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Title: Molecular Mechanism of Transporting a Polarizable Iodide Anion Across the Water-CCl4 Liquid/Liquid Interface

Abstract

The result of transferring a polarizable iodide anion across the H2O-CCl4 liquid/liquid interface was investigated. The computed transfer free energy profile or potential of mean force exhibits a minimum near the Gibbs dividing surface, and its characteristics are similar to those of found in a corresponding water vapor/liquid interface study involving a smaller minimum free energy. Molecular dynamics simulations also were carried out to compare the concentrations of NaCl, NaBr, and NaI at H2O-vapor and H2O-CCl4 interfaces. While the concentration of bromide and iodide ions were lower at the H2O-CCl4 interface when compared to the H2O-vapor interface, the chloride ion concentrations were similar at both interfaces. Analysis of the solvation structures of iodide and chloride ions revealed that the more polarizable iodide ion was less solvated than the chloride ion at the interface. This characteristic brought the iodide ion in greater contact with CCl4 than the chloride ion, resulting in repulsive interactions with CCl4, which reduced its propensity for the interface. This work was performed at the Pacific Northwest National Laboratory (PNNL) and was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE. Themore » DOE Division of Chemical Sciences and the Scientific Computing Staff, Office of Science provided computer resources at the National Energy Research Supercomputer Center (Berkeley, California) that supported this research.« less

Authors:
;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
908734
Report Number(s):
PNNL-SA-53038
Journal ID: ISSN 0021-9606; JCPSA6; KC0301020; TRN: US200722%%766
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics, 126(13); Journal Volume: 126; Journal Issue: 13
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MASS TRANSFER; FREE ENERGY; IODIDES; SOLVATION; WATER; CARBON TETRACHLORIDE; INTERFACES; MOLECULAR DYNAMICS METHOD; liquid interface; iodide anion; molecular dynamics simulation

Citation Formats

Wick, Collin D., and Dang, Liem X. Molecular Mechanism of Transporting a Polarizable Iodide Anion Across the Water-CCl4 Liquid/Liquid Interface. United States: N. p., 2007. Web. doi:10.1063/1.2717164.
Wick, Collin D., & Dang, Liem X. Molecular Mechanism of Transporting a Polarizable Iodide Anion Across the Water-CCl4 Liquid/Liquid Interface. United States. doi:10.1063/1.2717164.
Wick, Collin D., and Dang, Liem X. Sat . "Molecular Mechanism of Transporting a Polarizable Iodide Anion Across the Water-CCl4 Liquid/Liquid Interface". United States. doi:10.1063/1.2717164.
@article{osti_908734,
title = {Molecular Mechanism of Transporting a Polarizable Iodide Anion Across the Water-CCl4 Liquid/Liquid Interface},
author = {Wick, Collin D. and Dang, Liem X.},
abstractNote = {The result of transferring a polarizable iodide anion across the H2O-CCl4 liquid/liquid interface was investigated. The computed transfer free energy profile or potential of mean force exhibits a minimum near the Gibbs dividing surface, and its characteristics are similar to those of found in a corresponding water vapor/liquid interface study involving a smaller minimum free energy. Molecular dynamics simulations also were carried out to compare the concentrations of NaCl, NaBr, and NaI at H2O-vapor and H2O-CCl4 interfaces. While the concentration of bromide and iodide ions were lower at the H2O-CCl4 interface when compared to the H2O-vapor interface, the chloride ion concentrations were similar at both interfaces. Analysis of the solvation structures of iodide and chloride ions revealed that the more polarizable iodide ion was less solvated than the chloride ion at the interface. This characteristic brought the iodide ion in greater contact with CCl4 than the chloride ion, resulting in repulsive interactions with CCl4, which reduced its propensity for the interface. This work was performed at the Pacific Northwest National Laboratory (PNNL) and was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE. The DOE Division of Chemical Sciences and the Scientific Computing Staff, Office of Science provided computer resources at the National Energy Research Supercomputer Center (Berkeley, California) that supported this research.},
doi = {10.1063/1.2717164},
journal = {Journal of Chemical Physics, 126(13)},
number = 13,
volume = 126,
place = {United States},
year = {Sat Apr 07 00:00:00 EDT 2007},
month = {Sat Apr 07 00:00:00 EDT 2007}
}