Fluorides of ruthenium and chromium: Theoretical studies

The electronic and structural characteristics of CrF₅, CrF₄, RuF₅ and RuF₄ were studied. Ab initio (SCF-CI) calculations were performed with different structures and spin states for each complex. The favored conformation always corresponds to the highest multiplicity: doublet for CrF₅ in D_3h, triplet for CrF₄ in T_d, quadruplet for RuF₅ in C_4v and quintuplet for RuF₄ in D_4h symmetry.     

Two-dimensional Numerical Simulation of the Beam-Plasma-Discharge

A two-dimensional self consistent model of the Beam-Plasma-Discharge (BPD) has been developed to calculate the discharge ignition of a bandlike electron beam in a discharge chamber. The discharge was considered in Argon with an initial concentration of 10¹⁴ cm^?3. The model allows calculation of the time evolution of perpendicular profiles of electron density, temperature and the potential.     

Transport of gases in aromatic polyesters: Correlation with WAXD studies

Polymer packing density can be conveniently measured by either density-based measurements (direct or estimated free volume) or wide-angle X-ray diffraction (WAXD) spectra. Previously reported diffusivity and permeability values for various polyarylates and polyimides are examined on the basis of the packing density measured by these different techniques. It is shown that in these rigid glassy polymers, the mean intersegmental distance, the d-spacing, obtained from WAXD provides a better measure of the effect of polymer packing on diffusivity than either direct density measurements or estimated free volumes. It has been possible to correlate previously reported diffusivity and sorption data for various polyarylates and polycarbonate on the basis of the WAXD investigation, using the d-spacing and the amorphous peak width, respectively. The effect of polyarylate structure on d-spacing has been studied. A series of polyarylates have been synthesized with different substituents on the bridge carbon. In this series the d-spacing remains constant while the carbonyl group density and the glass transition temperatures are varied. However, small substituents on the aromatic ring cause significant changes in the d-spacing. These results can be used to tailor polyarylates with desired intersegmental distances and chain flexibility.     

Scanning LLL x-ray interferometry

A new formalism is presented for the theory of scanning LLL x-ray interferometry, which takes account also of the amount of x-ray absorption and of crystal yawing. It is based on the Takagi approach to the dynamical theory of x-ray diffraction and uses, to a great extent, the formalism of quantum mechanics, in order to reduce the algebraic complexity of the Ewald-von Laue approach. The formalism presented here is an easy-to-handle tool for the study of x-ray propagation in multicrystal systems and for the investigation into deviations of the travelling-fringe period from the spacing of diffracting planes, as it explains how interference features change when moving in paramater space.     

Spectroscopic imaging display and analysis.

A system for display of magnetic resonance (MR) spectroscopic imaging (SI) data is described which provides for efficient review and analysis of the multidimensional spectroscopic and spatial data format of this technique. Features include the rapid display of spectra from selected image voxels, formation of spectroscopic images, spectral and image data processing operations, methods for correlating spectroscopic image data with high resolution 1H MR images, and hardcopy facilities. Examples are shown for 31P and 1H spectroscopic imaging studies obtained in human and rat brain.     

Inertia-preserving secant updates

Corrections to the last two equations of Ref. 1 are given.     

Short-range order in miscible polymer blends: A monte carlo study

Local ordering in miscible binary polymer blends with strong attractive interactions between the two types of chains was investigated by computer simulation of allowable conformations on an incompressible cubic lattice. A tendency toward maximum ordering (in which chains pack in alternate parallel rows) is shown by the calculation of pair correlations and in “snapshots” of the mixtures. A specific directional interaction is not necessarily required for ordering. A comparison of these results with those recently obtained using mean-field theory is presented. The heat capacity of mixing was also calculated and found to be positive, with a value close to that reported experimentally.     

A model of the kinetics of macrocyclic BPA carbonate formation

Cyclic oligocarbonates are synthesized by two-phase interfacial reactions of aryl bischloroformates in the presence of an amine phase transfer catalyst and an alkali: nClOCOArOCOCl + 4nNaOH → (OArOCO)_n + 2nNaCl + nNa₂CO₃ + 2nH₂O. The organocarbonate product may be a macrocyclic oligomer or a linear chain polymer. A qualitative mechanism for this behavior has been proposed by Brunelle, Boden, and co-workers. Four steps are identifiable: activation of the aryl bischloroformate by the amine catalyst, hydrolysis of a portion of this intermediate at the aqueous/organic phase interface, oligomerization between activated and hydrolyzed moieties also at the interface, and chain terminating carbamate formation that leads to polymer. An important modification is made within the framework of the Brunelle and Boden mechanism. While the intramolecular cyclization reaction is formally second-order overall, it behaves as a first-order process. The kinetic constants for both this pseudo-first-order cyclization step and the corresponding second-order linearization step are simply related. It is speculated that the above relationship can be generalized for a whole class of pseudo-first- and second-order rate constants for similar macrocyclic reactions.     

Models of linear logic

We engage a study of nonmodal linear logic which takes times ⊗ and the linear conditional ⊸ to be the basic connectives instead of times and linear negation ()^⊥ as in Girard's approach. This difference enables us to obtain a very large subsystem of linear logic (called positive linear logic) without an involutionary negation (if the law of double negation is removed from linear logic in Girard's formulation, the resulting subsystem is extremely limited). Our approach enables us to obtain several natural models for various subsystems of linear logic, including a generic model for the so-called minimal linear logic. In particular, it is seen that these models arise spontaneously in the transition from set theory to multiset theory. We also construct a model of full (nonmodal) linear logic that is generic relative to any model of positive linear logic. However, the problem of constructing a generic model for positive linear logic remains open. Bibliography: 2 titles. Published inZapiski Nauchnykh Seminarov POMI, Vol. 220, 1995, pp. 23–35. Original     

A projective criterion to the coordinate partitioning method for multibody dynamics

Summary The paper discusses some developments in the coordinate partitioning method for the dynamic analysis of constrained/closed-loop multibody systems. First, the method is reformulated to a more compact form. Then, a simple and reliable projective criterion for choosing the best coordinates from the redundant ones is proposed, and some advantages are pointed out that may arise in the method by applying inverse kinematics algorithms. Finally, the problem of determination ofphysical reactions of constraints and closing conditions is discussed. A four-bar linkage mechanism serves for an illustration of some aspects of the paper.

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Ein Projektionskriterium zur Koordinatenwahl bei Mehrkörpersystemen mit kinematischen Schleifen

Übersicht Bei der Simulation der Bewegunsgleichungen von Mehrkörpersystemen mit kinematischen Schleifen in Minimalform stellt sich die Frage nach der Wahl günstiger verallgemeinerter Koordinaten. Hierfür wird ein Projektionskriterium vorgeschlagen, welches die Trennung der systembeschreibenden redundanten Koordinaten in die verallgemeinerten und davon abhängige Koordinaten gestattet. Durch Anwendung eines Verfahrens zur Rückwärtstransformation der kinematischen Beschreibung lassen sich in diesen explizite Schließbedingungen formulieren, was sich bei der Simulation vorteilhaft auswirkt; diese kann ohne Verletzung der Schließbedingungen erfolgen. Es wird auch gezeigt, wie auch bei Verwendung verallgemeinerter Koordinatenphysikalisch interpretierbare Reaktionen ermittelt werden können. Als Anwendungsbeispiel dient ein ebenes Viergelenk.

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On leave from the Department of Mechanics, Technical University of Radom, ul. Malczewskiego 29, 26-600 Radom, Poland