Recent developments in the chemistry of stable doubly bonded germanium compounds

During the last 10 years, several compounds of the type Ge=X (X = C, Ge, N, P, S) have been isolated as monomers. The stabilization of such derivatives, which are generally highly polymerizable, was achieved by using very bulky groups both on the germanium atom and on the heteroelement X. Conjugation (particularly in a few germenes and germaimines) and intramolecular or intermolecular coordination with oxygen or nitrogen, also contributes, in some cases, to the stabilization. The X-ray analyses of such compounds show a significant bond shortening of the double bond (8–10%) relative to the corresponding single bond and a planar or nearly planar germanium. These doubly bonded germanium derivatives are usually thermally stable but must be handled in an inert atmosphere because of their high sensitivity to oxygen and moisture; they are extremely reactive, much more than the corresponding carbon analogues. Nearly quantitative additions on the double bond have been observed with electrophiles and nucleophiles, and various types of cycloadditions also occur. Except in one case, a germylene behavior has not been observed, proving that such compounds retain their structural integrity in solution.     

Why define atoms in real space?

The physics of a system is determined by a variation of the action integral, i.e., by a variation of the space–time volume integral of the Lagrange function. If one demands that the properties of an atom in a molecule be derived from physics, the atom must generate its own space–time volume, requiring that its boundaries be defined in real space. The variations in the action are related to the actions of generators of infinitesimal unitary transformations. In the general case, the action integral is altered by generators acting in both the spacelike and timelike surface bounding the space–time volume, whereas for a total isolated system, the physics is totally determined by their action in just the spacelike surfaces at the two time endpoints. It is shown and illustrated for a one-dimensional system that the definition of an atom corresponds to the possibility of choosing a subsystem in such a way that the contributions to the change in action resulting from the evolution in time of its spatial boundaries vanishes identically. The properties of these subsystems and of the total system of which they are a part are, therefore, determined by one and the same action principle. This choice of subsystem corresponds to the possibility of augmenting the Lagrange function by the divergence of the gradient of the electron density a step that, while leaving the equations of motion unchanged, modifies the generating operators in the required manner. © 1994 John Wiley & Sons, Inc.     

Convex functions, subdifferentiability and renormings

This paper through discussing subdifferentiability and convexity of convex functions shows that a Banach space admits an equivalent uniformly [locally uniformly, strictly] convex norm if and only if there exists a continuous uniformly [locally uniformly, strictly] convex function on some nonempty open convex subset of the space and presents some characterizations of super-reflexive Banach spaces. Supported by NSFC     

Three-dimensional atom probe study of the segregation behaviour of Ni91Pt9 alloy after sputtering

To investigate local ordering and segregation phenomenon in a Ni91Pt9-alloy after sputtering and annealing a 3D optical atom probe (OAP) has been used. The specimen tips have been prepared from polycrystalline samples. To sputter the samples a separate preparation chamber with a scannable Ar-sputter-gun is connected to the OAP vessel. When necessary, the sample can be electrically heated to induce segregation and cure the altered layer. After a heat treatment of a Ni91 at. %Pt 9 at.% specimen at 1100 K the surface of a (111)-oriented specimen is enriched in platinum by a factor of two in relation to the bulk. The phenomenon of short-range ordering has been investigated on the surface and in the subsurface volume. A 3D reconstruction of this annealed NiPt specimen shows regions with high concentration of platinum that gives an indication at short-range ordering. Uniform sputtering of the tip without a heat treatment induces a decisive depletion of Pt on the surface and the following subatomic layers. The atom-probe results of specimens in thermal equilibrium are in close agreement to further surface sensitive results obtained from Ion Scattering Spectroscopy (ISS) and Auger Electron Spectroscopy (AES).     

The lead tetraacetate oxidation of bisacylhydrazones of α-diketones: A scope re-assesment

Oxidation of the title compounds yields, besides the reported isoimides 3 and/or the amides 4 , also the imides 5 . The observed product dichotomy is considered as the result of an intramolecular nucleophilic attack on the aroyl group, of the pressumed zwitterionic intermediate 2 , by O or N present in the ambident N-aroylimine site of 2 . The results of AM1 calculations agree with the product studies and both permit the formulation of a set of rules correlating structure and selectivity.     

A semi-analytical numerical method for time-dependent radiative transfer problems in slab geometry with coherent isotropic scattering

We describe a semi-analytical numerical method for coherent isotropic scattering time-dependent radiative transfer problems in slab geometry. This numerical method is based on a combination of two classes of numerical methods: the spectral methods and the Laplace transform (LTS_N) methods applied to the radiative transfer equation in the discrete ordinates (S_N) formulation. The basic idea is to use the essence of the spectral methods and expand the intensity of radiation in a truncated series of Laguerre polynomials in the time variable and then solve recursively the resulting set of “time-independent” S_N problems by using the LTS_N method. We show some numerical experiments for a typical model problem.