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101.
The photochemistry of 1,2-dihydronaphthalene oxide (254 nm) was reexamined and indan was found to be a primary photoproduct, as well as the traditionally assumed secondary photoproduct. Quenching studies demonstrated that indan, as a primary photoproduct, is derived from a triplet pathway, competing with a singlet route, back to the ground state surface. CASSCF calculations strongly suggest that the triplet pathway consists of a dissociation of the oxirane moiety to give a triplet carbene and aldehyde, which via hydrogen abstraction-decarbonylation-ISC recloses to give indan. Conical intersections corresponding to the presumed 1,2-hydrogen shift and 1,2-alkyl shift to give 2-tetralone and 1-indancarbaldehyde, respectively, were located computationally.  相似文献   
102.
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   
103.
We prove that quantile functions on spaces of random variables satisfy the Lipschitz condition with constant 1 with respect to any norm on a subspace of a space of random variables that majorizes L-norm. The considered random variables not necessarily belong to this Banach space. Bibliography: 3 titles. __________ Translated from Zapiski Nauchnykh Seminarov POMI, Vol. 351–358, 2008, pp. 253–258.  相似文献   
104.
105.
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   
106.
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   
107.
The effect of flow intensification in small-sized vortex cells on the flow pattern in the near wake downstream of a cylinder and the cylinder drag in laminar and turbulent flows is analyzed on the basis of a numerical simulation of the two-dimensional steady-state flow past a circular cylinder with rotating cylindrical bodies built into the cylinder contour. St. Petersburg, Saratov. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 4, pp. 88–96, July–August, 2000. The study was carried out with the support of the Russian Foundation for Basic Research (projects Nos. 99-01-01115 and 99-01-00772).  相似文献   
108.
The amplitudes of the spatial harmonics of the field are calculated for given displacements of the electrodes in a quadrupole mass filter relative to their optimum positions. The cases of radial and angular displacements of the electrodes, asymmetries in voltage supplied to the electrodes, and nonidentical rod diameters are considered. These data are required for calculating the actual shape of the mass peaks and will be useful in designing mass filters. Zh. Tekh. Fiz. 69, 96–101 (October 1999)  相似文献   
109.
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   
110.
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 |eTi|≤γ for every eE. 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(nr+1). © 1998 John Wiley & Sons, Inc. Random Struct. Alg., 12: 381–403, 1998  相似文献   
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