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1.
Roy Edward Bruns Paul Martin Kuznesof James Elton Moore 《Journal of Molecular Structure》1975,29(2):211-223
CNDO molecular orbital calculations have been performed to analyze donor—acceptor interactions between molecular chlorine and benzene, toluene, mesitylene and hexamethylbenzene and the, as yet, unreported chlorine—hexafluorobenzene and carbon disulfide—benzene pairs. The stabilization energy and the dipole moment and its derivative (?p/?RCICI) calculated for the benzene—chlorine complex are in good agreement with the estimated experimental values. The trends in the experimental stabilization energies and the Cl-Cl vibrational frequencies with increasing methyl substitution appear to be well reproduced by the calculations. The charge transferred from the benzene donor is polarized toward the outer chlorine atom or sulfur atom. For hexafluorobenzene-chlorine the direction of electronic charge polarization is reversed from that of the benzene and methylbenzene complexes. The calculated results are discussed within the framework of Muliiken's simplified resonance theory for complexes. 相似文献
2.
This paper attempts to give an integrated presentation of the application of micro-simulation to the study of markets, based on the purchase behaviour of individual consumers. We emphasize the methodological considerations which should govern the use of the approach, and in particular the need for evolutionary model-building; the technical problems which are only rarely specified in the literature; and the need to be eclectic in the selection of sub-model formulations. Case-studies are reported, and information is given on the scale of resources required for such projects. The presentation is backed with full references to relevant published work, to provide a practical aid to workers in the field. Much of the discussion is also relevant to the simulation of social systems other than markets. 相似文献
3.
Solutions of cellulose (degree of polymerization: 296 ± 16) in tris(ethylenediamine)cadmium(II)hydroxide-ethylenediamine-water (cadoxen), 1.015% (weight per volume) were diluted 1:1.5 with water. The ensuing isothermal precipitations were followed dilatometrically at temperatures ranging from 27.50 to 48.45°C. The precipitation data were characterized by a positive temperature coefficient. They generally conformed to a one-dimensional nucleation rate law; the Avrami exponents were close to unity. Alternatively, they fit a first-order reaction rate expression with respect to cellulose concentration. The low crystallinity of the precipitated cellulose leads to the interpretation of the kinetics in terms of the dissociation of a cellulose-cadoxen complex, rather than phase separation, as the rate-determining step. The nucleation rate law suggests a one-dimensional nonrandom cooperative chemical process, while the first-order rate law suggests a random process. 相似文献
4.
João P. Bender Mirian Feitein Elton Franceschi Marcos L. Corazza J. Vladimir Oliveira 《The Journal of chemical thermodynamics》2010,42(1):48-53
Experimental phase equilibrium data for binary systems involving ε-caprolactone, δ-hexalactone, and γ-caprolactone with carbon dioxide have been measured applying the synthetic method using a high-pressure, variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 21 MPa. For the systems investigated, (vapour + liquid) (VLE), (liquid + liquid) (LLE), and (vapour + liquid + liquid) (VLLE) equilibrium were visually recorded. It was observed that an increase in temperature or in carbon dioxide concentration led to a pronounced raise in transition pressure values. The experimental results were modelled using the Peng–Robinson equation of state with the conventional quadratic mixing rule, affording a satisfactory representation of the experimental values. 相似文献
5.
João P. Bender Mirian Feitein Marcio A. Mazutti Elton Franceschi Marcos L. Corazza J. Vladimir Oliveira 《The Journal of chemical thermodynamics》2010,42(2):229-233
Recently, production of biocompatible and biodegradable polymer microparticles has been a matter of growing interest in pharmaceutical and food areas such as drug or active compounds delivery. To conduct production of microparticles, polymeric particle coating, impregnation of active compounds in polymeric films, the knowledge of phase behaviour involving the biodegradable polymer in supercritical carbon dioxide in the presence of a modifier may be needed to allow developing new industrial applications. In this sense, the aim of this work was to investigate the phase behaviour of the ternary system formed by the biodegradable polymer poly(ε-caprolactone) in (carbon dioxide + dichloromethane). Experimental phase transition (bubble and cloud point) values were obtained by applying the static-synthetic method using a variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 21 MPa, in the CO2 overall composition range of (25–46) wt%, while polymer concentrations studied were (1, 3, 5, and 7) wt%. For the system investigated, depending on the polymer concentration, vapour–liquid, liquid–liquid, and vapour–liquid–liquid phase transitions were verified. 相似文献
6.
We study the spectrum of a one-dimensional Dirac operator pencil, with a coupling constant in front of the potential considered as the spectral parameter. Motivated by recent investigations of graphene waveguides, we focus on the values of the coupling constant for which the kernel of the Dirac operator contains a non-trivial square integrable function. In physics literature such a function is called a confined zero mode. Several results on the asymptotic distribution of coupling constants giving rise to zero modes are obtained. In particular, we show that this distribution depends in a subtle way on the sign variation and the presence of gaps in the potential. Surprisingly, it also depends on the arithmetic properties of certain quantities determined by the potential. We further observe that variable sign potentials may produce complex eigenvalues of the operator pencil. Some examples and numerical calculations illustrating these phenomena are presented. 相似文献
7.
By means of in situ IR spectroscopy we investigate the effect of dissolved alkali cations on the electro-oxidation of ethylene glycol on platinum in alkaline media. The results revealed that the increase in the oxidation currents (Li(+) < Na(+) < K(+)) is reflected in the increase in the ratio between carbonate and oxalate produced. 相似文献
8.
In this paper we prove that each ordered groupoid (resp. semigroup) S embeds in a complete distributive le-groupoid (resp.
le-semigroup) using the ordered groupoid (resp. semigroup) arising from S by the adjunction of a zero element. 相似文献
9.
Free-carrier absorption (FCA) has proven to be an important obstacle in the development of a silicon-based laser; however, FCA may serve as a potential advantage in active silicon-based switches or modulators. In this work, we present FCA modulation in slot waveguides with silicon nanocrystals (Si-ncs) embedded in SiO(2) as the low-index slot material. Slot waveguides were fabricated with and without Si-ncs, and the presence of Si-ncs was shown to increase the pump-induced FCA loss in the waveguides by a factor of 4.5. We modeled the Si-nc material using a four-level rate equation analysis to estimate the excited population of Si-ncs, allowing us to extract a value of 2.6 × 10(-17) cm(2) for the FCA cross section of the Si-nc material. 相似文献
10.
Journal of Solid State Electrochemistry - Controlling the Pt(111)-OHad stability by means of noncovalent interactions with hydrated cations, it was possible to modify natural changes in the... 相似文献