Screening and asymptotic decay of pair distributions in asymmetric electrolytes

Abstract

Thermodynamics of ternary electrolytes: Enhanced adsorption of macroions as minority component to liquid interfaces J. Chem. Phys. 130, 044502 (2009); 10.1063/1.3065071 Electric conductivities of 1:1 electrolytes in liquid methanol along the liquid-vapor coexistence curve up to the critical temperature. III. Tetraalkylammonium bromides Dressed ion theory of size-asymmetric electrolytes: Effective ionic charges and the decay length of screened Coulomb potential and pair correlations J. Chem. Phys. 122, 064502 (2005); 10.1063/1.1843811The screening length of charge-asymmetric electrolytes: A hypernetted chain calculation An accurate description of the screening behavior of asymmetric binary electrolyte solutions is obtained by applying the dressed ion theory to acquire the three leading terms in the asymptotic decay of the radial pair distribution function g i j (r) at large distances r. These terms give a surprisingly good representation of the distribution function for quite small r values. A minimum of two asymptotic terms are needed for representing g i j (r) at moderately large r in a quite wide concentration range. The relationships between the large r asymptotic behavior of charge-charge, density-density, and charge-density correlations are investigated by means of the dressed ion distribution functions. The role that the dielectric response function of the electrolyte plays for the asymptotic behavior is illuminated and the relationship between this function and the dressed ion charge distributions is given. Ionic effective charges, effective permittivities, and decay lengths and their higher order analogues are calculated for 1:2 electrolytes using the hypernetted chain approximation.

Decay behavior of screened electrostatic surface forces in ionic liquids: the vital role of non-local electrostatics

“…The same must apply † The general DIT and DMT formalisms 20,22,23,25,26 can be applied to other cases, but the simplified version used here has this limitation. In actual fact, the average density of j ions at point r is affected by the values of electrostatic potential ψ w in a whole neighborhood of this point.…”

Thermoreversible crosslinking of polyelectrolyte chains

“…49 The change in effective potentials is generated by the condition of having finite values of the potential given by Eq. [50][51][52][53][54][55] In the Fourier transform ͓see Eq. This transition does not appear in the standard Debye-Hückel results, which can be regained within the RPA approach by setting 1/a→ϱ in Eq.…”

The decay of pair correlation functions in ionic fluids: A dressed ion theory analysis of Monte Carlo simulations

“…At sufficiently high concentrations a second pole of ĥ QQ (k) at kϭiЈ will become important for the long-range correlations. If we include the term associated with this second pole the asymptotic expression for the charge-charge fluctuations h QQ (r) for dilute RPM electrolytes is 9,13 …”

“…All functions ĥ IJ (k) are coupled 9,19 and h QQ , h NN , and h QN all share the same decay length in general.…”

“…1,2,6-13 The numerical results of these studies have, however, been restricted to various approximations. [6][7][8][9][10][11][12][13] In this work we extract decay parameters of various ionion correlation functions from radial distributions calculated via Monte Carlo simulations of size-symmetric 1:1, 1:2, and 2:2 electrolytes in the primitive model. The motivation for this is partly to investigate how decay parameters can be extracted from simulations, partly to compare the results from the simulations with theoretical predictions and numerical results from calculations using the hypernetted chain ͑HNC͒ approximation.…”