Computational advances in organic chemistry: Molecular structure and reactivity. Edited by C. Ögretir and I. G. Csizmadia,NATO ASI Series C,Vol, 330.

We here report an AM 1 study for the reaction of different types of radicals with the acetone enolate ion 1 and other ambident nucleophiles. The theoretical reactivity order determined is phenyl > methyl > tert-butyl ? bicyclo-[2.2.1]hept-1-yl. The activation energy for the coupling of aliphatic radicals is ascribed mainly to nonbonded interactions. Considering possible solvent effects, we propose the same order of reactivity in solution. The coupling reaction of phenyl radical with 1 is an exothermic process with nonactivation energy in the gas phase. Any energy barrier in solution is here ascribed to desolvation of the anion. The regiochemistry of the coupling of radicals with ambident nucleophiles such as 1 , phenoxide, or phenylamide anions is also explained on a theoretical basis. © 1992 John Wiley & Sons, Inc.     

Continuous removal of radiolytic products from TBP extraction systems

In the actinide separation process using TBP as extractant, hydrolytic and radiolytic reactions cause a gradual decomposition of the extractant, resulting in the formation of degradation products which can affect process performance adversely. The TBP diluent has to be cleaned from these degradation products before it is reused. This paper deals with a procedure for solvent cleanup, using a fourstage continuous contactor for increasing the scrubbing efficiency.     

Classical Coulomb fluids in a confined geometry

It has already been argued that a classical (three-dimensional) Coulomb fluid confined between two parallel walls exhibits ideal gas features when the distance between the walls becomes small; this is confirmed in the present paper. Two-dimensional models of Coulomb fluids (with a logarithmic interaction), confined in a strip, are also studied. These models do not become ideal gases in the narrow strip limit. The correlation functions are also studied. There is a special temperature at which exact results are obtained. At that temperature, the two-dimensional, two-component plasma (two-dimensional Coulomb gas), which is a conductor when unconfined, becomes a dielectric as soon as it is confined in a strip of noninfinite width. This can be understood as a displacement of the Kosterlitz-Thouless transition by the confinement.     

Special geometry,cubic polynomials and homogeneous quaternionic spaces

The existing classification of homogeneous quaternionic spaces is not complete. We study these spaces in the context of certainN=2 supergravity theories, where dimensional reduction induces a mapping betweenspecial real, Kähler and quaternionic spaces. The geometry of the real spaces is encoded in cubic polynomials, those of the Kähler and quaternionic manifolds in homogeneous holomorphic functions of second degree. We classify all cubic polynomials that have an invariance group that acts transitively on the real manifold. The corresponding Kähler and quaternionic manifolds are then homogeneous. We find that they lead to a well-defined subset of the normal quaternionic spaces classified by Alekseevskiî (and the corresponding special Kähler spaces given by Cecotti), but there is a new class of rank-3 spaces of quaternionic dimension larger than 3. We also point out that some of the rank-4 Alekseevskiî spaces were not fully specified and correspond to a finite variety of inequivalent spaces. A simpler version of the equation that underlies the classification of this paper also emerges in the context ofW ₃ algebras.Communicated by K. Gawedzki     

Formant frequency discrimination by Japanese macaques (Macaca fuscata).

These studies investigated formant frequency discrimination by Japanese macaques (Macaca fuscata) using an AX discrimination procedure and techniques of operant conditioning. Nonhuman subjects were significantly more sensitive to increments in the center frequency of either the first (F1) or second (F2) formant of single-formant complexes than to corresponding pure-tone frequency shifts. Furthermore, difference limens (DLs) for multiformant signals were not significantly different than those for single-formant stimuli. These results suggest that Japanese monkeys process formant and pure-tone frequency increments differentially and that the same mechanisms mediate formant frequency discrimination in single-formant and vowel-like complexes. The importance of two of the cues available to mediate formant frequency discrimination, changes in the phase and the amplitude spectra of the signals, was investigated by independently manipulating these two parameters. Results of the studies indicated that phase cues were not a significant feature of formant frequency discrimination by Japanese macaques. Rather, subjects attended to relative level changes in harmonics within a narrow frequency range near F1 and F2 to detect formant frequency increments. These findings are compared to human formant discrimination data and suggest that both species rely on detecting alterations in spectral shape to discriminate formant frequency shifts. Implications of the results for animal models of speech perception are discussed.     

Observation of sharp resistance anomalies near Tc in granular superconductors

Granular films prepared from well-defined In clusters embedded in Kr (? 10-40 at % Kr) show sharp resistance anomalies very close to the superconducting transition temperature. The observed resistance peak(s), which go(es) above the normal state resistance R_N and which can be as high as ? 1.5 R_N, can be explained by a “mesoscopic” effect: Superconducting percolation aggregates of size ξ_ρ, larger than the superconducting coherence length ξ_S, but smaller than the quasiparticle relaxation length λ_Q*, have a superconducting gap, but are not yet able to carry a supercurrent.     

Regions of stability of high-power gyrotron oscillators

The problem of mode competition in a high-power gyrotron oscillator is considered. The regions of parameter space in which a preexisting large-amplitude mode is able to suppress competing satellites are determined for cases in which the coupling coefficients and cavity quality factors for the operating and satellite modes are different. In addition, the effect of beam quality on the regimes of stable single-mode operation is investigated. Generally speaking, the requirement of stable operation favors devices whose interaction length measured by the parameter μ is not too large. It is found that for μ near 10 the operation is relatively stable and μ near 17 is not     

On the localization of topological invariants

The approach of formal differential geometry to the topological invariants which can be localized is developed. The universal space and universal characteristic forms are constructed. They give rise to primary and secondary characteristic forms.