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Title: A molecular Debye-Hückel theory and its applications to electrolyte solutions: The size asymmetric case

Abstract

We developed a molecular Debye-Hückel theory for electrolyte solutions with size asymmetry, where the dielectric response of an electrolyte solution is described by a linear combination of Debye-Hückel-like 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 multi-component primitive models of electrolyte solutions.

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Guizhou Education Univ., Guiyang (People's Republic of China). Guizhou Provincial Key Lab. of Computational Nan-Material Science
  2. 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) (SC-22); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1355756
Alternate Identifier(s):
OSTI ID: 1393728
Report Number(s):
IS-J 9308
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC02-07CH11358; W-7405-430 ENG-82
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 12; Journal ID: ISSN 0021-9606
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 Debye-Hückel 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 Debye-Hückel 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 Debye-Hückel 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 Debye-Hückel theory and its applications to electrolyte solutions: The size asymmetric case},
author = {Xiao, Tiejun and Song, Xueyu},
abstractNote = {We developed a molecular Debye-Hückel theory for electrolyte solutions with size asymmetry, where the dielectric response of an electrolyte solution is described by a linear combination of Debye-Hückel-like 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 multi-component primitive models of electrolyte solutions.},
doi = {10.1063/1.4978895},
journal = {Journal of Chemical Physics},
number = 12,
volume = 146,
place = {United States},
year = {2017},
month = {3}
}

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Works referenced in this record:

Chemical and Electrochemical Electron-Transfer Theory
journal, October 1964


Modified Debye-Hueckel Approximation with Effective Charges: An Application of Dressed Ion Theory for Electrolyte Solutions
journal, June 1995

  • Kjellander, Roland
  • The Journal of Physical Chemistry, Vol. 99, Issue 25
  • DOI: 10.1021/j100025a048

Towards understanding the structure and capacitance of electrical double layer in ionic liquids
journal, October 2008


Structure in aqueous solutions of nonpolar solutes from the standpoint of scaled-particle theory
journal, January 1973

  • Stillinger, Frank H.
  • Journal of Solution Chemistry, Vol. 2, Issue 2-3
  • DOI: 10.1007/bf00651970

The linear extension of the Debye-Hückel theory of electrolyte solutions
journal, March 1970


General theory of asymmetric steric interactions in electrostatic double layers
journal, January 2016


Real Ionic Solutions in the Mean Spherical Approximation. 1. Simple Salts in the Primitive Model
journal, January 1996

  • Simonin, Jean-Pierre; Blum, Lesser; Turq, Pierre
  • The Journal of Physical Chemistry, Vol. 100, Issue 18
  • DOI: 10.1021/jp953567o

Dressed ion theory of size-asymmetric electrolytes: Effective ionic charges and the decay length of screened Coulomb potential and pair correlations
journal, February 2005

  • Forsberg, Björn; Ulander, Johan; Kjellander, Roland
  • The Journal of Chemical Physics, Vol. 122, Issue 6
  • DOI: 10.1063/1.1843811

Electron Transfer Reactions in Condensed Phases
journal, October 1984


Extension of the Debye–Hückel Theory of Electrolyte Solutions
journal, March 1969

  • Outhwaite, C. W.
  • The Journal of Chemical Physics, Vol. 50, Issue 6
  • DOI: 10.1063/1.1671378

Microscopic examination of free-energy relationships for electron transfer in polar solvents
journal, February 1987

  • Hwang, Jenn Kang; Warshel, Arieh
  • Journal of the American Chemical Society, Vol. 109, Issue 3
  • DOI: 10.1021/ja00237a013

Mean-field description of ionic size effects with nonuniform ionic sizes: A numerical approach
journal, August 2011


A molecular Debye-Hückel approach to the reorganization energy of electron transfer reactions in an electric cell
journal, October 2014

  • Xiao, Tiejun; Song, Xueyu
  • The Journal of Chemical Physics, Vol. 141, Issue 13
  • DOI: 10.1063/1.4896763

Reorganization energy of electron transfer processes in ionic fluids: A molecular Debye-Hückel approach
journal, March 2013

  • Xiao, Tiejun; Song, Xueyu
  • The Journal of Chemical Physics, Vol. 138, Issue 11
  • DOI: 10.1063/1.4794790

Ionic Liquids at Electrified Interfaces
journal, March 2014

  • Fedorov, Maxim V.; Kornyshev, Alexei A.
  • Chemical Reviews, Vol. 114, Issue 5
  • DOI: 10.1021/cr400374x

Colloquium : Scaled particle theory and the length scales of hydrophobicity
journal, January 2006


Exact mean-field theory of ionic solutions: non-Debye screening
journal, July 2003


Protein crystallization: from purified protein to diffraction-quality crystal
journal, January 2008

  • Chayen, Naomi E.; Saridakis, Emmanuel
  • Nature Methods, Vol. 5, Issue 2
  • DOI: 10.1038/nmeth.f.203

The Hofmeister effect and the behaviour of water at interfaces
journal, November 1985


Solvation dynamics in ionic fluids: An extended Debye–Hückel dielectric continuum model
journal, July 2009

  • Song, Xueyu
  • The Journal of Chemical Physics, Vol. 131, Issue 4
  • DOI: 10.1063/1.3187147

The Statistical Mechanical Basis of the Debye–Hüekel Theory of Strong Electrolytes
journal, August 1954

  • Kirkwood, John G.; Poirier, Jacques C.
  • The Journal of Physical Chemistry, Vol. 58, Issue 8
  • DOI: 10.1021/j150518a004

Morphometric Approach to the Solvation Free Energy of Complex Molecules
journal, August 2006


Predicting protein crystallization from a dilute solution property
journal, July 1994

  • George, A.; Wilson, W. W.
  • Acta Crystallographica Section D Biological Crystallography, Vol. 50, Issue 4
  • DOI: 10.1107/s0907444994001216

Ion Binding and Ion Specificity:  The Hofmeister Effect and Onsager and Lifshitz Theories
journal, April 1997

  • Ninham, Barry W.; Yaminsky, Vassili
  • Langmuir, Vol. 13, Issue 7
  • DOI: 10.1021/la960974y

Extended Debye-Hückel Theory for Studying the Electrostatic Solvation Energy
journal, January 2015


Symmetrical Poisson–Boltzmann and modified Poisson–Boltzmann theories
journal, January 1991

  • Outhwaite, Christopher W.; Molero, Miguel; Bhuiyan, Lutful B.
  • J. Chem. Soc., Faraday Trans., Vol. 87, Issue 19
  • DOI: 10.1039/ft9918703227

Primary and secondary effective charges for electrical double layer systems with asymmetric electrolytes
journal, October 2001

  • Ulander, Johan; Greberg, Hans; Kjellander, Roland
  • The Journal of Chemical Physics, Vol. 115, Issue 15
  • DOI: 10.1063/1.1398587

A molecular Debye-Hückel theory and its applications to electrolyte solutions
journal, September 2011

  • Xiao, Tiejun; Song, Xueyu
  • The Journal of Chemical Physics, Vol. 135, Issue 10
  • DOI: 10.1063/1.3632052

Dressed‐ion theory for electrolyte solutions: A Debye–Hückel‐like reformulation of the exact theory for the primitive model
journal, July 1994

  • Kjellander, Roland; Mitchell, D. John
  • The Journal of Chemical Physics, Vol. 101, Issue 1
  • DOI: 10.1063/1.468116

Morphological Thermodynamics of Fluids: Shape Dependence of Free Energies
journal, October 2004


General Restriction on the Distribution of Ions in Electrolytes
journal, September 1968

  • Stillinger, Frank H.; Lovett, Ronald
  • The Journal of Chemical Physics, Vol. 49, Issue 5
  • DOI: 10.1063/1.1670358

Asymmetric primitive-model electrolytes: Debye-Hückel theory, criticality, and energy bounds
journal, June 2001