Journal of Physical Chemistry, Vol.99, No.25, 10392-10407, 1995
Modified Debye-Huckel Approximation with Effective Charges - An Application of Dressed Ion Theory for Electrolyte-Solutions
The physical basis of the recent dressed ion theory (DIT) by Kjellander and Mitchell (Chem. Phys. Lett. 1992, 200, 76; J. Chem. Phys. 1994, 101, 603) is analyzed and illustrated. In DIT the exact theory for distribution functions in primitive model electrolytes is cast in a form that is virtually the same as in the Debye-Huckel (DH) theory. It is shown in the current work how the utilization of rigorous concepts and exact relationships from DIT (e.g. effective charges of ions and their relationship to the decay length of the pair distributions) can be used to improve the traditional DH approximation and its nonlinear counterpart in a very simple but still substantial manner. The resulting modified versions of the DH theories give values of thermodynamical quantities, effective charge, and decay length (different from the Debye length) for 1:1 and 2:2 aqueous electrolytes that compare well with results from more sophisticated theories and simulations. This constitutes an example-the simplest possible one-of how DIT can be used to improve existing approximations in a new manner.
Keywords:PRIMITIVE MODEL ELECTROLYTES;ONE-COMPONENT PLASMA;POISSON-BOLTZMANN;INTEGRAL-EQUATION;HARD SPHERES;MONTE-CARLO