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Title: Charge transfer effects of ions at the liquid water/vapor interface

Charge transfer (CT), the movement of small amounts of electron density between non-bonded pairs, has been suggested as a driving force for a variety of physical processes. Herein, we examine the effect of CT on ion adsorption to the water liquid-vapor interface. Using a CT force field for molecular dynamics, we construct a potential of mean force (PMF) for Na{sup +}, K{sup +}, Cl{sup −}, and I{sup −}. The PMFs were produced with respect to an average interface and an instantaneous interface. An analysis of the PMF relative to the instantaneous surface reveals that the area in which the anions experience a free energy minimum is quite narrow, and the cations feel a steeply repulsive free energy near the interface. CT is seen to have only minor effects on the overall free energy profiles. However, the long-ranged effects of ions are highlighted by the CT model. Due to CT, the water molecules at the surface become charged, even when the ion is over 15 Å away from the surface.
Authors:
;  [1]
  1. Department of Chemistry, University of New Orleans, New Orleans, Louisiana 70148 (United States)
Publication Date:
OSTI Identifier:
22252887
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 18; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ADSORPTION; ANIONS; CATIONS; ELECTRON DENSITY; FREE ENERGY; INTERFACES; LIQUIDS; MOLECULAR DYNAMICS METHOD; POTASSIUM IONS; SODIUM IONS; SURFACES; WATER; WATER VAPOR