Dielectric continuum estimate

Including a dielectric continuum estimate of the long ranged dipole-dipole interaction, using a dielectric constant of 78.5 for the continuum outside the sample space of Monte-Carlo simulation. 

Within the framework of the same dielectric continuum model for the solvent, the Gibbs free energy of solvation of an ion of radius and charge may be estimated by calculating the electrostatic work done when hypothetically charging a sphere at constant radius from q = 0 q = This yields the Bom equation [13]... 

M. Maroncelli, Continuum estimates of rotational dielectric friction and polar solvation, J. Chem. Phys., 106 (1997) 1545-55. 

In terms of traditional Transition State Theory (TST) for solution reactions [40,41], in which e.g. the activation free energy AG can be estimated with equilibrium solvation dielectric continuum theories [42-46], the nonequilibrium or dynamical solvation aspects enter the prefactor of the rate constant k, or in terms of the ratio of k to its TST approximation kTST, k, the transmission coefficient, k and kTST are related by [41]... 

P+ is the adiabatic electronic polarization energy of the medium, experienced by a positive ion. Vo is the minimum energy of a quasi-free electron in the liquid relative to an electron in vacuum. Then, if we consider the solvent as a dielectric continuum, Bom s equation [97] provides an expression to estimate P+ ... 

This method avoids the convergence and accuracy problems of molecular dynamics or Monte Carlo simulations of systems containing explicit solvent molecules, by evaluating the electrostatic free energy of just one solute conformation surrounded by a dielectric continuum, and by adding the surface term and an estimate of the loss of the configurational entropy upon binding.77... 

For two spherical complex ions of radii r, and r2 the free energy change required to rearrange the solvent shells of the two ions from the reactant state to the transition state is estimated (Marcus, 1956) from a classical dielectric continuum model of the solvent, giving (51) and (52), in which all quantities... 

The latest models propose to represent electrolyte solutions as a collections of hard spheres of equal size, ions, immersed in a dielectric continuum, the solvent. For such a system, what is called the Mean Spherical Approximation, MSA, has been successful in estimating osmotic and mean activity coefficients for aqueous 1 1 electrolyte solutions, and has provided a reasonable fit to experimental data for dilute solutions of concentrations up to -0.3 mol dm". The advantage in this approach is that only one... 

The slope of this correlation is about 50% larger than predicted by equation (31). This contrast may arise from an underestimate of the external radii of the complexes, or (more likely) some specific solvation effects and the inadequacies of the dielectric continuum model on which equation (31) is based. Equation (55) seems to be a good basis for estimating the contributions of Xs, provided the same procedure is used to estimate Relatively elaborate solvation models, in... 

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