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 »
- Authors:
-
- 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.
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
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.
@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}
}
Web of Science
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