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71.
Cláudio P. Ribeiro JR. Benny D. Freeman 《Journal of Polymer Science.Polymer Physics》2010,48(4):456-468
Experimental solubility and sorptive dilation data are reported for carbon dioxide and ethane in a crosslinked poly(ethylene oxide) (XLPEO) rubbery copolymer. Five different temperatures (253 ≤ T(K) ≤ 308) were considered, with a maximum gas pressure of 2.09 MPa (20.6 atm). The polymer was prepared by photopolymerization of a solution containing 70 wt % poly(ethylene glycol) methyl ether acrylate (PEGMEA) and 30 wt % poly(ethylene glycol) diacrylate (PEGDA). Sorption isotherms were described by the Flory‐Huggins model. For each gas, the Flory‐Huggins interaction parameter was a decreasing function of temperature and did not show a composition dependence. Dilation and sorption data were combined to calculate the partial molar volume (PMV) of the gases in the polymer, which was an increasing function of temperature. Based on a comparison with literature data for a XLPEO homopolymer prepared from pure PEGDA over the same range of operating conditions, an effect of the network composition on both gas solubility and PMV was found. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 456–468, 2010 相似文献
72.
73.
The effect of the inclusion of the exact exchange into self-interaction corrected generalized gradient approximation density
functional theory (GGA-DFT) for the simplest hydrogen abstraction reaction, H + H2 → H3 → H2 + H, is presented using a triple-zeta augmented 6-311++G(d,3pd) basis set. The introduction of the self-interaction correction has a considerably larger effect on molecular geometry and
vibrational frequencies than the inclusion of the exact exchange. We investigate the influence of the self-interaction error
on the shape of the potential energy surface around the transition state of the hydrogen abstraction reaction. The decomposition
of the self-interaction error into correlation and exchange parts shows that the exchange self-interaction error is the main
component of the energy barrier error. The best agreements with the experimental barrier height were achieved by self-interaction
corrected B3LYP, B-LYP and B3PW functionals with errors of 1.5, 2.9 and 3.0 kcal/mol, respectively.
Received: 13 August 1997 / Accepted: 14 November 1997 相似文献
74.
Billups WE Luo W Lee GA Chee J Arney BE Wiberg KB Artis DR 《The Journal of organic chemistry》1996,61(2):764-770
Bicyclo[4.1.0]hept-1,6-ene has been generated by elimination of 1-chloro-2-(trimethysilyl)bicyclo[4.1.0]heptane in the gas phase over solid fluoride at 25 degrees C. The cyclopropene dimerizes by a rapid ene reaction forming two diastereomeric cyclopropenes. In tetrahydrofuran or chloroform the ene dimers couple to form a single crystalline triene tetramer, whereas a mixture of tricyclohexane tetramers is formed when the neat dimers are allowed to warm to room temperature. Oxidation by dimethyldioxirane or dioxygen gives carbonyl products. Quantum mechanical calculations yielded an increase in strain of approximately 17 kcal/mol over that for 1,2-dimethylcyclopropene. The potential enegy barrier to flexing (folding) along the fused double bond of bicyclo[4.1.0]hept-1,6-ene is only approximately 1 kcal/mol at the highest level of theory investigated. 相似文献
75.
Kazukiyo Nagai Benny D. Freeman Anita J. Hill 《Journal of Polymer Science.Polymer Physics》2000,38(9):1222-1239
The effect of physical aging on the gas permeability, fractional free volume (FFV), and positron annihilation lifetime spectroscopy (PALS) parameters of dense, isotropic poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) films synthesized with TaCl5 and NbCl5 was characterized. As‐cast films were soaked in methanol until an equilibrium amount of methanol was absorbed by the polymer. When the films were removed from methanol, film thickness initially decreased rapidly and was almost constant after 70 h in air for both catalysts. This timescale was much longer than the timescale for complete methanol desorption (ca. 5 h). From the film‐thickness data, the reduction in FFV with time was estimated. For samples prepared with either catalyst, the kinetics of FFV reduction were well‐described by a simple model based on the notion either that free‐volume elements diffuse to the surface of the polymer film and are subsequently eliminated from the sample or that lattice contraction controls polymer densification. Methane permeability decreased rapidly during the first 70 h, which was the same timescale for the thickness change. The decrease in methane permeability was smaller in films prepared with NbCl5 than with TaCl5. The logarithm of methane permeability decreased linearly as reciprocal FFV increased, in accordance with free‐volume theory. The PALS results indicate that the concentration of larger free‐volume elements (as indicated by the intensity I4) decreased with aging time and that the other PALS parameters were not strongly influenced by aging. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1222–1239, 2000 相似文献
76.
For a pair of integers 1≤γ<r, the γ-chromatic number of an r-uniform hypergraph H=(V, E) is the minimal k, for which there exists a partition of V into subsets T1,…,Tk such that |e∩Ti|≤γ for every e∈E. In this paper we determine the asymptotic behavior of the γ-chromatic number of the random r-uniform hypergraph Hr(n, p) for all possible values of γ and for all values of p down to p=Θ(n−r+1). © 1998 John Wiley & Sons, Inc. Random Struct. Alg., 12: 381–403, 1998 相似文献
77.
Benny Sudakov 《Random Structures and Algorithms》2005,26(3):253-265
In this paper we present three Ramsey‐type results, which we derive from a simple and yet powerful lemma, proved using probabilistic arguments. Let 3 ≤ r < s be fixed integers and let G be a graph on n vertices not containing a complete graph Ks on s vertices. More than 40 years ago Erd?s and Rogers posed the problem of estimating the maximum size of a subset of G without a copy of the complete graph Kr. Our first result provides a new lower bound for this problem, which improves previous results of various researchers. It also allows us to solve some special cases of a closely related question posed by Erd?s. For two graphs G and H, the Ramsey number R(G, H) is the minimum integer N such that any red‐blue coloring of the edges of the complete graph KN, contains either a red copy of G or a blue copy of H. The book with n pages is the graph Bn consisting of n triangles sharing one edge. Here we study the book‐complete graph Ramsey numbers and show that R(Bn, Kn) ≤ O(n3/log3/2n), improving the bound of Li and Rousseau. Finally, motivated by a question of Erd?s, Hajnal, Simonovits, Sós, and Szemerédi, we obtain for all 0 < δ < 2/3 an estimate on the number of edges in a K4‐free graph of order n which has no independent set of size n1‐δ. © 2004 Wiley Periodicals, Inc. Random Struct. Alg., 2005 相似文献
78.
A new phase-shifting interferometric technique that uses an unknown phase step is described in which the phase step is determined by use of an algorithm called Probabilistic Global Search Lausanne (PGSL). One of the main sources of error in phase stepping is piezoelectric device (PZT) nonlinearity. The PGSL algorithm identifies the characteristics of the response of the PZT to the applied voltage through matching predicted and measured responses. The unknown phase step is also calculated with 0.097% error. This approach overcomes the limitations of existing techniques to determine unknown phase steps. Linear regression is subsequently applied for interference phase determination. 相似文献
79.
80.
We study the relation between stochastic and continuous transport-limited growth models. We derive a nonlinear integro-differential equation for the average shape of stochastic aggregates, whose mean-field approximation is the corresponding continuous equation. Focusing on the advection-diffusion-limited aggregation (ADLA) model, we show that the average shape of the stochastic growth is similar, but not identical, to the corresponding continuous dynamics. Similar results should apply to DLA, thus explaining the known discrepancies between average DLA shapes and viscous fingers in a channel geometry. 相似文献