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Title: The Poisson–Boltzmann model for implicit solvation of electrolyte solutions: Quantum chemical implementation and assessment via Sechenov coefficients

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5131020 · OSTI ID:1634059
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. The Ohio State Univ., Columbus, OH (United States)
+ Show Author Affiliations

Here, we present the theory and implementation of a Poisson-Boltzmann implicit solvation model for electrolyte solutions. This model can be combined with arbitrary electronic structure methods that provide an accurate charge density of the solute. A hierarchy of approximations for this model includes a linear approximation for weak electrostatic potentials, finite size of the mobile electrolyte ions, and a Stern-layer correction. Recasting the Poisson-Boltzmann equations into Euler-Lagrange equations then significantly simplifies the derivation of the free energy of solvation for these approximate models. The parameters of the model are either fit directly to experimental observables-e.g., the finite ion size-or optimized for agreement with experimental results. Experimental data for this optimization are available in the form of Sechenov coefficients that describe the linear dependence of the salting-out effect of solutes with respect to the electrolyte concentration. In the final part, we rationalize the qualitative disagreement of the finite ion size modification to the Poisson-Boltzmann model with experimental observations by taking into account the electrolyte concentration dependence of the Stern layer. A route toward a revised model that captures the experimental observations while including the finite ion size effects is then outlined. This implementation paves the way for the study of electrochemical and electrocatalytic processes of molecules and cluster models with accurate electronic structure methods.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1634059
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 151; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (88)

The Poisson-Boltzmann equation for biomolecular electrostatics: a tool for structural biology journal January 2002
Ab initio molecular simulations with numeric atom-centered orbitals journal November 2009
Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena journal February 1995
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient journal January 1993
Evaluation of Ion Binding to DNA Duplexes Using a Size-Modified Poisson-Boltzmann Theory journal November 2007
Ueber einige Gesetze der Vertheilung elektrischer Ströme in körperlichen Leitern mit Anwendung auf die thierisch-elektrischen Versuche journal January 1853
Effect of Electrolyte Concentration on the Stern Layer Thickness at a Charged Interface journal February 2016
Effect of Electrolyte Concentration on the Stern Layer Thickness at a Charged Interface journal February 2016
Polyelectrolyte electrostatics: Salt dependence, entropic, and enthalpic contributions to free energy in the nonlinear Poisson-Boltzmann model journal August 1995
Quantum Mechanical Continuum Solvation Models journal October 2005
Estimation of Dimerisation Constants from Complexatin-Induced Displacements of1H-NMR Chemical Shifts: Dimerisation of Caffeine journal May 1984
PB-AM: An open-source, fully analytical linear poisson-boltzmann solver journal November 2016
ImprovedSCF convergence acceleration journal January 1982
Remarks on the use of the apparent surface charges (ASC) methods in solvation problems: Iterative versus matrix-inversion procedures and the renormalization of the apparent charges journal December 1995
The Poisson-Boltzmann equation for biomolecular electrostatics: a tool for structural biology journal January 2002
Salting out and salting in of benzene in water: a consistency evaluation journal January 2018
Computational studies of polyurethanases from Pseudomonas journal January 2021
Convergence acceleration of iterative sequences. the case of scf iteration journal July 1980
A new method for incorporating solvent effect into the classical, ab initio molecular orbital and density functional theory frameworks for arbitrary shape cavity journal June 1995
Ab initio study of solvated molecules: a new implementation of the polarizable continuum model journal June 1996
Adaptive mesh refinement for hyperbolic partial differential equations journal March 1984
Local adaptive mesh refinement for shock hydrodynamics journal May 1989
The interpretation of protein structures: Estimation of static accessibility journal February 1971
Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects journal February 1981
Determination of sets of solute descriptors from chromatographic measurements journal May 2004
Ab initio molecular simulations with numeric atom-centered orbitals journal November 2009
Multigrid elliptic equation solver with adaptive mesh refinement journal November 2005
Structure, Stability, and Thermodynamics of Lamellar DNA-Lipid Complexes journal July 1998
Adsorption of large ions from an electrolyte solution: a modified Poisson–Boltzmann equation journal November 2000
COSMO-RS: a novel and efficient method for the a priori prediction of thermophysical data of liquids journal July 2000
Determination of the solubility behavior of some polycyclic aromatic hydrocarbons in water journal June 1978
Function-Space-Based Solution Scheme for the Size-Modified Poisson–Boltzmann Equation in Full-Potential DFT journal July 2016
Soft-Sphere Continuum Solvation in Electronic-Structure Calculations journal July 2017
DL_MG: A Parallel Multigrid Poisson and Poisson–Boltzmann Solver for Electronic Structure Calculations in Vacuum and Solution journal February 2018
High Order Compact Multigrid Solver for Implicit Solvation Models journal November 2018
Family of Oxygen–Oxygen Radial Distribution Functions for Water journal July 2015
A Universal Approach to Solvation Modeling journal June 2008
Activity Coefficients of Nonelectrolyte Solutes in Aqueous Salt Solutions. journal August 1952
Implicit Solvation Models:  Equilibria, Structure, Spectra, and Dynamics journal August 1999
Quantum Mechanical Continuum Solvation Models journal August 2005
New and Efficient Poisson−Boltzmann Solver for Interaction of Multiple Proteins journal June 2010
A Fast and Robust Poisson–Boltzmann Solver Based on Adaptive Cartesian Grids journal April 2011
Salting-Out Effect in Aqueous NaCl Solutions: Trends with Size and Polarity of Solute Molecules journal January 2012
Topological Modeling of the Setschenow Constant journal July 2004
Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena journal February 1995
Calculating total electrostatic energies with the nonlinear Poisson-Boltzmann equation journal September 1990
Polyelectrolyte theory. 3. The surface potential in mixed-salt solutions journal March 1981
Conformational energy of glycine in aqueous solutions and relative stability of the zwitterionic and neutral forms. An ab initio study journal April 1984
Individual Activity Coefficients of Ions in Aqueous Solutions journal September 1937
Electric Moments of Molecules in Liquids journal August 1936
The Hydrated Electron at the Surface of Neat Liquid Water Appears To Be Indistinguishable from the Bulk Species journal August 2016
Poisson–Boltzmann versus Size-Modified Poisson–Boltzmann Electrostatics Applied to Lipid Bilayers journal December 2014
Electrostatic Free Energy and Its Variations in Implicit Solvent Models journal March 2008
Use of the Poisson−Boltzmann Equation To Estimate The Electrostatic Free Energy Barrier for Dielectric Models of Biological Ion Channels journal July 1997
Monovalent and Divalent Salt Effects on Electrostatic Free Energies Defined by the Nonlinear Poisson−Boltzmann Equation:  Application to DNA Binding Reactions journal October 1997
Evaluation of Solvent Effects in Isotropic and Anisotropic Dielectrics and in Ionic Solutions with a Unified Integral Equation Method:  Theoretical Bases, Computational Implementation, and Numerical Applications journal December 1997
Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays journal May 2020
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
ωB97X-V: A 10-parameter, range-separated hybrid, generalized gradient approximation density functional with nonlocal correlation, designed by a survival-of-the-fittest strategy journal January 2014
Scales of solute hydrogen-bonding: their construction and application to physicochemical and biochemical processes journal January 1993
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient journal January 1993
Sur la constitution de la charge électrique à la surface d'un électrolyte journal January 1910
The Dielectric Polarization of Polar Liquids journal October 1939
A unified electrostatic and cavitation model for first-principles molecular dynamics in solution journal February 2006
A simple polarizable continuum solvation model for electrolyte solutions journal May 2011
Revised self-consistent continuum solvation in electronic-structure calculations journal February 2012
A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics journal August 1997
Excited states and solvatochromic shifts within a nonequilibrium solvation approach: A new formulation of the integral equation formalism method at the self-consistent field, configuration interaction, and multiconfiguration self-consistent field level journal August 1998
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways journal February 2014
A generalized Poisson and Poisson-Boltzmann solver for electrostatic environments journal January 2016
Salting-out effects by pressure-corrected 3D-RISM journal November 2016
Evaluating continuum solvation models for the electrode-electrolyte interface: Challenges and strategies for improvement journal February 2017
Transferable ionic parameters for first-principles Poisson-Boltzmann solvation calculations: Neutral solutes in aqueous monovalent salt solutions journal April 2017
Quantum chemistry in arbitrary dielectric environments: Theory and implementation of nonequilibrium Poisson boundary conditions and application to compute vertical ionization energies at the air/water interface journal June 2018
Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations journal April 2018
Continuum models of the electrochemical diffuse layer in electronic-structure calculations journal January 2019
Electrostatics of nanosystems: Application to microtubules and the ribosome journal August 2001
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
Intrinsically smooth discretisation of Connolly's solvent-excluded molecular surface journal July 2019
LI. A contribution to the theory of electrocapillarity journal April 1913
Electronic structure calculations of liquid-solid interfaces: Combination of density functional theory and modified Poisson-Boltzmann theory journal June 2008
Steric Effects in Electrolytes: A Modified Poisson-Boltzmann Equation journal July 1997
A Multigrid Tutorial, Second Edition book January 2000
Random sample consensus: a paradigm for model fitting with applications to image analysis and automated cartography journal June 1981
Evaluation of Ion Binding to DNA Duplexes Using a Size-Modified Poisson-Boltzmann Theory journal November 2007
Multi-Level Adaptive Solutions to Boundary-Value Problems journal April 1977
A unified electrostatic and cavitation model for first-principles molecular dynamics in solution text January 2005
A generalized Poisson and Poisson-Boltzmann solver for electrostatic environments text January 2016

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