101 research outputs found
Where is the Limit to which the Qualitative Theory of Chemical Reactivity can be Extended? Study of Dienophilic Activity of Cyanoethylenes
A qualitative quantum-chemical approach, based on the stabilization
energy method, is applied to discuss the mechanism and
some kinetic regularities observed in Diels-Alder (DA) reactions
of cyanoethylenes with cyclopentadiene and phencyclone. For the
former reaction series the polar effect predominates over the localizationeffect and both the regular activity sequence and the great
range of the rate constants can be understood as a result of the
charge transfer from diene to dienophile in a synchronous transition
state (TS). The inversion of the regulaT activity sequence
observed for the latter reaction series seems to be caused by localizationeffects in asynchronous TS. The relative weakening of the
charge transfer is associated with the increased role of electron
correlation. Possible distortions of the TS structure within a
reaction series are analyzed. The shift of the TS a<long the antisymmetricmode appears to be significant and should be taken into
account when considering the kinetic data. The. TS shift along
the symmetric coordinate is negligible. The influence of the prereaction
complex formation on DA reaction kinetics is found to be
inconsequential for the reactions under consideration
Continuous dielectric permittivity II: An Iterative Method for Calculating the Polar Component of the Molecular Solvation Gibbs Energy Under a Smooth Change in the Dielectric Permittivity of a Solution
An iterative method for calculating the polar component of the solvation
Gibbs energy under a smooth change in dielectric permittivity, both between a
substrate and a solvent and in a solvent is formulated on the basis of a
previously developed model. The method is developed in the approximation of the
local relationship D = \eps (r) E between the displacement vectors D and the
electric field intensity E.Comment: 36 pages,3 Figures, in English and in Russia
P-P Total Cross Sections at VHE from Accelerator Data
Comparison of P-P total cross-sections estimations at very high energies -
from accelerators and cosmic rays - shows a disagreement amounting to more than
10 %, a discrepancy which is beyond statistical errors. Here we use a
phenomenological model based on the Multiple-Diffraction approach to
successfully describe data at accelerator energies. The predictions of the
model are compared with data On the basis of regression analysis we determine
confident error bands, analyzing the sensitivity of our predictions to the
employed data for extrapolation. : using data at 546 and 1.8 TeV, our
extrapolations for p-p total cross-sections are only compatible with the Akeno
cosmic ray data, predicting a slower rise with energy than other cosmic ray
results and other extrapolation methods. We discuss our results within the
context of constraints in the light of future accelerator and cosmic ray
experimental results.Comment: 26 pages aqnd 11 figure
Triple F - a comet nucleus sample return mission
The Triple F (Fresh From the Fridge) mission, a Comet Nucleus Sample Return, has been proposed to ESA's Cosmic Vision program. A sample return from a comet enables us to reach the ultimate goal of cometary research. Since comets are the least processed bodies in the solar system, the proposal goes far beyond cometary science topics (like the explanation of cometary activity) and delivers invaluable information about the formation of the solar system and the interstellar molecular cloud from which it formed. The proposed mission would extract three sample cores of the upper 50cm from three locations on a cometary nucleus and return them cooled to Earth for analysis in the laboratory. The simple mission concept with a touch-and-go sampling by a single spacecraft was proposed as an M-class mission in collaboration with the Russian space agency ROSCOSMOS. © The Author(s) 2008
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