Halophilic reactions of a stable silylene with chloro and bromocarbons

A number of disilanes have been synthesized from a stable silylene, 1 (N,N'-di-tert-butyl-1,3-diaza-2-silacyclopent-4-en-2-ylidene), and a variety of halocarbons. It is proposed that disilane formation is a result of an initial halophilic interaction between the silylene and halocarbon. Formation of disilanes from 1 and CCl4, 2a, CHCl3, 2b, CH2Cl2, 2c, benzyl chloride, 2d, and bromobenzene, 5, are described here. An X-ray crystal structure of 2b was determined.     

Perturbed angular distributions in the presence of isotropic paramagnetic relaxation

The effect of paramagnetic relaxation on perturbed angular distributions is treated for nuclei interacting with their electronic shells via isotropic hyperfine interaction. The conditions are given under which Blume's analytical stochastic-model result for the nuclear perturbation factorsG _k (t) can be derived quantum mechanically. Systems with arbitrary nuclear spin, but electronic spinS=1/2 may be calculated without resorting to the assumption necessary forS>1/2. Explicit closed expressions forG _k (t) can be found for this particular case.     

Multiple-magnetic field 139La NMR and density functional theory investigation of the solid lanthanum(III) halides

Results from a solid-state ¹³⁹La NMR spectroscopic investigation of the anhydrous lanthanum(III) halides (LaX₃; X=F, Cl, Br, I) at applied magnetic fields of 7.0, 9.4, 11.7, 14.1, and 17.6 T are presented and highlight the advantages of working at high applied magnetic field strengths. The ¹³⁹La quadrupolar coupling constants are found to range from 15.55 to 24.0 MHz for LaCl₃ and LaI₃, respectively. The lanthanum isotropic chemical shifts exhibit an inverse halogen dependence with values ranging from −135 ppm for LaF₃ to 700 ppm for LaI₃, which represents nearly half of the total lanthanum chemical shift range. The spans of the magnetic shielding tensors also vary widely, from 35 to 650 ppm for the solid LaF₃ through LaI₃. DFT calculations of the ¹³⁹La electric field gradient and magnetic shielding tensors have been performed and provide a qualitative interpretation of the trends observed experimentally.     

Nonnegatively Curved Metrics on S 2 × ℝ2

We classify the complete metrics of nonnegative sectional curvature on M ² × ², where M ² is any compact 2-manifold.     

Mode-coupling approach to the dynamics of simple liquids

Summary A new derivation of the mode-coupling theory of liquid dynamics is presented which is applicable to both quantum and classical systems. A clear distinction between the basic underlying hyphotheses and the more technical approximations has been attempted. Asymptotic corrections to the dynamics of modes due to mode-coupling effects and selfconsistent mode-coupling theories emerge from the original idea as two markedly different branches of application. Paper presented at the workshop ?Highlights on Simple Liquids?, held in Turin at ISI on 1–3 May, 1989.     

Reaction Kinetics and Oxidation Mechanisms of the Conversion of Pyrite to Ferrous Sulphate: A Mössbauer Spectroscopy Study

Pyrite undergoes a series of exothermic reactions during mine roasting to porous hematite. At low temperatures, the first non-refractive phase to form is ferrous sulphate and could be a cheaper alternative to hematite roasting for the mining industry. In this study, pyrite powder is heated in air at temperatures between 200 and 370 °C for 1 to 256 h in a temperature and time series. The rate of oxidation of pyrite to ferrous sulphate is modelled by combining the Arrhenius equation with the Weibull function to extract reliable thermodynamic data, including the energy of activation, the frequency factor and the overall order of reaction. From the thermodynamic data obtained, two possible oxidation mechanisms are recognized, depending on the bond dissociation energies of the S–S and Fe–S bonds in pyrite.     

The effect of time step,thermostat, and strain rate on ReaxFF simulations of mechanical failure in diamond,graphene, and carbon nanotube

As the sophistication of reactive force fields for molecular modeling continues to increase, their use and applicability has also expanded, sometimes beyond the scope of their original development. Reax Force Field (ReaxFF), for example, was originally developed to model chemical reactions, but is a promising candidate for modeling fracture because of its ability to treat covalent bond cleavage. Performing reliable simulations of a complex process like fracture, however, requires an understanding of the effects that various modeling parameters have on the behavior of the system. This work assesses the effects of time step size, thermostat algorithm and coupling coefficient, and strain rate on the fracture behavior of three carbon‐based materials: graphene, diamond, and a carbon nanotube. It is determined that the simulated stress‐strain behavior is relatively independent of the thermostat algorithm, so long as coupling coefficients are kept above a certain threshold. Likewise, the stress‐strain response of the materials was also independent of the strain rate, if it is kept below a maximum strain rate. Finally, the mechanical properties of the materials predicted by the Chenoweth C/H/O parameterization for ReaxFF are compared with literature values. Some deficiencies in the Chenoweth C/H/O parameterization for predicting mechanical properties of carbon materials are observed. © 2015 Wiley Periodicals, Inc.     

Pulse FT NMR of non-equilibrium states of half-integer spin quadrupolar nuclei in single crystals

For quadrupolar nuclei with spin quantum numbers equal to 3/2, 5/2 and 7/2, the intensities of the NMR transitions in a single crystal are examined as a function of the rf excitation flip angle. Single-quantum NMR intensities are calculated using density matrix theory beginning under various non-equilibrium conditions and are compared with those determined experimentally. As a representative spin-3/2 system, the flip-angle dependence of the ²³Na NMR intensities of a single crystal of NaNO₃ was investigated beginning with the inversion of the populations associated with one of the satellite transitions. Subsequently, the populations of both satellite transitions were inverted using highly frequency-selective hyperbolic secant pulses. Calculated and experimental intensities are in good agreement. As an example of a spin-5/2 system, the flip-angle dependence of the ²⁷Al NMR transition intensities was determined using a single crystal of sapphire, Al₂O₃, starting under different nuclear spin population conditions. The experimental trends mimicked those predicted by the density matrix calculations but the agreement was not as good as for the spin-3/2 case. Some SIMPSON simulations were also carried out to confirm the results generated by our density matrix calculations. The theoretical flip-angle behavior of the NMR transition intensities obtained from a spin-7/2 spin system is also discussed.