Constant, Boltzmann dielectric

Another way of calculating the electrostatic component of solvation uses the Poisson-Boltzmann equations [22, 23]. This formalism, which is also frequently applied to biological macromolecules, treats the solvent as a high-dielectric continuum, whereas the solute is considered as an array of point charges in a constant, low-dielectric medium. Changes of the potential within a medium with the dielectric constant e can be related to the charge density p according to the Poisson equation (Eq. (41)). 

Not to be forgotten is the assumption that neither the presence of the electrolyte nor the interface itself changes the dielectric medium properties of the aqueous phase. It is assumed to behave as a dielectric continuum with a constant relative dielectric permittivity equal to the value of the bulk phase. The electrolyte is presumed to be made up of point charges, i.e. ions with no size, and responds to the presence of the charged interface in a competitive way described by statistical mechanics. Counterions are drawn to the surface by electrostatic attraction while thermal fluctuations tend to disperse them into solution, surface co-ions are repelled electrostatically and also tend to be dispersed by thermal motion, but are attracted to the accumulated cluster of counterions found near the surface. The end result of this electrical-thermodynamic conflict is an ion distribution which can be represented (approximately) by a Boltzmann distribution dependent on the average electrostatic potential at an arbitrary point multiplied by the valency of individual species, v/. 

The quantities Cp, hp, ks, and T denote the velocity of light in a vacuum, Planck s constant, Boltzmann s constant, and the temperature, respectively. The parameters Sj n represent the values of the imaginary dielectric response function s(iif) at the imaginary frequencies i-f , which can be computed from the imaginary part of the dielectric permittivity by means of a Kramers-Kronig relation ... 

The final class of methods that we shall consider for calculating the electrostatic compone of the solvation free energy are based upon the Poisson or the Poisson-Boltzmann equatior Ihese methods have been particularly useful for investigating the electrostatic properties biological macromolecules such as proteins and DNA. The solute is treated as a body of co stant low dielectric (usually between 2 and 4), and the solvent is modelled as a continuum high dielectric. The Poisson equation relates the variation in the potential (f> within a mediu of uniform dielectric constant e to the charge density p ... 

Since electrostatic effects dominate the thermodynamic cycle as shown in Figure 10-2, major development efforts have focused on the calculation of electrostatic energy for transferring the neutral and charged forms of the ionizable group from water with dielectric constant of about 80 to the protein with a low dielectric constant (see later discussions). This led to the development of continuum based models, where water and protein are described as uniform dielectric media, and enter into the linearized Poisson-Boltzmann (PB) electrostatic equation,... 

Relaxation processes are probably the most important of the interactions between electric fields and matter. Debye [6] extended the Langevin theory of dipole orientation in a constant field to the case of a varying field. He showed that the Boltzmann factor of the Langevin theory becomes a time-dependent weighting factor. When a steady electric field is applied to a dielectric the distortion polarization, PDisior, will be established very quickly - we can say instantaneously compared with time intervals of interest. But the remaining dipolar part of the polarization (orientation polarization, Porient) takes time to reach its equilibrium value. When the polarization becomes complex, the permittivity must also become complex, as shown by Eq. (5) ... 

B. Fellmuth et al. Dielectric-Constant Gas Thermometry and Determination of the Boltzmann Constant TEMP-MEKO 2004, Cavtat-Dubrovnik Croatia, ISBN number 953-6313-73-1... 

Since our solvents are permanent dipoles that develop an orientation under the influence of an outside electric field activity in opposition to the disordering influence of thermal agitation, such an orientation process is governed by the Boltzmann distribution law and results in the dielectric constant being strongly dependent on the absolute temperature. Thus, as the systems become cooler, the random motion of their molecules decreases and the electric field becomes very effective in orienting them the dielectric constant increases markedly with reduction in temperature at constant volume. 

Presently, there is no direct proof for such a mechanism in pure imidazole (e.g., by NMR) however, the observation that the ratio of the proton diffusion and conduction rates virtually coincide with the Boltzmann factor (i.e., exp(— E e)/ kT)), where is the electrostatic separation energy of two unit charges in a continuum of dielectric constant e) is a strong indication. 

The Gouy-Chapman model describes the properties of the diffuse region of the double-layer. This intuitive model assumes that counterions are point charges that obey a Boltzmann distribution, with highest concentration nearest the oppositely charged fiat surface. The polar solvent is assumed to have the same dielectric constant within the diffuse region. The effective surface... 

This definition for K holds only for monovalent ions and depends on the aqueous dielectric constant (c), Boltzmann s energy (k T), and the electronic charge (e). The Debye length varies inversely with the ionic strength of the solution and thus measures the ability of the ions to screen the protein/interface interactions. 

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