Computer simulations of NaCl association in polarizable water

Journal Article · Tue Mar 01 00:00:00 EST 1994 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.466363· OSTI ID:5283122

Smith, D E; Dang, L X ^[1]

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1. Theory, Modeling and Simulation, Molecular Science Research Center, Pacific Northwest Laboratory, Richland, Washington 99352 (United States)

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.

• DOE Contract Number: AC06-76RL01830
• OSTI ID: 5283122
• Journal Information: Journal of Chemical Physics; (United States), Vol. 100:5; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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