Dielectric response

In the large majority of present day uses of polymeric materials, the focus is on their mechanical performance. Properties are of a peculiar nature since polymer melts are different from low molar mass liquids and polymer solids differ from conventional crystalline solids. While the latter usually represent perfectly elastic bodies and low molar mass liquids develop viscous forces only, bulk polymers combine elastic and viscous properties in both the fluid and the solid state. Therefore they are generally addressed as viscoelastic and, in fact, polymers are the main representatives of this special class of materials. 

Viscoelastic behavior does not just mean a superposition of independent viscous and elastic forces, but it includes in addition a new phenomenon known as anelasticity , where both become coupled. It becomes apparent in the observation that part of the deformation, although being reversible, requires a certain time to become established when a load is applied. 

Different fields are concerned and they all need their own approaches 

We shall treat the first topic in this and the next chapter and large deformations, non-linear flow and the ultimate properties yield and break subsequently, in chapters 7 and 8. 

In electrical applications, polymers are mostly used as isolators. Since it is then important to be informed about possible electric losses, one needs to know their dielectric properties in dependence on frequency and temperature. As we shall see, description of the response of dielectric materials to applied time dependent electric fields is formally equivalent to the treatment of time dependent mechanical responses. Therefore, we shall discuss both together in one chapter. 

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In this section we consider electromagnetic dispersion forces between macroscopic objects. There are two approaches to this problem in the first, microscopic model, one assumes pairwise additivity of the dispersion attraction between molecules from Eq. VI-15. This is best for surfaces that are near one another. The macroscopic approach considers the objects as continuous media having a dielectric response to electromagnetic radiation that can be measured through spectroscopic evaluation of the material. In this analysis, the retardation of the electromagnetic response from surfaces that are not in close proximity can be addressed. A more detailed derivation of these expressions is given in references such as the treatise by Russel et al. [3] here we limit ourselves to a brief physical description of the phenomenon. 

Application of the exact continuum analysis of dispersion forces requires significant calculations and the knowledge of the frequency spectmm of the material dielectric response over wavelengths X = 2irc/j/ around 10-10 nm. Because of these complications, it is common to assume that a primary absorption peak at one frequency in the ultraviolet, j/uv. dominates the dielectric spectrum of most materials. This leads to an expression for the dielectric response... 

Relaxor Ferroelectrics. The general characteristics distinguishing relaxor ferroelectrics, eg, the PbMg 2N b2 302 family, from normal ferroelectrics such as BaTiO, are summari2ed in Table 2 (97). The dielectric response in the paraelectric-ferroelectric transition region is significantly more diffuse for the former. Maximum relative dielectric permittivities, referred to as are greater than 20,000. The temperature dependence of the dielectric... 

The treatment of electrostatics and dielectric effects in molecular mechanics calculations necessary for redox property calculations can be divided into two issues electronic polarization contributions to the dielectric response and reorientational polarization contributions to the dielectric response. Without reorientation, the electronic polarization contribution to e is 2 for the types of atoms found in biological systems. The reorientational contribution is due to the reorientation of polar groups by charges. In the protein, the reorientation is restricted by the bonding between the polar groups, whereas in water the reorientation is enhanced owing to cooperative effects of the freely rotating solvent molecules. 

J-K Hyun, CS Babu, T Ichiye. Apparent local dielectric response around ions m water A method for its determination and its applications. J Phys Chem 99 5187-5195, 1995. 

Interaction ofthe electrons in the framework of the self-consistent field approximation is accounted for by considering the induced density fluctuations as a response of independent particles to Oext + Poissons equation [2], This means, physically, that collective excitations of the electrons can occur, taken into account via a chain of electron-holeexcitations. These collective excitations show up in S(q, ) as a distinct energy loss feature. Figure 2 shows the shape of the real and imaginary parts of the dielectric function in RPA (er(q, ), Si(q, )) and the resulting dielectric response... 

Application of the formalism of the impulse approximation to the double differential cross section in terms of the dielectric response (Equation 12), that is, using free-electron-like final states E = p+q 2/2m in the calculation ofU(p+q, E +7ko)... 

In recent years, a class of methods has been developed for molecular dynamics simulations to be performed with an external pH parameter, like temperature or pressure [18, 43, 44, 70], These methods treat the solution as an infinite proton bath, and are thus referred to as constant pH molecular dynamics (PHMD). In PHMD, conformational dynamics of a protein is sampled simultaneously with the protonation states as a function of pH. As a result, protein dielectric response to the... 

The dielectric response of a solvated protein to a perturbing charge, such as a redox electron or a titrating proton, is related to the equilibrium fluctuations of the unperturbed system through linear response theory [49, 50]. In the spirit of free energy... 

Studies of ferredoxin [152] and a photosynthetic reaction center [151] have analyzed further the protein s dielectric response to electron transfer, and the protein s role in reducing the reorganization free energy so as to accelerate electron transfer [152], Different force fields were compared, including a polarizable and a non-polarizable force field [151]. One very recent study considered the effect of point mutations on the redox potential of the protein azurin [56]. Structural relaxation along the simulated reaction pathway was analyzed in detail. Similar to the Cyt c study above, several slow relaxation channels were found, which limited the ability to obtain very precise free energy estimates. Only semiquantitative values were... 

Master curves are important since they give directly the response to be expected at other times at that temperature. In addition, such curves are required to calculate the distribution of relaxation times as discussed earlier. Master curves can be made from stress relaxation data, dynamic mechanical data, or creep data (and, though less straightforwardly, from constant-strain-rate data and from dielectric response data). Figure 9 shows master curves for the compliance of poly(n. v-isoprene) of different molecular weights. The master curves were constructed from creep curves such as those shown in Figure 10 (32). The reference temperature 7, for the... 

These are the familiar orientational contributions to the DC dielectric response. This limit, /iE/kT <1, can be considered alternatively to be a restriction to nonsaturated alignments. For physical systems with orientational distributions intermediate between the isotropic and Ising limiting models the poling responses... 

This behaviour is one example of a wide range of phenomena which are manifestations of Jonscher s Universal Law of Dielectric Response (Jonscher, 1977, 1983). 

It is noteworthy that the neutron work in the merging region, which demonstrated the statistical independence of a- and j8-relaxations, also opened a new approach for a better understanding of results from dielectric spectroscopy on polymers. For the dielectric response such an approach was in fact proposed by G. Wilhams a long time ago [200] and only recently has been quantitatively tested [133,201-203]. As for the density fluctuations that are seen by the neutrons, it is assumed that the polarization is partially relaxed via local motions, which conform to the jS-relaxation. While the dipoles are participating in these motions, they are surrounded by temporary local environments. The decaying from these local environments is what we call the a-process. This causes the subsequent total relaxation of the polarization. Note that as the atoms in the density fluctuations, all dipoles participate at the same time in both relaxation processes. An important success of this attempt was its application to PB dielectric results [133] allowing the isolation of the a-relaxation contribution from that of the j0-processes in the dielectric response. Only in this way could the universality of the a-process be proven for dielectric results - the deduced temperature dependence of the timescale for the a-relaxation follows that observed for the structural relaxation (dynamic structure factor at Q ax) and also for the timescale associated with the viscosity (see Fig. 4.8). This feature remains masked if one identifies the main peak of the dielectric susceptibility with the a-relaxation. 

In its underlying physics, the use of susceptibilities to obtain E is related to the use of a generalized dielectric response function to determine the energy of a... 

Equation (4.4) stresses that the surface plasma wave propagates within the aluminium substrate whose frequency is modified by the dielectric response of the molecular adlayer. From the measurements reported, with hcog = 8.5 eV and hcob = 15 eV, one obtains e = 2.1 for CuPc, a value in agreement with those measured for other planar organic molecules, with an extended delocalization of 7T-electrons (Alonso et al, 2003). 

The switching or memory phenomena induced by electric field application or photo irradiation have been studied on Mott insulators, charge ordered insulators, and N-I transition systems and were found to be fast phase transitions in general. For the former two systems, the phase transitions caused a pronounced change in reflectance and conductivity from insulating to metallic features. The third system also exhibited a change in conductivity and dielectric response connected with the transports of solitons and/or domain walls, dynamic dimerization, and... 

The degree of correlation in dielectric response between interacting... 

The wave vector, k , and the screening length, 1/ , depend only on the density of the free-electron gas through the poles of the approximated inverse dielectric response function, whereas the amplitude, A , and the phase shift, a , depend also on the nature of the ion-core pseudopotential through eqs (6.96) and (6.97). For the particular case of the Ashcroft empty-core pseudopotential, where tfj fa) = cos qRc, the modulus and phase are given explicitly by... 

Indeed, things are slightly more complicated, because the electrons of the solvent can respond on the timescale of the absorption. Thus, in discussing solvent effects, it is helpful to separate the bulk dielectric response of the solvent, which is a function of s, into a fast component, depending on where n is the solvent index of refraction, and a slow component, which is the remainder after the fast component is removed from the bulk. The initially formed excited state interacts with the fast component in an equilibrium fashion, but with the slow component frozen in its ground-state-equilibrium polarization. The fast component accounts for almost the entire bulk dielectric response in very non-polar solvents, like alkanes, and about one-half of the response in highly polar solvents. 

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