Group divisible designs with three unequal groups and larger first index

We show the necessary conditions are sufficient for the existence of group divisible designs (or PBIBDs) with block size k=3 with three groups of size (n,2,1) for any n≥2 and any two indices with λ₁>λ₂.     

Integral equation formulation for buoyancy-driven convection problems

An integral equation formulation for buoyancy-driven convection problems is developed and illustrated. Buoyancy-driven convection in a bounded cylindrical geometry with a free surface is studied for a range of aspect ratios and Nusselt numbers. The critical Rayleigh number, the nature of the cellular motion, and the heat transfer enhancement are computed using linear theory. Green's functions are used to convert the linear problem into linear Fredholm integral equations. Theorems are proved which establish the properties of the eigenvalues and eigenfunctions of the linear integral operator which appears in these equations.     

Cadmium

Ohne Zusammenfassung     

Galvanomagnetic effects in anisotropic metals

The aim of this article is to present an introductory review of those aspects of the isothermal galvanomagnetic effects in metals (which here means the electrical resistance, magnetoresistance and Hall effect) which are peculiar to the existence of an anisotropic electrical conductivity. This anisotropy may be intrinsic to the solid, such as that arising from a non-cubic crystal structure, or it may be induced by the application of the external magnetic field. Such induced anisotropy can itself be divided into two classes : that arising directly from the effect of the Lorentz force upon the itinerant electrons, and that in which the external field is merely an agent which makes evident on a macroscopic scale an anisotropy which exists microscopically, even in the field-free case. The article traces the usual phenomenological formulation of the galvanomagnetic effects, and then particularizes this to the commonly-encountered experimental situations used to study the consequences of both induced and intrinsic anisotropy. The final section consists of a comprehensive compilation of relevant literature, arranged under the headings for the individual elemental metals and semimetals.     

A note on scalar Hertz potentials for gyrotropic media

The scalar Hertz potentials are generalized to the case of electromagnetic fields in gyrotropic media. Expressions for electromagnetic fields in terms of two potentials are presented and the system of differential equations for the potentials is derived. The result are summarized in the form of a theorem. The case of a stratified gyrotropic medium with parameters varying along the distinguished axis has been considered also. Scalar “superpotentials” satisfying a fourth-order partial differential equation are introduced. They allow expressions for electromagnetic fields to be found in terms of one scalar superpotential only. Basic results on scalar Hertz potentials in isotropic media are recalled. The research reported in this paper was carried out during S. Przeździecki's leave of absence from the Institute of Fundamental Technological Research, Polish Academy of Sciences, Świętokryzyska 21, PL-00-049 Warszawa, Poland.     

Trajectory integration with potential energy discontinuities

Many approximate methods of quantum chemistry yield potential energy surfaces with discontinuities. While clearly unphysical, such features often fall within the typical error bounds of the method, and cannot be easily eliminated. The integration of nuclear trajectories when the potential energy is locally discontinuous is obviously problematic. We propose a method to smooth out the discontinuities that are detected along a trajectory, based on the definition of a continuous function that fits locally the computed potential, and is used to integrate the trajectory across the discontinuity. With this correction, the energy conservation error can be reduced by about one order of magnitude, and a considerable improvement is obtained in the energy distribution among the internal coordinates.     

Group divisible designs with block size four and two groups

We give some constructions of new infinite families of group divisible designs, GDD(n,2,4;λ₁,λ₂), including one which uses the existence of Bhaskar Rao designs. We show the necessary conditions are sufficient for 3?n?8. For n=10 there is one missing critical design. If λ₁>λ₂, then the necessary conditions are sufficient for . For each of n=10,15,16,17,18,19, and 20 we indicate a small minimal set of critical designs which, if they exist, would allow construction of all possible designs for that n. The indices of each of these designs are also among those critical indices for every n in the same congruence class mod 12.     

Dications of fluorenylidenes. The relationship between redox potentials and antiaromaticity for meta- and para-substituted diphenylmethylidenefluorenes

[reaction: see text] Electrochemical oxidation of meta-substituted diphenylmethylidenefluorenes (3a-g) results in the formation of fluorenylidene dications that are shown to be antiaromatic through calculation of the nucleus independent chemical shift (NICS) for the 5- and 6-membered rings of the fluorenyl system. There is a strong linear correlation between the redox potential for the dication and both the calculated NICS and sigma(m). Redox potentials for formation of dications of analogously substituted tetraphenylethylenes shows that, with the exception of the p-methyl derivative, the redox potentials for these dications are less positive than for formation of the dications of 3a-g and for dications of p-substituted diphenylmethylidenefluorenes, 2a-g. The greater instability of dications of 2a-g and 3a-g compared to the reference system implies their antiaromaticity, which is supported by the positive NICS values. The redox potentials for formation of the dications of meta-substituted diphenylmethylidenes (3a-g) are more positive than for the formation of dications of para-substituted diphenylmethylidenes (2a-g), indicating their greater thermodynamic instability. The NICS values for dications of 3a-g are more antiaromatic than for dications of 2a-g, which is consistent with their greater instability of the dications of 3a-g. Although the substituted diphenylmethyl systems are not able to interact with the fluorenyl system through resonance because of their geometry, they are able to moderate the antiaromaticity of the fluorenyl cationic system. Two models have been suggested for this interaction, sigma to p donation and the ability of the charge on the substituted ring system to affect delocalization. Examination of bond lengths shows very limited variation, which argues against sigma to p donation in these systems. A strong correlation between NICS and sigma constants suggests that factors that affect the magnitude of the charge on the benzylic (alpha) carbon of the diphenylmethyl cation affect the antiaromaticity of the fluorenyl cation. Calculated atomic charges on carbons 1-8 and 10-13 show an increase in positive charge, and therefore greater delocalization of charge in the fluorenyl system, with increasing electronegativity of the substituent. The change in the amount of positive charge correlated strongly with NICS, supporting the model in which the amount of delocalization of charge is related to the antiaromaticity of the species. Thus, both aromatic and antiaromatic species are characterized by extensive delocalization of electron density.