Reinvestigation of the reactions of hexachlorocyclotriphosphazatriene with ethylenediamine and ethanolamine

Abstract is not available.

Hydrolytic reactions of tetrasulphur tetranitride in a homogeneous medium

The hydrolytic reactions of tetrasulphur tetranitride are studied in a homogeneous medium. Alkaline hydrolysis gives sulphite, thiosulphate, sulphate and sulphide whereas the products in acid hydrolysis are mainly sulphur dioxide, elemental sulphur and hydrogen sulphide, with traces of polythionates. Under optimum conditions, tetrasulphur tetranitride reacts with sulphite consuming 2 moles of sulphite per mole of sulphur nitride to give 2 moles of trithionate. The reaction of sulphur nitride with thiosulphuric acid gives pentathionate and tetrathionate.

Local hydrogen reactions of H*2 in a-Si:H

Hydrogen rearrangements at the H*2 complex are used as a model of low energy, local transitions in the two-hydrogen density of states of hydrogenated amorphous silicon (a-Si:H). These are used to account for the low activation energy motion of H observed by nuclear magnetic resonance, the low energy defect annealing of defects formed by bias stress in thin film transistors, and the elimination of hydrogen from the growth zone during the low temperature plasma deposition of a-Si:H. © 1998 Elsevier Science B.V. All rights reserved.

The theory of long distance electron transfer reactions

The rate of electron transport between distant sites was studied. The rate depends crucially on the chemical details of the donor, acceptor, and surrounding medium. These reactions involve electron tunneling through the intervening medium and are, therefore, profoundly influenced by the geometry and energetics of the intervening molecules. The dependence of rate on distance was considered for several rigid donor-acceptor "linkers" of experimental importance. Interpretation of existing experiments and predictions for new experiments were made.

The electronic and nuclear motion in molecules is correlated. A Born-Oppenheimer separation is usually employed in quantum chemistry to separate this motion. Long distance electron transfer rate calculations require the total donor wave function when the electron is very far from its binding nuclei. The Born-Oppenheimer wave functions at large electronic distance are shown to be qualitatively wrong. A model which correctly treats the coupling was proposed. The distance and energy dependence of the electron transfer rate was determined for such a model.

I. Efforts toward the synthesis of aliphatic iodonium salts. II. Flourine-19 nuclear magnetic resonance spectroscopy of cyclic and bicyclic systems

The synthesis of iodonium salts of the general formula [C₆H₅IR]⁺X^-, where R is an alkyl group and x- is a stabilizing anion, was attempted. For the choice of R three groups were selected, whose derivatives are known to be sluggish in S_N1 and S_N2 substitutions: cyclopropyl, 7, 7 -dimethyl-1-norbornyl, and 9 -triptycyl. The synthetic routes followed along classical lines which have been exploited in recent years by Beringer and students. Ultimately, the object of the present study was to study the reactions of the above salts with nucleophiles. In none of the three cases, however, was it possible to isolate a stable salt. A thermodynamic argument suggests that this must be due to kinetic instability rather than thermodynamic instability. Only iodocyclopropane and 1-iodoapocamphane formed isolable iododichlorides.

Several methylated 2, 2-difluoronorbornanes were prepared with the intent of correlating fluorine -19 chemical shifts with geometric features in a rigid system. The effect of a methyl group on the shielding of a β -fluorine is dependent upon the dihedral angle; the maximum effect (an upfield shift of the resonance) occurs at 0° and 180°, whereas almost no effect is felt at a dihedral angle of 120°. The effect of a methyl group on a γ -fluorine is to strongly shift the resonance downfield when fluorine and methyl group are in a 1, 3 - diaxial-like relationship. Molecular orbital calculations of fluorine shielding in a variety of molecules were carried out using the formalism developed by Pople; the results are, at best, in modest agreement with experiment.

Production of heavy and superheavy nuclei in massive fusion reactions

Within the framework of a dinuclear system (DNS) model, the evaporation-residue excitation functions and the quasi-fission mass yields in the 48Ca induced fusion reactions are investigated systematically and compared with available experimental data. Maximal production cross sections of superheavy nuclei based on stable actinide targets are obtained. Isotopic trends in the production of the superheavy elements Z = 110, 112–118 based on the actinide isotopic targets are analyzed systematically. Optimal evaporation channels and combinations as well as the corresponding excitation energies are proposed. The possible factors that influencing the isotopic dependence of the production cross sections are analyzed. The formation of the superheavy nuclei based on the isotopes U with different projectiles are also investigated and calculated.