Geometric and energetic considerations of surface fluctuations during ion transfer across the water-immiscible organic liquid interface

Molecular dynamics simulations and umbrella sampling free energy calculations are used to examine the thermodynamics, energetics, and structural fluctuations that accompany the transfer of a small hydrophilic ion (Cl−) across the water/nitrobenzene interface. By examining several constrained interfa...

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Bibliographic Details
Published in:The Journal of chemical physics 2016-07, Vol.145 (1), p.014701-014701
Main Authors: Karnes, John J., Benjamin, Ilan
Format: Article
Language:English
Subjects:
CHLORINE IONS
Deformation mechanisms
FREE ENERGY
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
INTERFACES
Molecular dynamics
MOLECULAR DYNAMICS METHOD
Organic liquids
Physics
Solvation
SURFACES
Variation
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Summary:Molecular dynamics simulations and umbrella sampling free energy calculations are used to examine the thermodynamics, energetics, and structural fluctuations that accompany the transfer of a small hydrophilic ion (Cl−) across the water/nitrobenzene interface. By examining several constrained interface structures, we isolate the energetic costs of interfacial deformation and co-transfer of hydration waters during the ion transfer. The process is monitored using both energy-based solvation coordinates and a geometric coordinate recently introduced by Morita and co-workers to describe surface fluctuations. Our simulations show that these coordinates provide a complimentary description of the water surface fluctuations during the transfer and are necessary for elucidating the mechanism of the ion transfer.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4954331