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71.
The Landau-Lifshitz fluctuating fluxes in fluctuating hydrodynamics are derived from the deterministic Boltzmann equation with the aid of a reduction method developed by Fujisaka and Mori. Thus it is shown that the hydrodynamic fluctuations innonequilibrium systems are generated by the reduction of variables from the-space distribution function to its five momentum moments, i.e., the hydrodynamic variables. This differs from the Bixon-Zwanzig and Fox-Uhlenbeck theories, in which the Landau-Lifshitz fluctuating fluxes are derived from the molecular fluctuating force in thestochastic Boltzmann-Langevin equation, which is, however, negligible in nonequilibrium systems. Thus the present method improves the Chapman-Enskog reduction method so as to include the hydrodynamic fluctuations generated by the reduction of variables.Supported in part by the Scientific Research Fund of the Ministry of Education. 相似文献
72.
Time-dependent density-functional theory(TDDFT)has been applied to calculate the electronic structure and second-order nonlinear optical(NLO) properties of some organic molecules.The two-dimensional(2-D)charge transfer charateristics of calculated molecules were studied and compared with corresponding experimental results.All the theoretical results agree well with the measurement.For 2-D molecule with two-fold symmetry,the dominant charge transfer is off-diagonal,while for three-fold symmetry 2-D molecule,the dominant charge transfer is not only between branches and central group but also among branches. 相似文献
73.
V. Ya. Kavun N. F. Uvarov A. B. Slobodyuk V. K. Goncharuk A. Yu. Kotenkov I. A. Tkachenko A. V. Gerasimenko V. I. Sergienko 《Russian Journal of Electrochemistry》2005,41(5):501-509
Methods of (19F, 1H) NMR and impedance spectroscopy are used to investigate the internal mobility and ionic conduction in solid solutions arising in the system PbF2-ZrF4 and polycrystals KSnZrF7, Li(Na)(NH4)6Zr4F23, and M2ZrF6 (M = K, NH4). Factors responsible for the form of ionic motions and their energetics at 170–550 K are considered. It is established that the phase transitions in these compounds are connected with the crystal transition to a superionic state and that the high ionic (superionic) conductivity of beta phases is due to the diffusion of fluoride ions, ammonium cations, and possibly alkali metal cations. The obtained data testify to a substantial role of chainlike aggregation of anionic groupings and a variableness of structural mechanisms of formation of such chains in fluorozirconates for the development of translational diffusion in these compounds.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 573–582.Original Russian Text Copyright © 2005 by Kavun, Uvarov, Slobodyuk, Goncharuk, Kotenkov, Tkachenko, Gerasimenko, Sergienko. 相似文献
74.
Marcos Mandaji Tiago Buckup Rafael Rech Ricardo Rego Bordalo Correia Tarso Ledur Kist 《Talanta》2007,71(5):1998-2002
The performance of fluorescence detectors in capillary electrophoresis is maximized when the excitation light intensity is modulated in time with optimal frequencies. This is especially true when photomultiplier tubes are used to detect the fluorescent light. The photomultiplier tube amplified raw output signal can in principle be captured directly by a personal computer sound card (PCSC) and processed by a lock-in emulated by software. This possibility is demonstrated in the present work and the performance of this new setup is compared with a traditional data acquisition system. The results obtained with this “PCSC and lock-in emulated by software” were of the same quality or even better compared to that obtained by conventional time integrators (Boxcars) and data acquisition boards. With PCSC the limits of detection (LOD) found for both naphthalene-2,3-dicarboxaldehyde-derivatized tyrosine and alanine were 3.3 and 3.5 fmol (injection of 5 nL of samples at 0.66 and 0.70 μmol/L), respectively. This is at least three times better compared to conventional systems when light emitting diodes (LEDs) are used as the excitation source in fluorescence detectors. The PCSC linear response range was also larger compared to conventional data acquisition boards. This scheme showed to be a practical and convenient alternative of data acquisition and signal processing for detection systems used in capillary electrophoresis. 相似文献
75.
Viktoriya V. Skripacheva Ella Kh. Kazakova Nelly A. Markarova Vladimir E. Kataev Ludmila V. Ermolaeva Wolf D. Habicher 《Journal of inclusion phenomena and macrocyclic chemistry》2002,42(1-2):77-81
The binding of different sized and shaped metal complexes [Co(His)2]ClO4(1), [Co(en)2C2O4]Cl (2) and [K18-crown-6]SCN (3)(en-ethylendiamine, His-L-histidynate-anion) with a new tetrasulfonatomethylcalix[4]resorcinarene([H8X]Na4) was investigated in neutral and alkaline aqueous media by NMR and pH-metrictitration methods and compared with those of recently studied NMe4Br (4). The resultsobtained indicate that the outer-sphere coordination of complexes 1–3 by[H8X]4- proceeds via the interaction of hydrophobic fragments of the guestswith both the negatively charged rim and the hydrophobic cavity as a -base. Thenature of binding does not change for cations 1, 2 and 4 on going from[H8X]4- in neutral to [H4X]8- in alkaline media, while the inclusionof 3 decreases on going from [H8X]4- to [H4X]8-. 相似文献
76.
Garth J Simpson 《Chemphyschem》2004,5(9):1301-1310
Recent observations of remarkably large chiroptical effects in second-harmonic generation (SHG) and sum-frequency generation (SFG) measurements suggest exciting possibilities for the development of new chiral-specific spectroscopies and novel chiral materials for nonlinear optics. Several fundamental studies designed to elucidate the molecular and macromolecular origins of the chiral responses are reviewed to provide a framework for development of this emerging field. In general, the chiral activity in SHG and SFG has the potential to arise from complex interactions between hosts of different competing effects. Fortunately, relatively simple electric dipole-allowed mechanisms routinely dominate the nonlinear optical chiral activities of most practical systemsexpressions can often be generated to link the. This substantial reduction in complexity allows for the development of simple models connecting the macroscopic nonlinear optical response to intuitive molecular and supramolecular properties. 相似文献
77.
Woods M Zhang S Ebron VH Sherry AD 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(19):4634-4640
The lanthanide(III) complexes of three tetraamide DOTA bearing pyridyl, phenolic and hydroxypyridyl substituents have been studied by NMR, luminescence and cyclic voltammetry. The relaxivity profiles of the gadolinium complexes of the pyridyl and phenolic ligands were flat and essentially the same between pH 2 and 8. The hydroxypyridyl ligand, however, exhibited two regions of enhanced relaxivity. The small relaxivity enhancement (25 %) at lower pH (pH 2-4) has been attributed to an increase in the prototropic exchange of the coordinated water molecule while the slightly larger enhancement (84 %) at higher pH (pH 6-9) reflects deprotonation of the ligand amide protons. Deprotonation of the amides results in the formation of an intramolecular acid-base pair interaction with the phenolic protons and this, in turn, causes a highly organized second hydration sphere to come into effect, thereby increasing the relaxivity. The water relaxivity of the Gd(3+)-hydroxypyridyl complex is further enhanced upon binding to serum albumin. 相似文献
78.
讨论了刚柔相嵌液晶高分子的向列相一各向同性相转变与其分子结构的关系.给出了该一级相变的赝二级相变温度T*与这类液晶高分子的液晶基元和间隔基的长度、柔顺性(相关长度)以及它们之间的相互作用的关系的解析表示式.分析了液晶基元与间隔基连接处的表观弯曲(接口效应)对T*的影响.文中的结论与实验相符. 相似文献
79.
A numerical model of the negative DC corona plasma along a thin wire in dry air is presented. The electron number density and electric field are determined from solution of the one-dimensional coupled continuity equations of charge carriers and Maxwell's equation. The electron kinetic energy distribution is determined from the spatially homogeneous Boltzmann equation. A parametric study is conducted to examine the effects of linear current density (0.1–100 A per cm of wire length), wire radius (10–1000 m), and air temperature (293–800 K) on the distribution of electrons and the Townsend second ionization coefficient. The results are compared to those previously determined for the positive corona discharge. In the negative corona, energetic electrons are present beyond the ionization boundary and the number of electrons is an order of magnitude greater than in the positive corona. The number of electrons increases with increasing gas temperature. The electron energy distribution does not depend on discharge polarity. 相似文献
80.
K. D. Hong G. F. Brand P. W. Fekete T. Idehara 《International Journal of Infrared and Millimeter Waves》1992,13(2):215-227
The gyrotrons developed at the University of Sydney are tunable sources of millimetre and submillimetre radiation. The generation of submillimetre wavelengths requires operation at the second harmonic of the electron cyclotron frequency, or higher. Our latest gyrotron, GYROTRON IVA, has successfully achieved second harmonic operation and obtained frequencies up to 590 GHz (=0.51 mm). The experimental results and conditions for second harmonic operation will be presented. The design of a new gyrotron, GYROTRON V, which is especially optimised for the second harmonic, will also be included. 相似文献