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Title: Computer simulations of NaCl association in polarizable water

Abstract

Classical molecular dynamics computer simulations have been used to investigate the thermodynamics and kinetics of sodium chloride association in polarizable water. The simulations make use of the three-site polarizable water model of Dang [J. Chem. Phys. [bold 97], 2659 (1992)], which accurately reproduces many bulk water properties. The model's static dielectric constant and relaxation behavior have been calculated and found to be in reasonable agreement with experimental results. The ion--water interaction potentials have been constructed through fitting to both experimental gas-phase binding enthalpies for small ion--water clusters and to the measured structures and solvation enthalpies of ionic solutions. Structural properties and the potential of mean force for sodium chloride in water have been calculated. In addition, Grote--Hynes theory has been used to predict dynamical features of contact ion-pair dissociation. All of the calculated ionic solution properties have been compared with results from simulations using the extended simple point charge (SPC/E), nonpolarizable water model [J. Phys. Chem. [bold 91], 6296 (1987)]. The dependence on polarizability is found to be small, yet measurable, with the largest effects seen in the solvation structure around the highly polarizable chlorine anion. This work validates the use of some nonpolarizable water models in simulations of manymore » condensed-phase systems of chemical and biochemical interest.« less

Authors:
;  [1]
  1. Theory, Modeling and Simulation, Molecular Science Research Center, Pacific Northwest Laboratory, Richland, Washington 99352 (United States)
Publication Date:
OSTI Identifier:
5283122
DOE Contract Number:  
AC06-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics; (United States)
Additional Journal Information:
Journal Volume: 100:5; Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; SODIUM CHLORIDES; STRUCTURE FACTORS; WATER; CLASSICAL MECHANICS; COMPUTERIZED SIMULATION; ENTHALPY; ION-MOLECULE COLLISIONS; KINETICS; POLARIZABILITY; POTENTIALS; THERMODYNAMICS; ALKALI METAL COMPOUNDS; CHLORIDES; CHLORINE COMPOUNDS; COLLISIONS; ELECTRICAL PROPERTIES; HALIDES; HALOGEN COMPOUNDS; HYDROGEN COMPOUNDS; ION COLLISIONS; MECHANICS; MOLECULE COLLISIONS; OXYGEN COMPOUNDS; PHYSICAL PROPERTIES; SIMULATION; SODIUM COMPOUNDS; THERMODYNAMIC PROPERTIES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Smith, D E, and Dang, L X. Computer simulations of NaCl association in polarizable water. United States: N. p., 1994. Web. doi:10.1063/1.466363.
Smith, D E, & Dang, L X. Computer simulations of NaCl association in polarizable water. United States. https://doi.org/10.1063/1.466363
Smith, D E, and Dang, L X. 1994. "Computer simulations of NaCl association in polarizable water". United States. https://doi.org/10.1063/1.466363.
@article{osti_5283122,
title = {Computer simulations of NaCl association in polarizable water},
author = {Smith, D E and Dang, L X},
abstractNote = {Classical molecular dynamics computer simulations have been used to investigate the thermodynamics and kinetics of sodium chloride association in polarizable water. The simulations make use of the three-site polarizable water model of Dang [J. Chem. Phys. [bold 97], 2659 (1992)], which accurately reproduces many bulk water properties. The model's static dielectric constant and relaxation behavior have been calculated and found to be in reasonable agreement with experimental results. The ion--water interaction potentials have been constructed through fitting to both experimental gas-phase binding enthalpies for small ion--water clusters and to the measured structures and solvation enthalpies of ionic solutions. Structural properties and the potential of mean force for sodium chloride in water have been calculated. In addition, Grote--Hynes theory has been used to predict dynamical features of contact ion-pair dissociation. All of the calculated ionic solution properties have been compared with results from simulations using the extended simple point charge (SPC/E), nonpolarizable water model [J. Phys. Chem. [bold 91], 6296 (1987)]. The dependence on polarizability is found to be small, yet measurable, with the largest effects seen in the solvation structure around the highly polarizable chlorine anion. This work validates the use of some nonpolarizable water models in simulations of many condensed-phase systems of chemical and biochemical interest.},
doi = {10.1063/1.466363},
url = {https://www.osti.gov/biblio/5283122}, journal = {Journal of Chemical Physics; (United States)},
issn = {0021-9606},
number = ,
volume = 100:5,
place = {United States},
year = {1994},
month = {3}
}