Partial Molar Volumes of Aqua Ions from First Principles

Partial molar volumes of ions in water solution are calculated through pressures obtained from ab initio molecular dynamics simulations. The correct definition of pressure in charged systems subject to periodic boundary conditions requires access to the variation of the electrostatic potential upon...

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Bibliographic Details
Published inJournal of chemical theory and computation Vol. 13; no. 8; pp. 3427 - 3431
Main Authors Wiktor, Julia, Bruneval, Fabien, Pasquarello, Alfredo
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 08.08.2017
Subjects
Deformation
First principles
Mathematical analysis
Molecular chains
Molecular dynamics
Nuclear Experiment
Nuclear Theory
Physics
Water
ab initio molecular dynamics
aqua-ions
partial molar volume
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Summary:Partial molar volumes of ions in water solution are calculated through pressures obtained from ab initio molecular dynamics simulations. The correct definition of pressure in charged systems subject to periodic boundary conditions requires access to the variation of the electrostatic potential upon a change of volume. We develop a scheme for calculating such a variation in liquid systems by setting up an interface between regions of different density. This also allows us to determine the absolute deformation potentials for the band edges of liquid water. With the properly defined pressures, we obtain partial molar volumes of a series of aqua ions in very good agreement with experimental values.
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ISSN:1549-9618
1549-9626
1549-9626
DOI:10.1021/acs.jctc.7b00474