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51.
The gas‐phase acidities (GA) of various aryl‐substituted fluoroalkanes, XC6H4CH(R1)R2, were calculated at the B3LYP/6‐311 + G(d,p)//B3LYP/6‐311 + G(d,p). The acidity values of alkanes having a common substituent X varied significantly with the change of R1 and R2. Their changes in acidity of 1 and 2 having two strong electron‐withdrawing groups (CF3 or C2F5) at the deprotonation site and 8 , 9 , 10 , 11 having no fluorine atom at β‐position were linearly correlated with the corrected number of fluorine atoms contained in the fluorinated alkyl group (R2 > 0.999). On the other hand, the GA values of β‐fluorine substituted alkanes ( 3 , 4 , 5 , 6 , 7 ) deviated in a stronger acid direction from the line. The enhanced acidity was attributed to the additional stabilization of the conjugate anion caused by the β‐fluorine negative hyperconjugation. The magnitude of β‐fluorine negative hyperconjugation of the fluorinated alkyl group (ΔGoβ‐F) given by the deviations from the line decreased with increasing electron‐withdrawing ability of substituent X on the benzene ring, indicating that β‐fluorine negative hyperconjugation competes with the electronic effect of the substituent X. The GAel values obtained by subtraction ΔGoβ‐F from the apparent GA value were successfully correlated in terms of the Yukawa–Tsuno equation. The obtained ρel and r?el values were linearly related to the GAel value of the respective phenyl‐substituted fluoroalkanes, supporting our previous conclusion that the ρ and r? values for the substituent effect caused by the electronic effects of the substituent on the acidity are determined by the thermodynamic stability of the parent ion (ring substituent = H). Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
52.
Masaaki Yamabe 《Macromolecular Symposia》1992,64(1):11-18
Perfluoro(vinyl ether) derivatives are extremely versatile monomers in preparing a variety of functional fluoropolymers. In this paper, two challenging topics in the development of novel fluoropolymers will be introduced. Carboxylated perfluoro(vinyl ether) can be copolymerized with tetrafluoroethylene to afford perfluorinated ion-exchange membranes, which realize the innovative process for pollution-free and energy-saving chlor-alkali production. Another topic includes the discovery of selective cyclo-polymerization of specially designed difunctional perfluoromonomers such as perfluoro(allyl vinyl ether) which is readily derived from the carboxylated perfluoro(vinyl ether). The novel perfluoropolymer with a cyclic structure in the main chain is characterized by an exceptional transparency, and has been commercialized with expectation of major applications in electronics industries. 相似文献
53.
54.
Chlorine isotope fractionation factor was determined by strongly basic anion-exchange chromatography with 0.1 mol/l HCl at 25 °C. The magnitude of the factor was calculated as a single-stage separation factor of 1.00030 with analytical precision of 0.00006 (1σ). The results showed that the lighter isotope () was preferentially fractionated into the resin phase, while the heavier one () enriched into the aqueous phase. This trend suggested that the hydrated Cl− ions in the aqueous phase were slightly more stable than the hydrated Cl− ions electrostatically interacting with the ion-exchange groups of the resin. 相似文献
55.
The vectorial Debye integral shows that tightly focused Laguerre-Gaussian (LG) beams have a residual intensity at the focal point for linear polarization, for a topological charge of m=1 and 2. We measured the shapes of linearly and circularly polarized LG beams and found that a central intensity appeared at m=1 and 2 for linear and right-handed circular polarization, however, it is completely canceled for left-handed circular polarization. In general, when the orbital angular momentum of the LG beam is parallel to the spin angular momentum of the photons, zero intensity is always achieved at the focus. 相似文献
56.
Takaharu Yaguchi Takayasu Matsuo Masaaki Sugihara 《Journal of Computational and Applied Mathematics》2010,234(4):1036-1048
The Ostrovsky equation describes gravity waves under the influence of Coriolis force. It is known that solutions of this equation conserve the L2 norm and an energy function that is determined non-locally. In this paper we propose four conservative numerical schemes for this equation: a finite difference scheme and a pseudospectral scheme that conserve the norm, and the same types of schemes that conserve the energy. A numerical comparison of these schemes is also provided, which indicates that the energy conservative schemes perform better than the norm conservative schemes. 相似文献
57.
Kensuke Aishima Takayasu Matsuo Kazuo Murota Masaaki Sugihara 《Journal of Computational and Applied Mathematics》2010,234(4):1179-1187
DLASQ is a routine in LAPACK for computing the singular values of a real upper bidiagonal matrix with high accuracy. The basic algorithm, the so-called dqds algorithm, was first presented by Fernando-Parlett, and implemented as the DLASQ routine by Parlett-Marques. DLASQ is now recognized as one of the most efficient routines for computing singular values. In this paper, we prove the asymptotic superquadratic convergence of DLASQ in exact arithmetic. 相似文献
58.
In this paper, we provide numerical means to compute the quasi-stationary (QS) distributions inM/GI/1/K queues with state-dependent arrivals andGI/M/1/K queues with state-dependent services. These queues are described as finite quasi-birth-death processes by approximating the general distributions in terms of phase-type distributions. Then, we reduce the problem of obtaining the QS distribution to determining the Perron-Frobenius eigenvalue of some Hessenberg matrix. Based on these arguments, we develop a numerical algorithm to compute the QS distributions. The doubly-limiting conditional distribution is also obtained by following this approach. Since the results obtained are free of phase-type representations, they are applicable for general distributions. Finally, numerical examples are given to demonstrate the power of our method. 相似文献
59.
Mitsuru Ohtake Kouhei Shikada Fumiyoshi Kirino Masaaki Futamoto 《Journal of magnetism and magnetic materials》2008
Co(0 0 0 1)hcp/Fe(1 1 0)bcc epitaxial magnetic bi-layer films were successfully prepared on SrTiO3(1 1 1) substrates. The crystallographic properties of Co/Fe epitaxial magnetic bi-layer films were investigated. Fe(1 1 0)bcc soft magnetic layer grew epitaxially on SrTiO3(1 1 1) substrate with two type variants, Nishiyama–Wasserman and Kurdjumov–Sachs relationships. An hcp-Co single-crystal layer is obtained on Ru(0 0 0 1)hcp interlayer, while hcp-Co layer formed on Au(1 1 1)fcc or Ag(1 1 1)fcc interlayer is strained and may involve fcc-Co phase. It has been shown possible to prepare Co/Fe epitaxial magnetic bi-layer films which can be usable for patterned media application. 相似文献
60.
Morimoto M Sato H Kobayashi M 《The Journal of the Acoustical Society of America》2004,116(3):1607-1613
Listening difficulty ratings, using words with high word familiarity, are proposed as a new subjective measure for the evaluation of speech transmission in public spaces to provide realistic and objective results. Two listening tests were performed to examine their validity, compared with intelligibility scores. The tests included a reverberant signal and noise as detrimental sounds. The subject was asked to repeat each word and simultaneously to rate the listening difficulty into one of four categories: (1) not difficult, (2) a little difficult, (3) fairly difficult, and (4) extremely difficult. After the tests, the four categories were reclassified into, not difficult [response (1)] and some level of difficulty, (the other 3 responses). Listening difficulty is defined as the percentage of the total number of responses indicating some level of difficulty [i.e. not (1)]. The results of two listening tests demonstrated that listening difficulty ratings can evaluate speech transmission performance more accurately and sensitively than intelligibility scores for sound fields with higher speech transmission performance. 相似文献