Free energy of a charge distribution in concentric dielectric continua

Abstract

A theoretical treatment for dealing with the energetics of an arbitrary charge distribution imbedded in a central spherical cavity surrounded by two concentric dielectric continua is described. The results provide a general means for treating environmental effects using the continuum model. The form of the solution is particularly suited to identifying the contributions of the various dielectric regions.

Solvent influence on the rotational isomerism in terephthalaldehyde

“…Such short-range nonspecific ordering effect leads to the lowering of the dielectric permittivity. Thus it is not strange that the dependence of G tc on ε for the It Ic equilibrium can be well described by means of these modifications [48,49] of the continuum model, which admit the decrease of the dielectric permittivity in the nearest surrounding of the dipole-containing cavity. Additionally, preferential orientation of solvent molecules was investigated using discrete solvation model via molecular dynamics.…”

“…Therefore the homogeneous dielectric medium considered in the Onsager-Böttcher theory must be replaced by a heterogeneous one. Two modifications of Onsager-Böttcher's model admit the spatial variation of ε, which is small (local) near the solute dipole and is large (bulk) at long distance from it [48,49]. The BlockWalker modification [48] assumes that the bulk ε value is not reached immediately after crossing the cavity boundary, but approaches it asymptotically, according to the relation ε(r ) = εe −k/r , where r is the distance from the center of the cavity and k is equal to a ln ε.…”

“…It is seen that they reasonably explain the changes in G (s) tc , going on from one solvent to another. The second modification, proposed by Beveridge and Schnuelle [49], considers two dielectric continua. The polar solute is still treated as a point dipole in the center of a spherical cavity of radius a and ε = 1.…”

Metaphotonics: An emerging field with opportunities and challenges

“…85,86,87,88,89,90,91,92,93,94 For these methods, the interactions between the quantum subsystem and the outer solvent is given by the induced polarization in the outer solvent and the electric field due to the charge distribution of the solvated quantum mechanical subsystem. The coupling between the quantum mechanical and the classical subsystems is accomplished by an effective interaction operator, which provides a modified quantum mechanical equation for finding the electronic wave function of the solvated molecule.…”

Advanced dielectric continuum models of solvation, their connection to microscopic solvent models, and application to electron transfer reactions

“…The total solvation energy [18,37], (26) is naturally divided into inertialess and inertial contributions; it reduces to the Born expression when rl = P1. The extra cavity parameter, namely the width 3 of the intersurface layer in Eq.…”