Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Submitted Manuscript

Publication Date

3-18-2021

Journal or Book Title

Journal of Physical Chemistry A

Volume

125

Issue

10

First Page

2173

Last Page

2183

DOI

10.1021/acs.jpca.0c10226

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.

Comments

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acs.jpca.0c10226. Posted with permission.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Published Version

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