Dielectric constant time/frequency dependence

At low frequencies when power losses are low these values are also low but they increase when such frequencies are reached that the dipoles cannot keep in phase. After passing through a peak at some characteristic frequency they fall in value as the frequency further increases. This is because at such high frequencies there is no time for substantial dipole movement and so the power losses are reduced. Because of the dependence of the dipole movement on the internal viscosity, the power factor like the dielectric constant, is strongly dependent on temperature. 

The dispersion interaction between an atom and a metal surface was first calculated by Lennard-Jones in 1932, who considered the metal as a perfect conductor for static and time-dependent fields, using a point dipole for the molecule [44], Although these results overestimate the dispersion energy, the correct l/d3 dependence was recovered (d is the metal-molecule distance). Later studies [45 17] extended the work of Lennard-Jones to dielectrics with a frequency-dependent dielectric constant [48] (real metals may be approximated in this way) and took into account electromagnetic retardation effects. Limiting ourselves to small molecule-metal distances, the dispersion interaction of a molecule characterized by a frequency-dependent isotropic polarizability a embedded in a dielectric medium with permittivity esol (note that no cavity is built around the molecule) reads ... 

At sufficiently high frequencies the orientation polarization lags behind the measuring field, resulting in a decrease of the permittivity. Simultaneously, the system absorbs energy that appears as a dielectric loss. The frequency-dependent dielectric constant is usually expressed as a complex permittivity e = e - ie". In the simplest case of a single relaxation time t, the real and imaginary part of e can be described with the well-known Debye equations ... 

There is an important practical distinction between electronic and dipole polarisation whereas the former involves only movement of electrons the latter entails movement of part of or even the whole of the molecule. Molecular movements take a finite time and complete orientation as induced by an alternating current may or may not be possible depending on the frequency of the change of direction of the electric field. Thus at zero frequency the dielectric constant will be at a maximum and this will remain approximately constant until the dipole orientation time is of the same order as the reciprocal of the frequency. Dipole movement will now be limited and the dipole polarisation effect and the dielectric constant will be reduced. As the frequency further increases, the dipole polarisation effect will tend to zero and the dielectric constant will tend to be dependent only on the electronic polarisation Figure 6.3). Where there are two dipole species differing in ease of orientation there will be two points of inflection in the dielectric constant-frequency curve. 

Treating the free electrons in a metal as a collection of zero-frequency oscillators gives rise51 to a complex frequency-dependent dielectric constant of 1 - a>2/(co2 - ia>/r), with (op = (47me2/m)l/2 the plasma frequency and r a collision time. For metals like Ag and Au, and with frequencies (o corresponding to visible or ultraviolet light, this simplifies to give a real part... 

The electrical properties of materials are important for many of the higher technology applications. Measurements can be made using AC and/or DC. The electrical properties are dependent on voltage and frequency. Important electrical properties include dielectric loss, loss factor, dielectric constant, conductivity, relaxation time, induced dipole moment, electrical resistance, power loss, dissipation factor, and electrical breakdown. Electrical properties are related to polymer structure. Most organic polymers are nonconductors, but some are conductors. 

In recent years many attempts have been made to extend the implicit solvent models to the description of time-dependent phenomena. One of these phenomena is nonequilibrium solvation [3] and it can be described effectively in a very simplified way, despite the fact that it actually depends on the details of the full frequency spectrum of the dielectric constant. Typical examples of nonequilibrium solvation are the absorption of light by the solute which produces an excited state which is no longer in equilibrium with the surrounding polarization of the medium [11-13], Another example is intermolecular charge transfer within the solute, also leading to a nonequilibrium polarization [14],... 

As expected, the capacitance of the cell increases when the frequency is decreased (Figure 1.25a) below the knee frequency, the capacitance tends to be less dependent on the frequency and should be constant at lower frequencies. This knee frequency is an important parameter of the EDLC it depends on the type of the porous carbon, the electrolyte as well as the technology used (electrode thickness, stack, etc.) [20], The imaginary part of the capacitance (Figure 1.25b) goes through a maximum at a given frequency noted as/0 that defines a time constant x0 = 1 lf0. This time constant was described earlier by Cole and Cole [33] as the dielectric relaxation time of the system, whereas... 

An innovative approach due to Haider et al. [113] may help to sidestep the challenges involved in explicit molecular dynamics simulation and obtain information on these slow dynamics. The authors use the results of dielectric reflectance spectroscopy to model the IL as a dielectric continuum, and study the solvation response of the IL in this framework. The calculated response is not a good description of the subpicosecond dynamics, a problem the authors ascribe to limited data on the high frequency dielectric response, but may be qualitatively correct at longer times. We have already expressed concern regarding the use of the dielectric continuum model for ILs in Section IV. A, but believe that if the wavelength dependence of the dielectric constant can be adequately modeled, this approach may be the most productive theoretical analysis of these slow dynamics. 

P. J. W. Debye, Polar Molecules (Dover, New York, reprint of 1929 edition) presents the fundamental theory with stunning clarity. See also, e.g., H. Frohlich, "Theory of dielectrics Dielectric constant and dielectric loss," in Monographs on the Physics and Chemistry of Materials Series, 2nd ed. (Clarendon, Oxford University Press, Oxford, June 1987). Here I have taken the zero-frequency response and multiplied it by the frequency dependence of the simplest dipolar relaxation. I have also put a> = if and taken the sign to follow the convention for poles consistent with the form of derivation of the general Lifshitz formula. This last detail is of no practical importance because in the summation Jf over frequencies fn only the first, n = 0, term counts. The relaxation time r is such that permanent-dipole response is dead by fi anyway. The permanent-dipole response is derived in many standard texts. 

In Fig. 11.1 the time dependent dielectric constant (left) and both dynamic dielectric constants (right) are plotted vs. reduced time, t/x, and reduced angular frequency, cox, respectively, for amorphous polyethylene terephthalate at 81° C. It illustrates a continuous increase of s(t) from 3.8 to 6. It also shows that the e (co) decreases with frequency in a similar way as e(t) increases with time. The maximum in s", situated at cox = 1, is equal to (fis— oo)/2 = 1.1. A Cole-Cole plot where s" is plotted vs. s is shown in Fig. 11.2. For a Debye model with only one relaxation time this should be a semi-circle. In reality the decrease of s from s to 00 is not so fast and the maximum in s" not so sharp as the Debye... 

The possibility of making use of dielectric measurements for the study of the relaxation times is largely dependent on the very polar nature of amino acids, peptides and proteins. We must therefore discuss briefly the relation between dielectric constant and dipole moment in polar liquids, the discussion being for the moment restricted to static fields, or fields of frequency small compared to the rotary diffusion constants of the molecules. 

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