Onsager behavior”

The most likely terminal position was given as Eq. (24), where it was mentioned that if the coefficient could be shown to scale linearly with time, then the Onsager regression hypothesis would emerge as a theorem. Hence the small-x behavior of... 

The first satisfactory explanation of these effects was given, in the twenties, by Debye, Hiickel, Onsager, and Falkenhagen (see, for instance, Ref. 8). Using a remarkably clever combination of microscopic and macroscopic concepts, they were able to describe the behavior of dilute electrolytes by the famous limiting laws . 

The distinct properties of liquid-crystalline polymer solutions arise mainly from extended conformations of the polymers. Thus it is reasonable to start theoretical considerations of liquid-crystalline polymers from those of straight rods. Long ago, Onsager [2] and Flory [3] worked out statistical thermodynamic theories for rodlike polymer solutions, which aimed at explaining the isotropic-liquid crystal phase behavior of liquid-crystalline polymer solutions. Dynamical properties of these systems have often been discussed by using the tube model theory for rodlike polymer solutions due originally to Doi and Edwards [4], This theory, the counterpart of Doi and Edward s tube model theory for flexible polymers, can intuitively explain the dynamic difference between rodlike and flexible polymers in concentrated systems [4]. 

More than half a century ago, Bawden and Pirie [77] found that aqueous solutions of tobacco mosaic virus (TMV), a charged rodlike virus, formed a liquid crystal phase at as very low a concentration as 2%. To explain such remarkable liquid crystallinity was one of the central themes in the famous 1949 paper of Onsager [2], However, systematic experimental studies on the phase behavior in stiff polyelectrolyte solutions have begun only recently. At present, phase equilibrium data on aqueous solutions qualified for quantitative discussion are available for four stiff polyelectrolytes, TMV, DNA, xanthan (a double helical polysaccharide), and fd-virus. 

Reynolds (Rl, R2) was one of the earlier investigators to appreciate the random nature of turbulence. The dimensionless parameter bearing his name is widely used as a measure of the physical characteristics of steady, uniform flow. Such a measure is essentially macroscopic and does not describe the local or transient behavior at a point in the stream. In recent years much effort has been devoted to understanding the basic mechanism of momentum transport by turbulence. The early work of Prandtl (P6), Taylor (Tl), Karmdn (Kl), and Howarth (K4) laid a basis for the statistical theory of turbulence which is apparently in reasonable agreement with experiment. More recently Onsager (03), Corrsin (C6), and Kolmogoroff (K10) extended the statistical theory of turbulence to describe the available experimental data in terms of kinetic-energy... 

Onsager Theory for C(t) for Non-Debye Solvents. Generally solvents have more complex dielectric responses than described by the Debye equation (Eq. (18)). To obtain the time dependence of the reaction field R from Eqs. (12, (15), (16) and (7) an appropriate model for dielectric behavior of a specific liquid should be employed. One of the most common dielectric relaxation is given by the Debye-type form, which is applicable to normal alcohols. 

Bagchi and co-workers [47-50] have explored the role of translational diffusion in the dynamics of solvation by employing a Smoluchowski-Vlasov equation (see also Calef and Wolyness [37] and Nichols and Calef [42]). A significant contribution to polarization relaxation is observed in certain cases. It is found that the Onsager inverted snowball model is correct only when the rotational diffusion mechanism of solvation dominates the polarization relaxation. The Onsager model significantly breaks down when there is an important translational contribution to the polarization relaxation [47-50]. In fact, translational effects can rapidly accelerate solvation near the probe. In certain cases, the predicted behavior can actually approach the uniform continuum result that rs = t,. 

A much better representation of the dielectric behavior of polar liquids is given by the Onsager equation... 

The two mass action equilibria previously indicated have been used in conjunction with a modified form of the Shedlovsky conductance function to analyze the data in each of the cases listed in Table I. Where the data were precise enough, both K2 and K were calculated. As mentioned previously, the K s so evaluated are practically the same as those obtained for ion pairing in solutions of electrolytes in ammonia and amines. This is encouraging since it implies a fairly normal behavior (in the electrolyte sense) for dilute solutions of metals. Further support of the proposed mass action equilibria can be found in the conductance measurements of sodium in NH8 solutions with added salt. Bems, Lepoutre, Bockelman, and Patterson (4) assumed an additional equilibrium between sodium and chloride ions, associated to form NaCl, to compute the concentration of ionic species, monomers, and dimers when the common ion electrolyte is added. Calculated concentrations of conducting species are employed in the Onsager-Kim extension of the conductance theory for low-field conductance of a mixture of ions. Values of [Na]totai ranging from 5 X 10 4 to 6 X 10 2 and of the ratio of NaCl to [Na]totai ranging from zero to 28.5 are included in the calculations. 

According to the Onsager theory and to computer simulations of the behavior of hard sphero-cylinders [37], in the absence of additional interactions no LC ordering is predicted for rods with L/D < 4, and therefore DNA double helices with a number of base pairs N < 24 would lack the anisotropy to display mesophase behavior at any concentration (Fig. 10). 

Treating the fluctuation potential, we will depart a bit from the scheme used for the (unary) electrostatic potential. As a zero iteration the modified Onsager-Samaras approximation will be taken [25], that preserves a proper asymptotic behavior of this potential along the p-axis (see for details elsewhere [24]). 

Krauss and Brus [15] measured the dielectric constant of CdSe dots, and found a value of 8. Hence, at room temperature we find r0ns — 70 A (angstrom) (however, note that the dielectric constant of the matrix is not identical to that of the dot). Since the length scale of the dots is of the order of a few nanometers, the Coulomb interaction seems to be an important part of the problem. This according to the theory in Ref. 16 is an indication of possible deviations from the universal 1 /2 power-law behavior. It is also an indication that an ejected electron is likely to return to the dot and not escape to the bulk (since the force is attractive). In contrast, if the Onsager radius is small, an ejected electron would most likely escape to the bulk, leaving the dot in state off forever (i.e., Polya... 

We now begin the analysis of the phase diagram by studying its high-temperature and low-temperature behaviors. Beforehand, in the following section, we will recall the main steps of the Onsager method in the form which is most convenient for further generalizations. 

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