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Title: Charged Nanoparticle Attraction in Multivalent Salt Solution: A Classical-Fluids Density Functional Theory and Molecular Dynamics Study

Abstract

Here, negatively charged nanoparticles (NPs) in 1:1, 1:2, and 1:3 electrolyte solutions are studied in a primitive ion model using molecular dynamics (MD) simulations and classical density functional theory (DFT). We determine the conditions for attractive interactions between the like-charged NPs. Ion density profiles and NP–NP interaction free energies are compared between the two methods and are found to be in qualitative agreement. The NP interaction free energy is purely repulsive for monovalent counterions, but can be attractive for divalent and trivalent counterions. Using DFT, the NP interaction free energy for different NP diameters and charges is calculated. The depth and location of the minimum in the interaction depend strongly on the NPs’ charge. For certain parameters, the depth of the attractive well can reach 8–10 kBT, indicating that kinetic arrest and aggregation of the NPs due to electrostatic interactions is possible. Rich behavior arises from the geometric constraints of counterion packing at the NP surface. Layering of counterions around the NPs is observed and, as secondary counterion layers form the minimum of the NP–NP interaction free energy shifts to larger separation, and the depth of the free energy minimum varies dramatically. We find that attractive interactions occur with andmore » without NP overcharging.« less

Authors:
 [1];  [1];  [1]
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  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1871980
Alternate Identifier(s):
OSTI ID: 1249083
Report Number(s):
SAND2022-5402J; SAND-2016-1264J
Journal ID: ISSN 1520-6106; 705532
Grant/Contract Number:  
NA0003525; AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 120; Journal Issue: 26; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Counterions; DFT calculations; Density functional theory; Free energy; Ions; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Salerno, K. Michael, Frischknecht, Amalie L., and Stevens, Mark J. Charged Nanoparticle Attraction in Multivalent Salt Solution: A Classical-Fluids Density Functional Theory and Molecular Dynamics Study. United States: N. p., 2016. Web. doi:10.1021/acs.jpcb.6b01392.
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Salerno, K. Michael, Frischknecht, Amalie L., & Stevens, Mark J. Charged Nanoparticle Attraction in Multivalent Salt Solution: A Classical-Fluids Density Functional Theory and Molecular Dynamics Study. United States. https://doi.org/10.1021/acs.jpcb.6b01392
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Salerno, K. Michael, Frischknecht, Amalie L., and Stevens, Mark J. Fri . "Charged Nanoparticle Attraction in Multivalent Salt Solution: A Classical-Fluids Density Functional Theory and Molecular Dynamics Study". United States. https://doi.org/10.1021/acs.jpcb.6b01392. https://www.osti.gov/servlets/purl/1871980.
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@article{osti_1871980,
title = {Charged Nanoparticle Attraction in Multivalent Salt Solution: A Classical-Fluids Density Functional Theory and Molecular Dynamics Study},
author = {Salerno, K. Michael and Frischknecht, Amalie L. and Stevens, Mark J.},
abstractNote = {Here, negatively charged nanoparticles (NPs) in 1:1, 1:2, and 1:3 electrolyte solutions are studied in a primitive ion model using molecular dynamics (MD) simulations and classical density functional theory (DFT). We determine the conditions for attractive interactions between the like-charged NPs. Ion density profiles and NP–NP interaction free energies are compared between the two methods and are found to be in qualitative agreement. The NP interaction free energy is purely repulsive for monovalent counterions, but can be attractive for divalent and trivalent counterions. Using DFT, the NP interaction free energy for different NP diameters and charges is calculated. The depth and location of the minimum in the interaction depend strongly on the NPs’ charge. For certain parameters, the depth of the attractive well can reach 8–10 kBT, indicating that kinetic arrest and aggregation of the NPs due to electrostatic interactions is possible. Rich behavior arises from the geometric constraints of counterion packing at the NP surface. Layering of counterions around the NPs is observed and, as secondary counterion layers form the minimum of the NP–NP interaction free energy shifts to larger separation, and the depth of the free energy minimum varies dramatically. We find that attractive interactions occur with and without NP overcharging.},
doi = {10.1021/acs.jpcb.6b01392},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 26,
volume = 120,
place = {United States},
year = {Fri Apr 08 00:00:00 EDT 2016},
month = {Fri Apr 08 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acs.jpcb.6b01392
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