Chemical bonding in Si5(2-) and NaSi5(-) via photoelectron spectroscopy and ab initio calculations

Photoelectron spectroscopy and ab initio calculations are used to investigate the electronic structure and chemical bonding of Si5(-) and Si5(2-) in NaSi5(-). Photoelectron spectra of Si5(-) and NaSi5(-) are obtained at several photon energies and are compared with theoretical calculations at four different levels of theory, TD-B3LYP, R(U)OVGF, UCCSD(T), and EOM-CCSD(T), all with 6-311+G(2df) basis sets. Excellent agreement is observed between experiment and theory, confirming the obtained ground-state structures for Si5(-) and Si5(2-), which are both found to be trigonal bipyramid with D3h symmetry at several levels of theory. Chemical bonding in Si5, Si5(-), and Si5(2-) is analyzed using NPA, molecular orbitals, ELF, and NICS indices. The bonding in Si5(2-) is compared with that in the isoelectronic and isostructural B5H5(2-) species, but they are found to differ due to the involvement of electron densities, which are supposed to be lone pairs in the skeletal bonding in Si5(2-).     

3-Cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines in the synthesis of substituted 3-(aminomethyl)pyridines

The reactions of substituted 3-cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines with lithium aluminum hydride in anhydrous diethyl ether afforded the corresponding 3-aminomethyl derivatives, which were used in the synthesis of the corresponding amides.     

Low-mass ions observed in plasma desorption mass spectrometry of high explosives

The low-mass ions observed in both positive and negative plasma desorption mass spectrometry (PDMS) of the high explosives HMX, RDX, CL-20, NC, PETN and TNT are reported. Possible identities of the most abundant ions are suggested and their presence or absence in the different spectra is related to the properties of the explosives as matrices in PDMS. The detection of abundant NO+ and NO2- ions for HMX, RDX and CL-20, which are efficient matrices, indicates that explosive decomposition takes place in PDMS of these three substances and that a contribution from the corresponding chemical energy release is possible. The observation of abundant C2H4N+ and CH2N+ ions, which have high protonation properties, might also explain the higher protein charge states observed with these matrices. Also, the observation of NO2-, possibly formed by electron scavenging which increases the survival probability of positively charged protein molecular ions, completes the pattern. TNT does not give any of these ions and it is thereby possible to explain why it does not work as a PDMS matrix. For NC and PETN, decomposition does not seem to be as pronounced as for HMX, RDX and CL-20, and also no particularly abundant ions with high protonation properties are observed. The fact that NC works well as a matrix might be related to other properties of this compound, such as its high adsorption ability.     

Interfacial micellar structures from novel amphiphilic star polymers

An amphiphilic heteroarm star polymer containing 12 alternating hydrophobic/hydrophilic arms of polystyrene (PS) and poly(acrylic acid) (PAA) connected to a well-defined rigid aromatic core was studied at the air-water and the air-solid interfaces. At the air-water interface, the molecules spontaneously form pancakelike micellar aggregates which measure up to several microns in diameter and 5 nm in thickness. Upon reduction of the surface area per molecule to 7 nm2, the two-dimensional micelles merged into a dense monolayer. We suggest that confined phase separation of dissimilar polymer arms occurred upon their segregation on the opposite sides of the rigid disklike aromatic core, forcing the rigid cores to adopt a face-on orientation with respect to the interface. Upon transfer onto solid supports the PS chains face the air-film interface making it completely hydrophobic, and the PAA chains were found to collapse and form a thin flattened underlayer. This study points toward new strategies to create large 2D microstructures with facial amphiphilicity and suggests a profound influence of star molecular architecture on the self-assembly of amphiphiles at the air-water interface.     

Synthesis and Acidity of 5-Phenyltetrazol-2-ylalkanoic Acids and the Corresponding 5-(5-Phenyltetrazol-2-ylalkyl)tetrazoles

We have obtained 5-phenyltetrazol-2-ylalkanoic acids and their derivatives containing terminal nitrile, amide, and tetrazol-5-yl groups. Tetrazolylalkanoic acids with two (pK _a 4.93) and three (pK _a 5.45) bridging methylene groups are weaker acids than the corresponding ditetrazoles pK _a 4.68 and 5.29 respectively). However, the acidity of 5-phenyltetrazol-2-ylacetic acid (pK _a 3.12), is higher than acidity of the corresponding ditetrazole (pK _a 3.27).     

Phase Transitions in Electro- and Magnetorheological Fluids

The model of internal structural phase transformations occurring in electro- and magnetorheological fluids under the action of external electric (magnetic) field is presented. The model describes both types of experimentally observed transformations such as the formation of linear chain clusters and bulk dense phases composed of suspension particles. The main qualitative result of this work is the conclusion that the appearance of chain clusters precedes the suspension separation into bulk phases with different particle densities and considerably affects the phase equilibrium diagrams. This conclusion agrees with the results of known experiments.     

Linear polynuclear tetrazole-containing compounds

Linear polynuclear tetrazole-containing compounds were synthesized. Alkylation of 5-[-(5-phenyl-2-tetrazolyl)alkyl]tetrazoles with ethyl bromoacetate and chloroacetamide gave the corresponding esters and amides. Treatment of the latter with tetrachlorosilane-sodium azide afforded compounds containing three tetrazole rings linked through polymethylene bridges. Acid ionization constants of the products possessing an NH-tetrazole ring (pK _a = 2.9–3.2) and the corresponding carboxylic acids (pK _a = 2.9–3.1) in aqueous methanol were determined by potentiometric titration.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1580–1586.Original Russian Text Copyright © 2004 by Morozova, Komissarov, Esikov, Zubarev, Malin, Ostrovskii.     

Generalized coulomb barrier transmission coefficient for solar neutrino and astrophysical problems

For astrophysical calculations, it is customary to extrapolate higher-energy (20keV) data using the Gamow transmission coefficient in estimating the nonresonance nuclear fusion reaction cross sections (E) for charged particles at low energies (<20 keV). We present a general extrapolation method based on a more realistic Coulomb barrier transmission coefficient, which can accommodate simultaneously both nonresonance and resonance contributions.     

The large-scale vortex structures in plasma-like media and the electric explosion of conductors

Formation of large-scale hydrodynamic convective patterns in plasma-like current-carrying media is considered. This process is shown to be described by the same equations, as Benard rolls, except that a temperature field must be replaced by a magnetic field. A simple low-mode model of spatial pattern formation for a case of cylindrical liquid-metal conductor with current is proposed and investigated. Nonlinear interaction of perturbations of the magnetic field and the velocity field results in an increase of effective conductor resistance even when transport coefficients are constant. In our opinion, it is this instability, that is of first importance at the initial stages of the electric explosion of conductors. In particular, it leads to conductor stratification and electric current interruption. (c) 1996 American Institute of Physics.