A molecular DebyeHückel theory and its applications to electrolyte solutions: The size asymmetric case
Abstract
We developed a molecular DebyeHückel theory for electrolyte solutions with size asymmetry, where the dielectric response of an electrolyte solution is described by a linear combination of DebyeHückellike response modes. Furthermore, as the size asymmetry of an electrolyte solution leads to a charge imbalanced border zone around a solute, the dielectric response to the solute is characterized by two types of charge sources, namely, a bare solute charge and a charge distribution due to size asymmetry. These two kinds of charge sources are screened by the solvent differently, our theory presents a method to calculate the mean electric potential as well as the electrostatic contributions to thermodynamic properties. Finally, the theory was successfully applied to binary as well as multicomponent primitive models of electrolyte solutions.
 Authors:
 Guizhou Education Univ., Guiyang (People's Republic of China). Guizhou Provincial Key Lab. of Computational NanMaterial Science
 Iowa State Univ., Ames, IA (United States). Dept. of Chemistry and Ames Lab.
 Publication Date:
 Research Org.:
 Ames Laboratory (AMES), Ames, IA (United States)
 Sponsoring Org.:
 USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC22); National Natural Science Foundation of China (NNSFC)
 OSTI Identifier:
 1355756
 Alternate Identifier(s):
 OSTI ID: 1393728
 Report Number(s):
 ISJ 9308
Journal ID: ISSN 00219606
 Grant/Contract Number:
 AC0207CH11358; W7405430 ENG82
 Resource Type:
 Journal Article: Accepted Manuscript
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 146; Journal Issue: 12; Journal ID: ISSN 00219606
 Publisher:
 American Institute of Physics (AIP)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Xiao, Tiejun, and Song, Xueyu. A molecular DebyeHückel theory and its applications to electrolyte solutions: The size asymmetric case. United States: N. p., 2017.
Web. doi:10.1063/1.4978895.
Xiao, Tiejun, & Song, Xueyu. A molecular DebyeHückel theory and its applications to electrolyte solutions: The size asymmetric case. United States. doi:10.1063/1.4978895.
Xiao, Tiejun, and Song, Xueyu. Tue .
"A molecular DebyeHückel theory and its applications to electrolyte solutions: The size asymmetric case". United States.
doi:10.1063/1.4978895. https://www.osti.gov/servlets/purl/1355756.
@article{osti_1355756,
title = {A molecular DebyeHückel theory and its applications to electrolyte solutions: The size asymmetric case},
author = {Xiao, Tiejun and Song, Xueyu},
abstractNote = {We developed a molecular DebyeHückel theory for electrolyte solutions with size asymmetry, where the dielectric response of an electrolyte solution is described by a linear combination of DebyeHückellike response modes. Furthermore, as the size asymmetry of an electrolyte solution leads to a charge imbalanced border zone around a solute, the dielectric response to the solute is characterized by two types of charge sources, namely, a bare solute charge and a charge distribution due to size asymmetry. These two kinds of charge sources are screened by the solvent differently, our theory presents a method to calculate the mean electric potential as well as the electrostatic contributions to thermodynamic properties. Finally, the theory was successfully applied to binary as well as multicomponent primitive models of electrolyte solutions.},
doi = {10.1063/1.4978895},
journal = {Journal of Chemical Physics},
number = 12,
volume = 146,
place = {United States},
year = {Tue Mar 28 00:00:00 EDT 2017},
month = {Tue Mar 28 00:00:00 EDT 2017}
}

A molecular DebyeHückel approach to the reorganization energy of electron transfer reactions in an electric cell
Electron transfer near an electrode immersed in ionic fluids is studied using the linear response approximation, namely, mean value of the vertical energy gap can be used to evaluate the reorganization energy, and hence any linear response model that can treat Coulomb interactions successfully can be used for the reorganization energy calculation. Specifically, a molecular DebyeHückel theory is used to calculate the reorganization energy of electron transfer reactions in an electric cell. Applications to electron transfer near an electrode in molten salts show that the reorganization energies from our molecular DebyeHückel theory agree well with the results from MD simulations. 
Multidensity integral equation theory for highly asymmetric electrolyte solutions
Integral equation theory based on a recently developed multidensity formalism [Mol. Phys. {bold 78}, 1247 (1993)] is proposed to study highly asymmetric electrolyte (polyelectrolyte) solutions. The system studied consists of large and highly charged polyions and small counterions having one or two elementary charges. The potential energy of interaction between counterions and polyions is separated into two parts, a strongly attractive part responsible for the association and a nonassociative part. Due to the strong asymmetry in size we can treat each counterion as bondable to a limited number of polyions {ital n}, while each polyion can bond arbitrary number ofmore » 
Long Range DebyeHückel Correction for Computation of Gridbased Electrostatic Forces Between Biomacromolecules
Brownian dynamics (BD) simulations can be used to study very large molecular systems, such as models of the intracellular environment, using atomicdetail structures. Such simulations require strategies to contain the computational costs, especially for the computation of interaction forces and energies. A common approach is to compute interaction forces between macromolecules by precomputing their interaction potentials on threedimensional discretized grids. For longrange interactions, such as electrostatics, gridbased methods are subject to finite size errors. We describe here the implementation of a DebyeHückel correction to the gridbased electrostatic potential used in the SDA BD simulation software that was applied to simulatemore »