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Continuum radial dielectric functions for ion and dipole solution systems
Author(s) -
Ehrenson S.
Publication year - 1989
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540100108
Subject(s) - electrostriction , permittivity , dipole , dielectric , vacuum permittivity , debye , ion , chemistry , ionic bonding , debye–hückel equation , lorentz transformation , condensed matter physics , statistical physics , physics , relative permittivity , classical mechanics , quantum mechanics , electrode , piezoelectricity , acoustics , electrolyte
Radial dielectric constant (permittivity) functions for ionic solute, polar solvent systems of the type obtainable from the Lorentz‐Debye continuum field formulations are reexamined. Major interest is focused on the assumptions underlying these formulations and their expression in limiting field behavior. The analysis is extended to dipolar solutes and the importance of two types of corrections are evaluated. The first draws connections with the concept of the reaction field as employed by Onsager. This correction is shown to be significant as regards range of predicted saturation effects and for dipole moment self‐consistency, for the same type molecule serving as solute and solvent. The second type correction involves the phenomenon of electrostriction whose effects appear much more limited both in range and on the intensity of the fields necessary for its observation. Application of the permittivity functions developed to compute modified Born model hydration energies for a variety of ions is illustrated. Excellent asymptotic approximations for all radial permittivity equations of interest are also presented which should enhance their future utility.