Structural considerations from dielectric measurements on the aliphatic alcohols

Precise static dielectric constants are reported for methanol, ethanol, andn-propanol at 10,25, and 40° C and at pressures up to 3 kbar. The measurements were carried out by a low-frequency bridge method using a threeterminal, all-glass cell. An uncertainty of 0.05% is claimed for the data. The results are compared to data from previous investigations, whith the agreement in the absolute magnitude poor but the agreement in the pressure coefficient reasonable in most cases. The data are analyzed in terms of the Kirkwood correlation factorg _K as obtained from the Fröhlich equation. In all cases, theg _K factor decreases with increased pressure. The problems involved in calculating this factor from the experimental data are discussed, and it is shown that the trends ing _K are very dependent upon the assumptions made in isolating the liquid dipole moment from its gas-phase value. This fact also indicates that an interpretation of theg _K values in terms of stepwise association of correlation dipoles is premature at this time.     

The arylation of nitroalkanes and nitronate salts with aryllead triacetates

Nitroalkanes and their nitronate salts undergo α-arylation in good yield when treated with an aryllead triacetate in dimethyl sulfoxide.     

Spatially constrained minimization of macromolecules

A structural minimization procedure which converges rapidly and restricts the atomic shifts is outlined. It is implemented by adding a harmonic penalty term for the displacements of atomic positions and resetting the reference coordinates with respect to which the constraints are computed during the minimization. The resetting serves to reduce the constraint energy of the minimized structure to negligible levels.     

Etude de la reactivite d'ylures de sulfonium et de pyridinium stabilises par un groupement cyanoformyle

The sulfonium and pyridinium ylides stabilized by a cyanoformyl group, in an acidic medium, lead to sulfonium and pyridinium salts which are equivalents of pyridinium or sulfonium ketene salts. This originality has been used to prepare new stabilized ylides, or derivatives of substituted arylacetic acids or 4-hydroxy thiazoles.     

Molecular Structures from Density Functional Calculations with Simulated Annealing

The geometrical structure of any aggregate of atoms is one of its basic properties and, in principle, straightforward to predict. One chooses a structure, determines the total energy E of the system of electrons and ions, and repeats the calculation for all possible geometries. The ground state structure is that with the lowest energy. A quantum mechanical calculation of the exact wave function Ψ would lead to the total energy, but this is practicable only in very small molecules. Furthermore, the number of local minima in the energy surface increases dramatically with increasing molecular size. While traditional ab initio methods have had many impressive successes, these difficulties have meant that they have focused on systems with relatively few local minima, or have used experiment or experience to limit the range of geometries studied. On the other hand, calculations for much larger molecules and extended systems are often forced to use simplifying assumptions about the interatomic forces that limit their predictive capability. The approach described here avoids both of these extremes: Total energies of predictive value are calculated without using semi-empirical force laws, and the problem of multiple minima in the energy surface is addressed. The density functional formalism, with a local density approximation for the exchange-correlation energy, allows one to calculate the total energy for a given geometry in an efficient, if approximate, manner. Calculations for heavier elements are not significantly more difficult than for those in the first row and provide an ideal way to study bonding trends. When coupled with finite-temperature molecular dynamics, this formalism can avoid many of the energetically unfavorable minima in the energy surface. We show here that the method leads to surprising and exciting results.     

The determination of vanadium,molybdenum and tungsten by infrared spectroscopy

The infrared spectra of the 8-hydroxyquinolinates of molybdenum, vanadium and tungsten in the region 3–15 μ were investigated. It was found possible to determine the elements quantitatively, singly or in pairs, with an error of about 3%. Molybdenum was determined at 10.80 μ and 10.93 μ, vanadium at 10.50 μ, and tungsten at 10.61 μ or 10.90 μ.     

Bioluminescent reporter bacteria detect contaminants in soil samples

Applied Biochemistry and Biotechnology - Reporter strains of bacteria were tested using soil samples from several sites near a leaking fuel oil storage facility. The reporter bacteria utilized the...     

Single nanocrystal arrays on patterned poly(ethylene glycol) copolymer microstructures using selective wetting and drying

Single nanocrystal arrays were fabricated on sub-microwells of poly(ethylene glycol) (PEG) copolymer using selective wetting on the hydrophilic regions of the exposed substrate surface and subsequent drying. Templates were produced by molding a thin film of a PEG-based random copolymer on hydrophilic substrates such as glass or silicon dioxide. The polymeric microstructures provide a topographical barrier around the well, which makes it possible to create nanocrystal arrays with controlled geometrical features. The size of the nanocrystal was found to decrease with decreasing well size and also decrease with decreasing topological height. A simple empirical equation was derived to predict the size of the crystal as a function of the pattern size and height, which is in good agreement with the experimental data.     

Sequential versus direct multiphoton absorption

We present results of exact calculations on a three-level Morse oscillator modeling HF which suggest that multiphoton absorption proceeds by sequential single-level transitions, transitions arising from coupling between non-adjacent states being dynamically negligible. The time-dependent Schrödinger equation is integrated in the Floquet formalism.     

Oxygen sensitivity of algal H2- production

Applied Biochemistry and Biotechnology - Photoproduction of H2 by green algae utilizes electrons originating from the photosynthetic oxidation of water and does not require metabolic intermediates....