Debye dynamic model

A very much simplified lattice-dynamical model is that of Debye. In the Debye approximation, discussed in the following section, a single phonon branch is assumed, with frequencies proportional to the magnitude of the wavevector q. 

Considerable progress has been made in going beyond the simple Debye continuum model. Non-Debye relaxation solvents have been considered. Solvents with nonuniform dielectric properties, and translational diffusion have been analyzed. This is discussed in Section II. Furthermore, models which mimic microscopic solute/solvent structure (such as the linearized mean spherical approximation), but still allow for analytical evaluation have been extensively explored [38, 41-43], Finally, detailed molecular dynamics calculations have been made on the solvation of water [57, 58, 71]. 

An Evaluation of the Debye-Onsager Model. The simplest treatment for solvation dynamics is the Debye-Onsager model which we reviewed in Section II.A. It assumes that the solvent (i) is well modeled as a uniform dielectric continuum and (ii) has a single relaxation time (i.e., the solvent is a Debye solvent ) td (Eq. (18)). The model predicts that C(t) should be a single... 

A number of theoretical models for solvation dynamics that go beyond the simple Debye Onsager model have recently been developed. The simplest is an extension of Onsager model to include solvents with a non-Debye like (dielectric continuum and the probe can be represented by a spherical cavity. Newer theories allow for nonspherical probes [46], a nonuniform dielectric medium [45], a structured solvent represented by the mean spherical approximation [38-43], and other approaches (see below). Some of these are discussed in this section. Attempts are made where possible to emphasize the comparison between theory and experiment. 

The actual dependence of pATsp on the temperature is rather complicated because of the dependence of the specific heat Cp on T, which is given by Debye s theory of specific heat for the reacting oxides and corresponding lattice dynamical model for crystalline solids. Simple assumptions regarding the net change in specific heats of the components involved in the dissolution reactions, however, allow one to avoid these complications [3]. 

We shall now almost exclusively concentrate on the fractal time random walk excluding inertial effects and the discrete orientation model of dielectric relaxation. We shall demonstrate how in the diffusion limit this walk will yield a fractional generalization of the Debye-Frohlich model. Just as in the conventional Debye relaxation, a fractional generalization of the Debye-Frohlich model may be derived from a number of very different models of the relaxation process (compare the approach of Refs. 22, 23, 28 and 34—36). The advantage of using an approach based on a kinetic equation such as the fractional Fokker-Planck equation (FFPE) however is that such a method may easily be extended to include the effects of the inertia of the dipoles, external potentials, and so on. Moreover, the FFPE (by use of a theorem of operational calculus generalized to fractional exponents and continued fraction methods) clearly indicates how many existing results of the classical theory of the Brownian motion may be extended to include fractional dynamics. 

The INS spectroscopy of water ice is particularly demanding of the current world-wide suite of neutron spectrometers. Excellent energy transfer resolution is required, to provide data capable of discriminating between competing dynamical models. However, low Q values are also needed, to reduce the impact of the Debye-Waller factor from this very light molecular species (H2O has a Sachs-Teller mass about 2 amu). 

Debye s model assumptions are not valid for supercritical water, because the dilute limit is doubted. Microscopically there are many degrees of freedom and all these motions are not totally decoupled from the others, because the eigenstate of motions are not well known the structurally disordered matter. Dielectric measurements can only probe slow dynamics which can be described by stochastic processes and classical Debye s model could be rationalized [65, 66). 

There have been a limited number of theoretical Investigations on phonon frequencies and eigenvectors of the La. (Ba,Sr) CuO, [29-31] and YBa2Cu.O. - [32-35] superconductors. Unscreened lattice dynamical models [30,35], yielding only the bare phonon frequencies, gave fair agreement with experimentally determined total phonon density of states, mean square atomic vibrational amplitudes and Debye temperatures. Weber [29] has shown that the effect of... 

The recoil-free fraction / is temperature dependent, because (x ) decreases with decreasing temperature and hence forces / to increase. However,/does not reach unity even at 7=0 due to the fact that x ) 0 at 7= 0 because of the quantum-mechanical zero-point motion of the atoms (nuclei). In order to express / in terms of the usual experimental variables, the mean square amplitude (x ) is calculated using lattice dynamic models (e.g., Einstein. Debye) 16], [15],... 

A number of models describing supercapacitor resistor and capacitor behaviors used to mimic their performances in power systems have been reported and include classical equivalent, ladder circuit, and lumped or distributed parameter electrical and Debye polarization cell models [6]. An established design of a dynamic model of the often-used polymer electrolyte membrane fuel cell (PEMFC) is included in MATLAB and Simulink software to simulate performance under varying conditions specific to applications. 

The concentration of salt in physiological systems is on the order of 150 mM, which corresponds to approximately 350 water molecules for each cation-anion pair. Eor this reason, investigations of salt effects in biological systems using detailed atomic models and molecular dynamic simulations become rapidly prohibitive, and mean-field treatments based on continuum electrostatics are advantageous. Such approximations, which were pioneered by Debye and Huckel [11], are valid at moderately low ionic concentration when core-core interactions between the mobile ions can be neglected. Briefly, the spatial density throughout the solvent is assumed to depend only on the local electrostatic poten-... 

We discuss the rotational dynamics of water molecules in terms of the time correlation functions, Ciit) = (P [cos 0 (it)]) (/ = 1, 2), where Pi is the /th Legendre polynomial, cos 0 (it) = U (0) U (it), u [, Is a unit vector along the water dipole (HOH bisector), and U2 is a unit vector along an OH bond. Infrared spectroscopy probes Ci(it), and deuterium NMR probes According to the Debye model (Brownian rotational motion), both... 

Finally, it must be recalled that the transport properties of any material are strongly dependent on the molecular or ionic interactions, and that the dynamics of each entity are narrowly correlated with the neighboring particles. This is the main reason why the theoretical treatment of these processes often shows similarities with models used for thermodynamic properties. The most classical example is the treatment of dilute electrolyte solutions by the Debye-Hiickel equation for thermodynamics and by the Debye-Onsager equation for conductivity. 

NFS spectra of the molecular glass former ferrocene/dibutylphthalate (FC/DBP) recorded at 170 and 202 K are shown in Fig. 9.12a [31]. It is clear that the pattern of the dynamical beats changes drastically within this relatively narrow temperature range. The analysis of these and other NFS spectra between 100 and 200 K provides/factors, the temperature dependence of which is shown in Fig. 9.12b [31]. Up to about 150 K,/(T) follows the high-temperature approximation of the Debye model (straight line within the log scale in Fig. 9.12b), yielding a Debye tempera-ture 6x) = 41 K. For higher temperatures, a square-root term / v/(r, - T)/T,... 

Fig. 9.12 (a) NFS spectra of FC/DBP with quantum beat and dynamical beat pattern, (b) Temperature-dependent /-factor. The solid line is a fit using the Debye model with 0D = 41 K below 150 K. Above, a square-root term / - V(Tc - T)/Tc was added to account for the drastic decrease of /. At Tc = 202 K the glass-to-liquid transition occurs. (Taken Ifom [31])... 

Even if we consider a single solvent, e g., water, at a single temperature, say 298K, depends on the solute and in fact on the coordinate of the solute which is under consideration, and we cannot take xF as a constant. Nevertheless, in the absence of a molecular dynamics simulation for the solute motion of interest, XF for polar solvents like water is often approximated by the Debye model. In this model, the dielectric polarization of the solvent relaxes as a single exponential with a relaxation time equal to the rotational (i.e., reorientational) relaxation time of a single molecule, which is called Tp) or the Debye time [32, 347], The Debye time may be associated with the relaxation of the transverse component of the polarization field. However the solvent fluctuations and frictional relaxation occur on a faster scale given by [348,349]... 

Fig. 3.16 Scaling presentation of the dynamic structure factor from a M =36,000 PE melt at 509 K as a function of the Rouse scaling variable. The solid lines are a fit with the reptation model (Eq. 3.39). The Q-values are from above Q=0.05,0.077,0.115,0.145 A The horizontal dashed lines display the prediction of the Debye-Waller factor estimate for the confinement size (see text)...

In an early attempt to model the dynamics of the chromatin fiber, Ehrlich and Langowski [96] assumed a chain geometry similar to the one used later by Katritch et al. [89] nucleosomes were approximated as spherical beads and the linker DNA as a segmented flexible polymer with Debye-Huckel electrostatics. The interaction between nucleosomes was a steep repulsive Lennard-Jones type potential attractive interactions were not included. 

A more detailed view of the dynamies of a ehromatin chain was achieved in a recent Brownian dynamics simulation by Beard and Schlick [65]. Like in previous work, the DNA is treated as a segmented elastic chain however, the nueleosomes are modeled as flat cylinders with the DNA attached to the cylinder surface at the positions known from the crystallographic structure of the nucleosome. Moreover, the electrostatic interactions are treated in a very detailed manner the charge distribution on the nucleosome core particle is obtained from a solution to the non-linear Poisson-Boltzmann equation in the surrounding solvent, and the total electrostatic energy is computed through the Debye-Hiickel approximation over all charges on the nucleosome and the linker DNA. 

A principal drawback of the hat-curved model revealed here and also in Section V is that we cannot exactly describe the submillimeter (v) spectrum of water (cf. solid and dashed lines in Figs. 32d-f). It appears that a plausible reason for such a difference is rather fundamental, since in Sections V and VI a dipole is assumed to move in one (hat-curved) potential well, to which only one Debye relaxation process corresponds. We remark that the decaying oscillations of a nonrigid dipole are considered in this section in such a way that the law of these oscillations is taken a priori—that is, without consideration of any dynamical process. 

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