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Lawlor DA Bean DE Fowler PW Keeffe JR Kudavalli JS O'Ferrall RA Rao SN 《Journal of the American Chemical Society》2011,133(49):19729-19742
Measurements of pK(R) show that the cycloheptadienyl cation is less stable than the cyclohexadienyl (benzenium) cation by 18 kcal mol(-1). This difference is ascribed here to "hyperaromaticity" of the latter. For the cycloheptadienyl cation a value of K(R) = [ROH][H(+)]/[R(+)] is assigned by combining a rate constant for reaction of the cation with water based on the azide clock with a rate constant for the acid-catalyzed formation of the cation accompanying equilibration of cycloheptadienol with its trifluoroethyl ether in TFE-water mixtures. Comparison of pK(R) = -16.1 with pK(R) = -2.6 for the cyclohexadienyl cation yields the difference in stabilities of the two ions. Interpretation of this difference in terms of hyperconjugative aromaticity is supported by the effect of benzannelation in reducing pK(R) for the benzenium ion: from -2.6 down to -3.5 for the 1H-naphthalenium and -6.0 for the 9H-anthracenium ions, respectively. MP2/6-311+G** and G3MP2 calculations of hydride ion affinities of benzenium ions show an order of stabilities for substituents at the methylene group consistent with their hyperconjugative abilities, i.e., (H(3)Si)(2) > cyclopropyl > H(2) > Me(2)> (HO)(2) > F(2). Calculations of ring currents show a similar ordering. No conventional ring current is seen for the cycloheptadienyl cation, whereas currents in the F(2)-substituted benzenium ion are consistent with antiaromaticity. Arenium ions where the methylene group is substituted with a single OH group show characteristic energy differences between conformations, with C-H or C-OH bonds respectively occupying or constrained to axial positions favorable to hyperconjugation. The differences were found to be 8.8, 6.3, 2.4, and 0.4 kcal mol(-1) for benzenium, naphthalenium, phenanthrenium, and cyclohexenyl cations, respectively. 相似文献
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We outline current developments in our understanding of dynamical arrest, that phenomenon in which many particles stop moving in a collective manner. However in addition to the question of true dynamical arrest itself, we emphasize the development of new tools that can describe relatively sharp changes in the way that ergodic systems may be explored. We discuss the concept of new order parameters (dynamically available volume), and indicate how they may be applied to understand dramatic slowing phenomena present in particle systems, and other arenas of soft and complex matter. 相似文献
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We study the onset of the bootstrap percolation transition as a model of generalized dynamical arrest. Our results apply to two dimensions, but there is no significant barrier to extending them to higher dimensionality. We develop a new importance-sampling procedure in simulation, based on rare events around "holes", that enables us to access bootstrap lengths beyond those previously studied. By framing a new theory in terms of paths or processes that lead to emptying of the lattice we are able to develop systematic corrections to the existing theory and compare them to simulations. Thereby, for the first time in the literature, it is possible to obtain credible comparisons between theory and simulation in the accessible density range. 相似文献
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