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An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol?1)·T?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. 相似文献
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Abstract Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood. 相似文献
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Joaquín Barberá Mariel A. Godoy Paulina I. Hidalgo José A. Ulloa Jorge M. Vergara 《Liquid crystals》2013,40(6):679-688
Novel liquid crystal materials based on 1,3,5-benzenetrisamide derivatives with three pendant 2-phenyl-5-(mono-, di-, and/or tri-n-alkoxyphenyl)-1,3,4-oxadiazole arms (Ia–c, IIa–c) were prepared. The mesomorphic properties of these compounds were characterised and studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. The formation of a columnar mesophase was found to be dependent on the number of alkoxy side chains. The compounds Ib and IIb, with a total of six alkoxy chains, and compounds Ic and IIc, with nine alkoxy chains, exhibited an enantiotropic hexagonal columnar (Colh ) phase with high isotropisation temperatures; however, compounds Ia and IIa with a total of three alkoxy chains formed a crystalline phase. Compounds IIb and c were room temperature liquid crystals. 相似文献
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Novel liquid crystal materials base on amino-thiadiazoles, specifically 5-(3,4-di-, and/or 3,4,5-tri-n-alkoxy)phenyl-2-amino-1,3,4-thiadiazoles (3a–f, n?=?10, 12, 14) and 5-(3,4-di- and/or 3,4,5-tri-n-alkoxy)phenyl-2-(4-amino)phenyl-1,3,4-thiadiazoles (6a–f, n?=?10, 12, 14) were synthesised. The mesomorphic properties of these compounds were studied by differential scanning calorimetry and polarising optical microscopy. All the compounds in series 3a–f and series 6a–f display an enantiotropic columnar phase. The mesomorphic properties were found to be dependent on the number of the side alkoxy chains, and on the length of the rigid core, and on the position of the thiadiazole ring. The best results were obtained with compounds of series 3a–f. 相似文献
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We develop a realistic model of Rabi oscillations in a quantum-dot photodiode. Based in a multiexciton density matrix formulation we show that for short pulses the two-level model fails and higher levels should be taken into account. This affects some of the experimental conclusions, such as the inferred efficiency of the state rotation (population inversion) and the deduced value of the dipole interaction. We also show that the damping observed cannot be explained using constant rates with fixed pulse duration. We demonstrate that the damping observed is in fact induced by an off-resonant excitation to or from the continuum of wetting layer states. Our model describes the nonlinear decoherence behavior observed in recent experiments. 相似文献
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Luis G.G.V. Dias da Silva Sergio E. Ulloa Tigran V. Shahbazyan 《Physica E: Low-dimensional Systems and Nanostructures》2006,32(1-2):37
We study the interplay between impurity scattering and Coulomb interaction effects in the absorption spectrum of neutral bound magnetoexcitons confined in quantum-ring structures. Impurity scattering breaks the rotational symmetry of the ring system, introducing characteristic features in the optical emission. Signatures of the optical Aharonov–Bohm effect are still present for weak scattering and strong Coulomb screening. Furthermore, an impurity-induced modulation of the absorption strength is present even for a strong impurity potential and low screening. This behavior is likely responsible of recent experimental observations in quantum-ring structures. 相似文献