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Title: Ions interacting in solution: Moving from intrinsic to collective properties

Abstract

A crucial determinant of Hofmeister effects is the direct interaction of ions in solution with the charged groups on the surface of larger particles. Understanding ion–ion interactions in solution is therefore a necessary first step to explaining Hofmeister effects. Here, we advocate an approach to modeling these types of properties where state of the art Ab Initio Molecular Dynamics (AIMD) simulation of ions in solution is used to establish benchmark values for the intrinsic properties of ions in solution such as solvation structures and ion–ion Potentials of Mean Force (PMFs). This information can then be combined with or used to parametrize and improve reduced models, which use approximations such as the continuum solvent model.(CSM) These reduced models can then be used to calculate collective and concentration dependent properties of electrolyte solution and so make accurate predictions about complex systems of relevance for direct applications. We provide an example of this approach using AIMD calculations of the sodium chloride dimer to calculate osmotic coefficients of all 20 alkali halide electrolytes. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. TD and CJM were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MDB was supported by MS$$^{3}$$ (Materials Synthesis and Simulation Across Scales) Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.

Authors:
ORCiD logo; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1339824
Report Number(s):
PNNL-SA-115774
Journal ID: ISSN 1359-0294; KC0301050
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Current Opinion in Colloid & Interface Science; Journal Volume: 23; Journal Issue: C
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Duignan, Timothy T., Baer, Marcel D., and Mundy, Christopher J.. Ions interacting in solution: Moving from intrinsic to collective properties. United States: N. p., 2016. Web. doi:10.1016/j.cocis.2016.05.009.
Duignan, Timothy T., Baer, Marcel D., & Mundy, Christopher J.. Ions interacting in solution: Moving from intrinsic to collective properties. United States. doi:10.1016/j.cocis.2016.05.009.
Duignan, Timothy T., Baer, Marcel D., and Mundy, Christopher J.. Wed . "Ions interacting in solution: Moving from intrinsic to collective properties". United States. doi:10.1016/j.cocis.2016.05.009.
@article{osti_1339824,
title = {Ions interacting in solution: Moving from intrinsic to collective properties},
author = {Duignan, Timothy T. and Baer, Marcel D. and Mundy, Christopher J.},
abstractNote = {A crucial determinant of Hofmeister effects is the direct interaction of ions in solution with the charged groups on the surface of larger particles. Understanding ion–ion interactions in solution is therefore a necessary first step to explaining Hofmeister effects. Here, we advocate an approach to modeling these types of properties where state of the art Ab Initio Molecular Dynamics (AIMD) simulation of ions in solution is used to establish benchmark values for the intrinsic properties of ions in solution such as solvation structures and ion–ion Potentials of Mean Force (PMFs). This information can then be combined with or used to parametrize and improve reduced models, which use approximations such as the continuum solvent model.(CSM) These reduced models can then be used to calculate collective and concentration dependent properties of electrolyte solution and so make accurate predictions about complex systems of relevance for direct applications. We provide an example of this approach using AIMD calculations of the sodium chloride dimer to calculate osmotic coefficients of all 20 alkali halide electrolytes. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. TD and CJM were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MDB was supported by MS$^{3}$ (Materials Synthesis and Simulation Across Scales) Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.},
doi = {10.1016/j.cocis.2016.05.009},
journal = {Current Opinion in Colloid & Interface Science},
number = C,
volume = 23,
place = {United States},
year = {Wed Jun 01 00:00:00 EDT 2016},
month = {Wed Jun 01 00:00:00 EDT 2016}
}