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161.
162.
163.
We estimate the possible influence of spectral line profile (Lorentz profile, Van Vleck–Weisskopf profile, and profile obtained by solving kinetic equation) on the rotation part of the dielectric permittivity of water-vapor monomers. Spectral regions corresponding to long-wavelength (static) and high-frequency (optical) limiting cases as well as regions in close proximity to resonances of various intensities are considered. The studied effects are compared with the corresponding effects on water-vapor absorption coefficient, which are related to factors determining the line-shape structure. 相似文献
164.
165.
Rate constants have been measured by pulse radiolysis for the reactions of the carbonate radical, CO3·?, with a number of organic and inorganic reactants as a function of temperature, generally over the range 5 to 80°C. The reactants include the substitution-inert cyano complexes of FeII, MoIV, and WIV, the simple inorganic anions SO32?, ClO2?, NO2?, I?, and SCN?, several phenolates, ascorbate, tryptophan, cysteine, cystine, methionine, triethylamine, and allyl alcohol. The measured rate constants ranged from less than 105 to 3 × 109 M?1 s?1, the activation energies ranged from ?11.4 to 18.8 kJ mol?1, and the pre-exponential factors ranged from log A = 6.4 to 10.7. The activation energies for the metal complexes and inorganic anions generally decrease with increasing driving force for the reaction, as expected for an outer sphere electron transfer. For highly exothermic reactions, however, the activation energy appears to increase, probably reflecting the temperature dependence of diffusion. For many of the organic reactants, the activation energies were low and independent of driving force, suggesting that the oxidation is via an inner sphere mechanism. 相似文献
166.
O. B. Lykova 《Ukrainian Mathematical Journal》1992,44(1):28-40
A survey is presented of some results relating to the development of the Bogolyubov-Mitropol'skii method of integral manifolds.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 44, No. 1, pp. 33–46, January, 1992. 相似文献
167.
Alec B. Scranton John Klier Nikolaos A. Peppas 《Journal of Polymer Science.Polymer Physics》1991,29(2):211-224
The dilute solution complexation equilibrium between linear macromolecules and smaller complementary oligomers is considered when: (1) the oligomers are free in solution; and (2) the oligomers are covalently attached at one end to the polymer. A general statistical mechanical framework is developed and is illustrated using a simple random walk model for polymer conformation. The statistical mechanical partition functions are formulated using a generating function technique, allowing thermodynamic averages in the complexed state to be calculated. Loops, trains, and tails of all possible length are allowed in the conformation of a complexed oligomer. Simulation results for the free oligomer case are compared with those obtained for oligomers covalently attached to the polymeric molecular. The model provides a theoretical explanation for the experimentally observed enhancement of complexation of oligomers grafted to the complementary polymers. 相似文献
168.
A potential of mean torque is derived for a solute at infinite dilution in a uniaxial liquid crystal solvent, which contains terms originating from the dispersion interaction, and the electrostatic interaction between quadrupole moments on both molecules. It is shown that the electrostatic term is non-zero only if the solute-solvent vectors are distributed with lower than spherical symmetry. If this distribution has cylindrical symmetry then both the electrostatic and dispersion terms in the potential of mean torque are shown to depend on order parameters for the orientational distribution of the solute-solvent vectors, as well as on the order parameters of the solvent molecules. 相似文献
169.
Dielectric relaxation measurements of 5 mole % 4-n-hexyloxycyanobenzene (I) dissolved in 4-n-pentyloxyphenyl-trans-4-n-octylcyclohexylcarboxylate (II) were carried out from 1 kHz to 10 MHz in the nematic, smectic A and smectic B phases. The relaxation frequency of I parallel to the director is about 05 MHz in the SBphase and increases rapidly at the transition from SB to SA. 相似文献
170.
Peroxyoxalate chemiluminescence may be used for sensitive postcolumn detection of phenothiazine analytes separated by high performance liquid chromatography with appropriate optimization of measurement conditions such as solvent, pH and oxalate ester. Detectability of fluorescent analytes by chemical excitation varies greatly, but analytes with low oxidation potentials are generally more readily detected at low levels, as demonstrated for phenothiazines, an important class of fluorescent drugs. Some improvement in detection limits is observed for fluphenazine when chemiluminescence detection is compared to conventional fluorescence detection. Because of the specificity of chemical excitation, fewer interferences from fluorescent impurities in a urine matrix are observed. 相似文献