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71.
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We have studied by ESR and ENDOR spectroscopy the free radicals produced in γ-irradiated inclusion compound formed between the ketone 10-nonadecanone and urea. Only one type of long lived radical is formed by the removal of an α-proton from the ketone. The hyperfine (hf) coupling constants of the α- and β-protons of the radicals have been measured by ESR at different temperatures in the range 110–292 K and at different orientations of the crystals. The hf coupling of the γ-protons of the radical and of the urea protons have been studied by ENDOR. The temperature and angular dependences of the coupling constants have been analyzed in terms of the internal and overall motions of the radical inside the hexagonal channels formed by the urea molecules. It has been found that the radical cannot perform complete reorientations around the long molecular axis, but it undergoes restricted rotational diffusion. This process is explained by assuming a coupling between the rotational and translational degrees of freedom of the radical inside the urea channels. 相似文献
73.
Cooperative games are considered where only those coalitions of players are feasible that respect a given precedence structure on the set of players. Strengthening the classical symmetry axiom, we obtain three axioms that give rise to a unique Shapley value in this model. The Shapley value is seen to reflect the expected marginal contribution of a player to a feasible random coalition, which allows us to evaluate the Shapley value nondeterministically. We show that every exact algorithm for the Shapley value requires an exponential number of operations already in the classical case and that even restriction to simple games is #P-hard in general. Furthermore, we outline how the multi-choice cooperative games of Hsiao and Raghavan can be treated in our context, which leads to a Shapley value that does not depend on pre-assigned weights. Finally, the relationship between the Shapley value and the permission value of Gilles, Owen and van den Brink is discussed. Both refer to formally similar models of cooperative games but reflect complementary interpretations of the precedence constraints and thus give rise to fundamentally different solution concepts. 相似文献
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Prof. A. D. Drozdov 《Archive of Applied Mechanics (Ingenieur Archiv)》1995,65(2):99-109
Summary Dynamic stability of an elastic bar with voids is considered. Using the Lyapunov approach some new sufficient stability conditions are obtained and explicit expressions for the critical load are derived. 相似文献
77.
Andrzej Kaim 《Journal of polymer science. Part A, Polymer chemistry》2007,45(2):232-241
The competitiveness of the combination and disproportionation reactions between a 1‐phenylpropyl radical, standing for a growing polystyryl macroradical, and a 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) radical in the nitroxide‐mediated free‐radical polymerization of styrene was quantitatively evaluated by the study of the transition geometry and the potential energy profiles for the competing reactions with the use of quantum‐mechanical calculations at the density functional theory (DFT) UB3‐LYP/6‐311+G(3df, 2p)//(unrestricted) Austin Model 1 level of theory. The search for transition geometries resulted in six and two transition structures for the radical combination and disproportionation reactions, respectively. The former transition structures, mainly differing in the out‐of‐plane angle of the N? O bond in the transition structure TEMPO molecule, were correlated with the activation energy, which was determined to be in the range of 8.4–19.4 kcal mol?1 from a single‐point calculation at the DFT UB3‐LYP/6‐311+G(3df, 2p)//unrestricted Austin Model 1 level. The calculated activation energy for the disproportionation reaction was less favorable by a value of more than 30 kcal mol?1 in comparison with that for the combination reaction. The approximate barrier difference for the TEMPO addition and disproportionation reaction was slightly smaller for the styrene polymerization system than for the acrylonitrile polymerization system, thus indicating that a β‐proton abstraction through a TEMPO radical from the polymer backbone could diminish control over the radical polymerization of styrene with the nitroxide even more than in the latter system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 232–241, 2007 相似文献
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Wolfgang Staubach 《Journal d'Analyse Mathématique》2003,91(1):389-400
In this paper, we present an explicit calculation of the heat kernel, fundamental solution and Schwartz kernel of the resolvent
for the Heisenberg Laplacian using Wiener path integrals and their realizations via the Trotter product formula. This also
gives another derivation of mehler’s formula. 相似文献