% for a reduction of 4.5% of the cross section size of the fiber. The predicted compression factor is 3 times larger than that experimentally obtained in such propagation length of the pulse in a hollow-core photonic bandgap fiber.     

Electron and ion mobilities in argon plasma with fluorine as additive

Results of the numerical evaluation of the electron and ion mobilities in plasmas from mixtures of argon and fluorine are given. The temperature dependence of the number densities of the components and their mobilities as a function of temperature for low-pressure (from 0.1 kPa to 1.0 kPa) and low-temperature (from 500 K to 5000 K) argon plasmas with 20% and 30% of added fluorine are evaluated. It is assumed that the system is kept under constant pressure and that a corresponding state of local themodynamical equilibrium is attained in it. The previously derived expression for the modified Debye radius, offering the possibility to treat the plasmas as weakly non-ideal in the whole temperature range, is used and the cut-off at the Landau length rather than at the smallest ionic radius is introduced. This alteration in the evaluation procedure gives different changes in the final numerical results for all the relevant quantities. It was found that the equilibrium plasma composition depends considerably on the presence of fluorine in the whole temperature range for both the pressures; the addition of fluorine significantly enhances the number densities of all relevant charged constituents. This fact influences the electron and ion collision frequencies as well as their mobilities.     

Selective Limit Theorems for Random Walks on Parabolic Biangle and Triangle Hypergroups

Let K be respectively the parabolic biangle and the triangle in and be a sequence in [0, +[ such that lim_p (p)=+. According to Koornwinder and Schwartz,⁽⁷⁾ for each there exist a convolution structure (*_(p)) such that (K, *_(p)) is a commutative hypergroup. Consider now a random walk on (K, *_(p)), assume that this random walk is stopped after j(p) steps. Then under certain conditions given below we prove that the random variables on K admit a selective limit theorems. The proofs depend on limit relations between the characters of these hypergroups and Laguerre polynomials that we give in this work.     

The quantification of total lead in lipstick specimens by total reflection X‐ray fluorescence spectrometry

Lipstick is known to contain lead, and this has been a general area of concern. Methods of quantifying lead in lipstick currently require the use of rather harsh digestion procedures given that lipstick specimens are high in their lipid content and contain many refractory materials. A simple method of performing lead analysis in lipstick specimens based on total reflection X‐ray fluorescence spectrometry (TXRF) is presented here. Samples were prepared by melting lipstick specimens along with a non‐ionic surfactant and an yttrium internal standard followed by homogenization. Solid prepared samples were then finely streaked directly onto a quartz reflector, and TXRF measurements made for 900‐s live time. The method was found to produce a mean limit of detection for lead of 0.04μg/g. Precisions were found to be on the order of 11–38% relative standard deviation (RSD) and apparent recoveries for lead between 92% and 106% (n = 8). Although the spreading technique may result in thickness variations that may contribute to the higher than expected variances about the determined lead concentrations, the method presented in this work does show promise as a means of performing routine lead analysis in lipstick specimens without the need for harsh digestion procedures. Copyright © 2015 John Wiley & Sons, Ltd.