Title

A Systematic Way to Extend the Debye–Hückel Theory beyond Dilute Electrolyte Solutions

Publication Date

3-4-2021

Department

Ames Laboratory; Chemistry

Campus Units

Ames Laboratory, Chemistry

OSTI ID+

1773050

Report Number

IS-J 10447

DOI

10.1021/acs.jpca.0c10226

Journal Title

Journal of Physical Chemistry A

Volume Number

125

Issue Number

10

First Page

2173

Last Page

2183

Abstract

An extended Debye–Hückel theory with fourth order gradient term is developed for electrolyte solutions; namely, the electric potential φ(r) of the bulk electrolyte solution can be described by ∇2φ(r) = κ2φ(r) + LQ2∇4φ(r), where the parameters κ and LQ are chosen to reproduce the first two roots of the dielectric response function of the bulk solution. Three boundary conditions for solving the electric potential problem are proposed based upon the continuity conditions of involving functions at the dielectric boundary, with which a boundary element method for the electric potential of a solute with a general geometrical shape and charge distribution is derived. Solutions for the electric potential of a spherical ion and a diatomic molecule are found and used to calculate their electrostatic solvation energies. The validity of the theory is successfully demonstrated when applied to binary as well as multicomponent primitive models of electrolyte solutions.

DOE Contract Number(s)

AC02-07CH11358

Language

en

Publisher

Iowa State University Digital Repository, Ames IA (United States)

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