skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A molecular Debye-Huckel theory of solvation in polar fluids: An extension of the Born model

Abstract

A dielectric response theory of solvation beyond the conventional Born model for polar fluids is presented. The dielectric response of a polar fluid is described by a Born response mode and a linear combination of Debye-Hückel-like response modes that capture the nonlocal response of polar fluids. The Born mode is characterized by a bulk dielectric constant, while a Debye-Hückel mode is characterized by its corresponding Debye screening length. Both the bulk dielectric constant and the Debye screening lengths are determined from the bulk dielectric function of the polar fluid. The linear combination coefficients of the response modes are evaluated in a self-consistent way and can be used to evaluate the electrostatic contribution to the thermodynamic properties of a polar fluid. In conclusion, our theory is applied to a dipolar hard sphere fluid as well as interaction site models of polar fluids such as water, where the electrostatic contribution to their thermodynamic properties can be obtained accurately.

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Guizhou Education Univ., Guiyang (People's Republic of China); Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1415821
Alternate Identifier(s):
OSTI ID: 1411490
Report Number(s):
IS-J-9538
Journal ID: ISSN 0021-9606; TRN: US1800857
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 21; 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-Huckel theory of solvation in polar fluids: An extension of the Born model. United States: N. p., 2017. Web. doi:10.1063/1.4998255.
Xiao, Tiejun, & Song, Xueyu. A molecular Debye-Huckel theory of solvation in polar fluids: An extension of the Born model. United States. doi:10.1063/1.4998255.
Xiao, Tiejun, and Song, Xueyu. Wed . "A molecular Debye-Huckel theory of solvation in polar fluids: An extension of the Born model". United States. doi:10.1063/1.4998255. https://www.osti.gov/servlets/purl/1415821.
@article{osti_1415821,
title = {A molecular Debye-Huckel theory of solvation in polar fluids: An extension of the Born model},
author = {Xiao, Tiejun and Song, Xueyu},
abstractNote = {A dielectric response theory of solvation beyond the conventional Born model for polar fluids is presented. The dielectric response of a polar fluid is described by a Born response mode and a linear combination of Debye-Hückel-like response modes that capture the nonlocal response of polar fluids. The Born mode is characterized by a bulk dielectric constant, while a Debye-Hückel mode is characterized by its corresponding Debye screening length. Both the bulk dielectric constant and the Debye screening lengths are determined from the bulk dielectric function of the polar fluid. The linear combination coefficients of the response modes are evaluated in a self-consistent way and can be used to evaluate the electrostatic contribution to the thermodynamic properties of a polar fluid. In conclusion, our theory is applied to a dipolar hard sphere fluid as well as interaction site models of polar fluids such as water, where the electrostatic contribution to their thermodynamic properties can be obtained accurately.},
doi = {10.1063/1.4998255},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 21,
volume = 147,
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:

Works referenced in this record:

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

Derivation of an integral equation for pair correlation functions in molecular fluids
journal, September 1973

  • Chandler, David
  • The Journal of Chemical Physics, Vol. 59, Issue 5
  • DOI: 10.1063/1.1680393

A model of solvent structure around ions
journal, March 1979

  • Chan, Derek Y. C.; Mitchell, D. John; Ninham, Barry W.
  • The Journal of Chemical Physics, Vol. 70, Issue 6
  • DOI: 10.1063/1.437833

On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I
journal, May 1956

  • Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 24, Issue 5
  • DOI: 10.1063/1.1742723

Choosing the reference system for liquid state perturbation theory
journal, July 1984


A Continuum Solvent Model of the Multipolar Dispersion Solvation Energy
journal, August 2013

  • Duignan, Timothy T.; Parsons, Drew F.; Ninham, Barry W.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 32
  • DOI: 10.1021/jp403595x

Statistical Mechanical Theory of Ionic Solutions Based on the Interaction Site Model: Dielectric Properties and Pair Correlation Functions
journal, March 1981

  • Ohba, Masaharu; Arakawa, Kiyoshi
  • Journal of the Physical Society of Japan, Vol. 50, Issue 3
  • DOI: 10.1143/jpsj.50.743

Molecular Distribution in Liquids
journal, October 1939

  • Kirkwood, John G.
  • The Journal of Chemical Physics, Vol. 7, Issue 10
  • DOI: 10.1063/1.1750344

Role of Repulsive Forces in Determining the Equilibrium Structure of Simple Liquids
journal, June 1971

  • Weeks, John D.; Chandler, David; Andersen, Hans C.
  • The Journal of Chemical Physics, Vol. 54, Issue 12
  • DOI: 10.1063/1.1674820

The shape of the nonlocal dielectric function of polar liquids and the implications for thermodynamic properties of electrolytes: A comparative study
journal, January 1996

  • Kornyshev, Alexei A.; Sutmann, Godehard
  • The Journal of Chemical Physics, Vol. 104, Issue 4
  • DOI: 10.1063/1.470741

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

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


Improved Generalized Born Solvent Model Parameters for Protein Simulations
journal, March 2013

  • Nguyen, Hai; Roe, Daniel R.; Simmerling, Carlos
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 4
  • DOI: 10.1021/ct3010485

G ENERALIZED B ORN M ODELS OF M ACROMOLECULAR S OLVATION E FFECTS
journal, October 2000


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

A Continuum Model of Solvation Energies Including Electrostatic, Dispersion, and Cavity Contributions
journal, August 2013

  • Duignan, Timothy T.; Parsons, Drew F.; Ninham, Barry W.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 32
  • DOI: 10.1021/jp403596c

Thermodynamic Parameters for the Solvation of Monatomic Ions in Water
journal, December 1999

  • Fawcett, W. Ronald
  • The Journal of Physical Chemistry B, Vol. 103, Issue 50
  • DOI: 10.1021/jp991802n

An integral equation theory for the dense dipolar hard-sphere fluid
journal, August 1977


Effective pair potentials in charged molecular systems: Water mediated interactions
journal, October 2002

  • Bagatella-Flores, N.; González-Mozuelos, P.
  • The Journal of Chemical Physics, Vol. 117, Issue 13
  • DOI: 10.1063/1.1503333

Static longitudinal dielectric function of model molecular fluids
journal, February 1992

  • Raineri, Fernando O.; Resat, Haluk; Friedman, Harold L.
  • The Journal of Chemical Physics, Vol. 96, Issue 4
  • DOI: 10.1063/1.461952

Exploring protein native states and large-scale conformational changes with a modified generalized born model
journal, March 2004

  • Onufriev, Alexey; Bashford, Donald; Case, David A.
  • Proteins: Structure, Function, and Bioinformatics, Vol. 55, Issue 2
  • DOI: 10.1002/prot.20033

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

Gaussian Field Model of Dielectric Solvation Dynamics
journal, January 1996

  • Song, Xueyu; Chandler, David; Marcus, R. A.
  • The Journal of Physical Chemistry, Vol. 100, Issue 29
  • DOI: 10.1021/jp960887e

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


Dressed molecule theory for liquids and solutions: An exact charge renormalization formalism for molecules with arbitrary charge distributions
journal, December 2003

  • Ramirez, Rosa; Kjellander, Roland
  • The Journal of Chemical Physics, Vol. 119, Issue 21
  • DOI: 10.1063/1.1623179

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

Theory of polar liquids: I. Dipolar hard spheres
journal, November 1973


The structure of electrolytes at charged surfaces: Ion–dipole mixtures
journal, September 1980

  • Carnie, Steven L.; Chan, Derek Y. C.
  • The Journal of Chemical Physics, Vol. 73, Issue 6
  • DOI: 10.1063/1.440468

Relation between the local field at large distances from a charge or dipole and the dielectric constant
journal, January 1980

  • Pollock, E. L.; Alder, B. J.; Pratt, L. R.
  • Proceedings of the National Academy of Sciences, Vol. 77, Issue 1
  • DOI: 10.1073/pnas.77.1.49

Computation of methodology-independent ionic solvation free energies from molecular simulations. II. The hydration free energy of the sodium cation
journal, June 2006

  • Kastenholz, Mika A.; Hünenberger, Philippe H.
  • The Journal of Chemical Physics, Vol. 124, Issue 22
  • DOI: 10.1063/1.2201698

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


Beyond Poisson–Boltzmann: Images and correlations in the electric double layer. I. Counterions only
journal, April 1988

  • Attard, Phil; Mitchell, D. John; Ninham, Barry W.
  • The Journal of Chemical Physics, Vol. 88, Issue 8
  • DOI: 10.1063/1.454678

Gradient models in molecular biophysics: progress, challenges, opportunities
journal, January 2013

  • Bardhan, Jaydeep P.
  • Journal of the Mechanical Behavior of Materials, Vol. 22, Issue 5-6
  • DOI: 10.1515/jmbm-2013-0024

The Spatial Structure in Liquid Water
journal, August 1994


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

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

Ultrafast Photochemistry in Liquids
journal, April 2013


On the theory of dipolar fluids and ion–dipole mixtures
journal, July 1978

  • Chan, Derek Y. C.; Mitchell, D. John; Ninham, Barry W.
  • The Journal of Chemical Physics, Vol. 69, Issue 2
  • DOI: 10.1063/1.436635

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

Solution of a model for the solvent‐electrolyte interactions in the mean spherical approximation
journal, September 1974


Implicit Solvation Models:  Equilibria, Structure, Spectra, and Dynamics
journal, August 1999

  • Cramer, Christopher J.; Truhlar, Donald G.
  • Chemical Reviews, Vol. 99, Issue 8
  • DOI: 10.1021/cr960149m

DL_POLY_3: new dimensions in molecular dynamics simulations via massive parallelism
journal, January 2006

  • Todorov, Ilian T.; Smith, William; Trachenko, Kostya
  • Journal of Materials Chemistry, Vol. 16, Issue 20, p. 1911-1918
  • DOI: 10.1039/b517931a

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

Mean spherical model for hard ions and dipoles: Thermodynamics and correlation functions
journal, May 1980

  • Vericat, Fernando; Blum, Lesser
  • Journal of Statistical Physics, Vol. 22, Issue 5
  • DOI: 10.1007/bf01011340

The screening length of charge-asymmetric electrolytes: A hypernetted chain calculation
journal, August 1998

  • McBride, Andrew; Kohonen, Markus; Attard, Phil
  • The Journal of Chemical Physics, Vol. 109, Issue 6
  • DOI: 10.1063/1.476810

Exact Solution of the Mean Spherical Model for Fluids of Hard Spheres with Permanent Electric Dipole Moments
journal, November 1971

  • Wertheim, M. S.
  • The Journal of Chemical Physics, Vol. 55, Issue 9
  • DOI: 10.1063/1.1676751

The missing term in effective pair potentials
journal, November 1987

  • Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P.
  • The Journal of Physical Chemistry, Vol. 91, Issue 24
  • DOI: 10.1021/j100308a038

Self-Consistent-Field Calculation of Pauli Repulsion and Dispersion Contributions to the Solvation Free Energy in the Polarizable Continuum Model
journal, February 1997

  • Amovilli, Claudio; Mennucci, Benedetta
  • The Journal of Physical Chemistry B, Vol. 101, Issue 6
  • DOI: 10.1021/jp9621991

Mean Spherical Model Integral Equation for Charged Hard Spheres I. Method of Solution
journal, March 1972

  • Waisman, Eduardo; Lebowitz, Joel L.
  • The Journal of Chemical Physics, Vol. 56, Issue 6
  • DOI: 10.1063/1.1677644

Macroscopic theory for equilibrium properties of ionic-dipolar mixtures and application to an ionic model fluid
journal, May 1998

  • Weiss, V. C.; Schröer, W.
  • The Journal of Chemical Physics, Vol. 108, Issue 18
  • DOI: 10.1063/1.476210

Mean Spherical Model Integral Equation for Charged Hard Spheres. II. Results
journal, March 1972

  • Waisman, Eduardo; Lebowitz, Joel L.
  • The Journal of Chemical Physics, Vol. 56, Issue 6
  • DOI: 10.1063/1.1677645