A molecular DebyeHuckel 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 DebyeHückellike response modes that capture the nonlocal response of polar fluids. The Born mode is characterized by a bulk dielectric constant, while a DebyeHückel 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 selfconsistent 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:

 Guizhou Education Univ., Guiyang (People's Republic of China); Ames Lab. and Iowa State Univ., Ames, IA (United States)
 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):
 ISJ9538
Journal ID: ISSN 00219606; TRN: US1800857
 Grant/Contract Number:
 AC0207CH11358
 Resource Type:
 Journal Article: Accepted Manuscript
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 147; Journal Issue: 21; 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 DebyeHuckel 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 DebyeHuckel 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 DebyeHuckel 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 DebyeHuckel 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 DebyeHückellike response modes that capture the nonlocal response of polar fluids. The Born mode is characterized by a bulk dielectric constant, while a DebyeHückel 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 selfconsistent 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 = {00219606},
number = 21,
volume = 147,
place = {United States},
year = {2017},
month = {12}
}
Works referenced in this record:
Modified DebyeHueckel 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
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
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
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
Choosing the reference system for liquid state perturbation theory
journal, July 1984
 Lado, F.
 Molecular Physics, Vol. 52, Issue 4
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
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
Molecular Distribution in Liquids
journal, October 1939
 Kirkwood, John G.
 The Journal of Chemical Physics, Vol. 7, Issue 10
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
An analytical longitudinal dielectric function of primitive electrolyte solutions and its application in predicting thermodynamic properties
journal, October 2015
 Xiao, Tiejun
 Electrochimica Acta, Vol. 178
The analytical expression for the static nonlocal dielectric function of a polar liquid with due account of the overscreening effect
journal, January 2004
 Medvedev, Igor G.
 Electrochimica Acta, Vol. 49, Issue 2
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
Reorganization energy of electron transfer processes in ionic fluids: A molecular DebyeHückel approach
journal, March 2013
 Xiao, Tiejun; Song, Xueyu
 The Journal of Chemical Physics, Vol. 138, Issue 11
Colloquium : Scaled particle theory and the length scales of hydrophobicity
journal, January 2006
 Ashbaugh, Henry S.; Pratt, Lawrence R.
 Reviews of Modern Physics, Vol. 78, Issue 1
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
G ENERALIZED B ORN M ODELS OF M ACROMOLECULAR S OLVATION E FFECTS
journal, October 2000
 Bashford, Donald; Case, David A.
 Annual Review of Physical Chemistry, Vol. 51, Issue 1
Protein crystallization: from purified protein to diffractionquality crystal
journal, January 2008
 Chayen, Naomi E.; Saridakis, Emmanuel
 Nature Methods, Vol. 5, Issue 2
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
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
An integral equation theory for the dense dipolar hardsphere fluid
journal, August 1977
 Patey, G. N.
 Molecular Physics, Vol. 34, Issue 2
Effective pair potentials in charged molecular systems: Water mediated interactions
journal, October 2002
 BagatellaFlores, N.; GonzálezMozuelos, P.
 The Journal of Chemical Physics, Vol. 117, Issue 13
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
Exploring protein native states and largescale 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
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
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
Extended DebyeHückel Theory for Studying the Electrostatic Solvation Energy
journal, January 2015
 Xiao, Tiejun
 ChemPhysChem, Vol. 16, Issue 4
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
A molecular DebyeHückel theory and its applications to electrolyte solutions
journal, September 2011
 Xiao, Tiejun; Song, Xueyu
 The Journal of Chemical Physics, Vol. 135, Issue 10
Theory of polar liquids: I. Dipolar hard spheres
journal, November 1973
 Rushbrooke, G. S.; Stell, G.; Høye, J. S.
 Molecular Physics, Vol. 26, Issue 5
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
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
Computation of methodologyindependent 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
The linear extension of the DebyeHückel theory of electrolyte solutions
journal, March 1970
 Outhwaite, C. W.
 Chemical Physics Letters, Vol. 5, Issue 2
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
Gradient models in molecular biophysics: progress, challenges, opportunities
journal, January 2013
 Bardhan, Jaydeep P.
 Journal of the Mechanical Behavior of Materials, Vol. 22, Issue 56
The Spatial Structure in Liquid Water
journal, August 1994
 Kusalik, P. G.; Svishchev, I. M.
 Science, Vol. 265, Issue 5176
Extension of the Debye–Hückel Theory of Electrolyte Solutions
journal, March 1969
 Outhwaite, C. W.
 The Journal of Chemical Physics, Vol. 50, Issue 6
Microscopic examination of freeenergy 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
A molecular DebyeHückel 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
Ultrafast Photochemistry in Liquids
journal, April 2013
 Rosspeintner, Arnulf; Lang, Bernhard; Vauthey, Eric
 Annual Review of Physical Chemistry, Vol. 64, Issue 1
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
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
Solution of a model for the solvent‐electrolyte interactions in the mean spherical approximation
journal, September 1974
 Blum, L.
 The Journal of Chemical Physics, Vol. 61, Issue 5
Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics
journal, August 1999
 Cramer, Christopher J.; Truhlar, Donald G.
 Chemical Reviews, Vol. 99, Issue 8
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. 19111918
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
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
The screening length of chargeasymmetric electrolytes: A hypernetted chain calculation
journal, August 1998
 McBride, Andrew; Kohonen, Markus; Attard, Phil
 The Journal of Chemical Physics, Vol. 109, Issue 6
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
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
SelfConsistentField 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
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
Macroscopic theory for equilibrium properties of ionicdipolar 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
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