A New Approach in the Theory of Spatially-Restricted Nonlocal Dielectric Media
A new method for the calculation of electric field distributions in the systems with spatiallyrestricted regions filled with polar media with nonlocal dielectric characteristics is proposed. The presence of regions with different dielectric properties in the system (as exemplified by the presence of an ion-filled cavity in which there is no polar medium surrounding the ion) is automatically taken into account within this procedure. The field distribution inside a uniform and isotropic nonlocal dielectric medium outside the spherical cavity containing a spherically symmetric charge distribution (the system represents the ion inside the polar solvent) has illustrated this new approach. In contrast to the previously suggested approach (dielectric approximation), where calculations of this characteristic required complex numerical and analytical calculations, the new method requires only single integration in order to determine the distribution of the potential of the electric field inside the polar medium with an arbitrary law of spatial dispersion of its dielectric permittivity (which can be specified eithter analytically or numerically).
Keywordsspatial dispersion of dielectric permittivity volume cutting effect nonlocal electrostatics solvation energy dielectric permittivity
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- 5.Vorotyntsev, M.A. and Kornyshev, A.A., Physical significance of an effective dielectric constant that depends on the distance from the electrode, Sov. Electrochem., 1979, vol. 15, p. 560.Google Scholar
- 6.Vorotyntsev, M.A., Kornyshev, A.A., and Rubinshtein, A.I., Possible mechanisms of “controlling” ionic interaction at the electrode-solution interface, Sov. Electrochem., 1980, vol. 16, p. 65.Google Scholar
- 7.Vorotyntsev, M.A. and Kornyshev, A.A., Electrostatic interaction on a metal-insulator interface, Sov. Phys.–JETP, 1980, vol. 51, p. 509.Google Scholar
- 12.Vorotyntsev, M.A., Izotov, V.Yu., and Kornyshev, A.A., Differential capacitance of the electric double layer in dilute solutions of surface-inactive electrolytes and upon the specific adsorption of ions: nonlocal and nonlinear effects, Sov. Electrochem., 1983, vol. 19, p. 364.Google Scholar
- 13.Vorotyntsev, M.A. and Kornyshev, A.A., Models to describe collective properties of the metal/solvent interface in electric double-layer theory, Sov. Electrochem., 1984, vol. 20, p. 1.Google Scholar
- 14.Vorotyntsev, M.A. and Holub, K., Image forces at the metal/electrolyte solution interface: their dependence on electrode charge and electrolyte concentration, Sov. Electrochem., 1984, vol. 20, p. 243.Google Scholar
- 17.Kornyshev, A.A., Nonlocal electrostatics of salvation, in The Chemical Physics of Solvation, Dogonadze, R.R., Kalman, E., Kornyshev, A.A., and Ulstrup, J., Eds., Amsterdam: Elsevier, 1985.Google Scholar
- 18.Vorotyntsev, M.A. and Kornyshev, A.A., Elektrostatika sred s prostranstvennoi dispersiei (Electrostatics of Media with Spatial Dispersion), Moscow: Nauka, 1993.Google Scholar
- 20.Rubashkin, A.A., Vorotyntsev, M.A., Antipov, E.M., and Aldoshin, S.M., Nonlocal electrostatic theory of ion solvation: A combination of the overscreening effect in the dielectric response of the medium with a smeared ion charge distribution, Dokl. Phys. Chem., 2015, vol. 464, p. 198.CrossRefGoogle Scholar
- 36.Zubarev, D.N., Neravnovesnaya statisticheskaya termodinamika (Non-Equilibrium Statistical Thermodynamics), Moscow: Nauka, 1971.Google Scholar
- 37.Landau, L.D. and Lifshitz, E.M., Course of Theoretical Physics, Vol. 3: Quantum Mechanics Non-Relativistic Theory, Oxford: Pergamon, 1965, 2nd ed.Google Scholar