Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Pair and many-body interactions between ligated Au nanoparticles

Abstract

Here, we report the results of molecular dynamics simulations of the properties of a pseudo-atom (united atom) model of dodecane thiol ligated 5-nm diameter gold nanoparticles (AuNPs) in a vacuum as a function of ligand coverage and particle separation in three states of aggregation, namely, the isolated AuNPs, the isolated pair of AuNPs, and a square lattice of four AuNPs. Our calculations show that the ligand density along a radius emanating from the core of an isolated AuNP has the same gross features for all values of the coverage; it oscillates around a constant value up to a distance along the chain corresponding to the position of the fourth pseudo-atom and then smoothly decays to zero, reflecting both the restricted conformations of the chain near the core surface and the larger numbers of conformations available further from the core. Interaction between two AuNPs generates changes in the ligand distributions of each. We examine the structure and general shape of the ligand envelope as a function of the coverage and demonstrate that the equilibrium structure of the envelope and the deformation of that envelope generated by interaction between the NPs are coverage-dependent so that the shape, depth, and position of themore » minimum of the potential of mean force display a systematic dependence on the ligand coverage. We propose an accurate analytical description of the calculated potential of mean force as a function of a set of parameters that scale linearly with the ligand coverage. Noting that the conformational freedom of the ligands implies that multiparticle induced deviations from additivity of the pair potential of mean force are likely important; we define and calculate a “bond stretching” effective pair potential of mean force for a square lattice of particles that contains, implicitly, both the three- and four-NP contributions. We find that the bond stretching effective pair potential of mean force in this cluster has a different minimum and a different well depth from the isolated pair potential of mean force. Previous work has found that the three-particle contribution to deviation from pair additivity is monotonically repulsive, whereas we find that the combined three- and four-particle contributions have an attractive well, implying that the three- and four-particle contributions are of comparable magnitude but opposite sign, thereby suggesting that even higher order correction terms likely play a significant role in the behavior of dense assemblies of many nanoparticles.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Science Foundation (NSF); Camille and Henry Dreyfus Foundation
OSTI Identifier:
1524665
Grant/Contract Number:  
DMR-1420709; SI-14-014; NSF/CHE-1346572
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ligands; Interatomic potentials; Molecular dynamics; Elastic modulus; Many body problems; Nanoparticles

Citation Formats

Liepold, Christopher, Smith, Alex, Lin, Binhua, de Pablo, Juan, and Rice, Stuart A. Pair and many-body interactions between ligated Au nanoparticles. United States: N. p., 2019. Web. doi:10.1063/1.5064545.
Copy to clipboard
Liepold, Christopher, Smith, Alex, Lin, Binhua, de Pablo, Juan, & Rice, Stuart A. Pair and many-body interactions between ligated Au nanoparticles. United States. https://doi.org/10.1063/1.5064545
Copy to clipboard
Liepold, Christopher, Smith, Alex, Lin, Binhua, de Pablo, Juan, and Rice, Stuart A. Mon . "Pair and many-body interactions between ligated Au nanoparticles". United States. https://doi.org/10.1063/1.5064545. https://www.osti.gov/servlets/purl/1524665.
Copy to clipboard
@article{osti_1524665,
title = {Pair and many-body interactions between ligated Au nanoparticles},
author = {Liepold, Christopher and Smith, Alex and Lin, Binhua and de Pablo, Juan and Rice, Stuart A.},
abstractNote = {Here, we report the results of molecular dynamics simulations of the properties of a pseudo-atom (united atom) model of dodecane thiol ligated 5-nm diameter gold nanoparticles (AuNPs) in a vacuum as a function of ligand coverage and particle separation in three states of aggregation, namely, the isolated AuNPs, the isolated pair of AuNPs, and a square lattice of four AuNPs. Our calculations show that the ligand density along a radius emanating from the core of an isolated AuNP has the same gross features for all values of the coverage; it oscillates around a constant value up to a distance along the chain corresponding to the position of the fourth pseudo-atom and then smoothly decays to zero, reflecting both the restricted conformations of the chain near the core surface and the larger numbers of conformations available further from the core. Interaction between two AuNPs generates changes in the ligand distributions of each. We examine the structure and general shape of the ligand envelope as a function of the coverage and demonstrate that the equilibrium structure of the envelope and the deformation of that envelope generated by interaction between the NPs are coverage-dependent so that the shape, depth, and position of the minimum of the potential of mean force display a systematic dependence on the ligand coverage. We propose an accurate analytical description of the calculated potential of mean force as a function of a set of parameters that scale linearly with the ligand coverage. Noting that the conformational freedom of the ligands implies that multiparticle induced deviations from additivity of the pair potential of mean force are likely important; we define and calculate a “bond stretching” effective pair potential of mean force for a square lattice of particles that contains, implicitly, both the three- and four-NP contributions. We find that the bond stretching effective pair potential of mean force in this cluster has a different minimum and a different well depth from the isolated pair potential of mean force. Previous work has found that the three-particle contribution to deviation from pair additivity is monotonically repulsive, whereas we find that the combined three- and four-particle contributions have an attractive well, implying that the three- and four-particle contributions are of comparable magnitude but opposite sign, thereby suggesting that even higher order correction terms likely play a significant role in the behavior of dense assemblies of many nanoparticles.},
doi = {10.1063/1.5064545},
journal = {Journal of Chemical Physics},
number = 4,
volume = 150,
place = {United States},
year = {Mon Jan 28 00:00:00 EST 2019},
month = {Mon Jan 28 00:00:00 EST 2019}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.5064545
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Anisotropic self-assembly of spherical polymer-grafted nanoparticles
journal, March 2009

  • Akcora, Pinar; Liu, Hongjun; Kumar, Sanat K.
  • Nature Materials, Vol. 8, Issue 4
  • DOI: 10.1038/nmat2404

Wetting Properties of Passivated Metal Nanocrystals at Liquid−Vapor Interfaces: A Computer Simulation Study
journal, November 2006

  • Tay, Kafui A.; Bresme, Fernando
  • Journal of the American Chemical Society, Vol. 128, Issue 43
  • DOI: 10.1021/ja061901w

Three-body effects in triplets of capped gold nanocrystals
journal, August 2016

Fabrication and Mechanical Properties of Large-Scale Freestanding Nanoparticle Membranes
journal, June 2010

Wafer-scale self-assembled plasmonic thin films
journal, July 2011

Solvation of Metal Nanoparticles in a Subcritical — Supercritical Fluid:  A Computer Simulation Study
journal, May 2004

  • Lal, Moti; Plummer, Martin; Richmond, Nicola J.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 19
  • DOI: 10.1021/jp036776e

Free energy from constrained molecular dynamics
journal, November 1998

  • Sprik, Michiel; Ciccotti, Giovanni
  • The Journal of Chemical Physics, Vol. 109, Issue 18
  • DOI: 10.1063/1.477419

Understanding interactions between capped nanocrystals: Three-body and chain packing effects
journal, September 2009

  • Schapotschnikow, Philipp; Vlugt, Thijs J. H.
  • The Journal of Chemical Physics, Vol. 131, Issue 12
  • DOI: 10.1063/1.3227043

The calculation of free-energy differences by constrained molecular-dynamics simulations
journal, September 1998

  • den Otter, W. K.; Briels, W. J.
  • The Journal of Chemical Physics, Vol. 109, Issue 11
  • DOI: 10.1063/1.477019

Electroluminescence from single monolayers of nanocrystals in molecular organic devices
journal, December 2002

  • Coe, Seth; Woo, Wing-Keung; Bawendi, Moungi
  • Nature, Vol. 420, Issue 6917
  • DOI: 10.1038/nature01217

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995

Alkanethiolate Gold Cluster Molecules with Core Diameters from 1.5 to 5.2 nm:  Core and Monolayer Properties as a Function of Core Size
journal, January 1998

  • Hostetler, Michael J.; Wingate, Julia E.; Zhong, Chuan-Jian
  • Langmuir, Vol. 14, Issue 1
  • DOI: 10.1021/la970588w

An accurate integral equation for the pair and triplet distribution functions of a simple liquid
journal, March 1981

  • Haymet, A. D. J.; Rice, Stuart A.; Madden, William G.
  • The Journal of Chemical Physics, Vol. 74, Issue 5
  • DOI: 10.1063/1.441427

Photophysical, Photochemical and Photocatalytic Aspects of Metal Nanoparticles
journal, August 2002

  • Kamat, Prashant V.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 32
  • DOI: 10.1021/jp0209289

Solvent Effects in the Adsorption of Alkyl Thiols on Gold Structures:  A Molecular Simulation Study
journal, July 2007

  • Pool, René; Schapotschnikow, Philipp; Vlugt, Thijs J. H.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 28
  • DOI: 10.1021/jp071491d

Melting and Equilibrium Shape of Icosahedral Gold Nanoparticles
text, January 2003

Localized Surface Plasmon Resonances by Ag Nanoparticles on SiN for Solar Cell Application
journal, May 2010

  • Yoo, Won Jong; Yang, Cheng; Zhang, Gang
  • Journal of the Korean Physical Society, Vol. 56, Issue 5
  • DOI: 10.3938/jkps.56.1488

Soft Hedgehogs on Coarse Carpets: A Molecular Simulation Study of Capped Nanocrystals Interacting with Self-Assembled Monolayers of Alkylthiols on a Gold (111) Surface
journal, January 2010

  • Schapotschnikow, Philipp; Vlugt, Thijs J. H.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 6
  • DOI: 10.1021/jp910554e

Solvent-driven symmetry of self-assembled nanocrystal superlattices-A computational study
journal, October 2012

  • Kaushik, Ananth P.; Clancy, Paulette
  • Journal of Computational Chemistry, Vol. 34, Issue 7
  • DOI: 10.1002/jcc.23152

Orientational Ordering of Passivating Ligands on CdS Nanorods in Solution Generates Strong Rod–Rod Interactions
journal, December 2013

  • Widmer-Cooper, Asaph; Geissler, Phillip
  • Nano Letters, Vol. 14, Issue 1
  • DOI: 10.1021/nl403067p

Explicit all-atom modeling of realistically sized ligand-capped nanocrystals
journal, March 2012

  • Kaushik, Ananth P.; Clancy, Paulette
  • The Journal of Chemical Physics, Vol. 136, Issue 11
  • DOI: 10.1063/1.3689973

Interaction Between Polymer Brush-Coated Spherical Nanoparticles: Effect of Solvent Quality
journal, October 2012

  • LoVerso, Federica; Egorov, Sergei A.; Binder, Kurt
  • Macromolecules, Vol. 45, Issue 21
  • DOI: 10.1021/ma301651z

Anisotropic Three-Particle Interactions between Spherical Polymer-Grafted Nanoparticles in a Polymer Matrix
journal, January 2017

An optimized united atom model for simulations of polymethylene melts
journal, July 1995

  • Paul, Wolfgang; Yoon, Do Y.; Smith, Grant D.
  • The Journal of Chemical Physics, Vol. 103, Issue 4
  • DOI: 10.1063/1.469740

Structural and Dynamic Properties of Water near Monolayer-Protected Gold Clusters with Various Alkanethiol Tail Groups
journal, April 2010

  • Yang, An-Cheng; Weng, Cheng-I
  • The Journal of Physical Chemistry C, Vol. 114, Issue 19
  • DOI: 10.1021/jp910101t

Nanogold: A Quantitative Phase Map
journal, May 2009

  • Barnard, Amanda S.; Young, Neil P.; Kirkland, Angus I.
  • ACS Nano, Vol. 3, Issue 6
  • DOI: 10.1021/nn900220k

Structure and Thermodynamics of Self-Assembled Monolayers on Gold Nanocrystallites
journal, August 1998

  • Luedtke, W. D.; Landman, Uzi
  • The Journal of Physical Chemistry B, Vol. 102, Issue 34
  • DOI: 10.1021/jp981745i

Biosensing with plasmonic nanosensors
journal, June 2008

  • Anker, Jeffrey N.; Hall, W. Paige; Lyandres, Olga
  • Nature Materials, Vol. 7, Issue 6
  • DOI: 10.1038/nmat2162

Sampling of molecular conformations by molecular dynamics techniques
journal, June 1993

Optimization of the OPLS-AA Force Field for Long Hydrocarbons
journal, March 2012

  • Siu, Shirley W. I.; Pluhackova, Kristyna; Böckmann, Rainer A.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 4
  • DOI: 10.1021/ct200908r

Fully Atomistic Simulations of the Response of Silica Nanoparticle Coatings to Alkane Solvents
journal, December 2012

  • Peters, Brandon L.; Lane, J. Matthew D.; Ismail, Ahmed E.
  • Langmuir, Vol. 28, Issue 50
  • DOI: 10.1021/la3023166

Structure, Wrinkling, and Reversibility of Langmuir Monolayers of Gold Nanoparticles
journal, December 2006

  • Schultz, David G.; Lin, Xiao-Min; Li, Dongxu
  • The Journal of Physical Chemistry B, Vol. 110, Issue 48
  • DOI: 10.1021/jp063820s

Effects of Functional Groups and Ionization on the Structure of Alkanethiol-Coated Gold Nanoparticles
journal, September 2014

  • Bolintineanu, Dan S.; Lane, J. Matthew D.; Grest, Gary S.
  • Langmuir, Vol. 30, Issue 37
  • DOI: 10.1021/la502795z

Effect of the solvent quality on the structural rearrangement of spherical brushes: coarse-grained models
journal, January 2012

  • Lo Verso, Federica; Yelash, Leonid; Egorov, Sergei A.
  • Soft Matter, Vol. 8, Issue 15
  • DOI: 10.1039/c2sm06836b

Thiol-Functionalized, 1.5-nm Gold Nanoparticles through Ligand Exchange Reactions:  Scope and Mechanism of Ligand Exchange
journal, February 2005

  • Woehrle, Gerd H.; Brown, Leif O.; Hutchison, James E.
  • Journal of the American Chemical Society, Vol. 127, Issue 7
  • DOI: 10.1021/ja0457718

The role of ligands in the mechanical properties of Langmuir nanoparticle films
journal, January 2017

  • Griesemer, Sean D.; You, Siheng Sean; Kanjanaboos, Pongsakorn
  • Soft Matter, Vol. 13, Issue 17
  • DOI: 10.1039/c7sm00319f

Emerging use of nanostructure films containing capped gold nanoparticles in biosensors
journal, December 2010

Melting and equilibrium shape of icosahedral gold nanoparticles
journal, August 2004

Blue Moon Sampling, Vectorial Reaction Coordinates, and Unbiased Constrained Dynamics
journal, September 2005

  • Ciccotti, Giovanni; Kapral, Raymond; Vanden-Eijnden, Eric
  • ChemPhysChem, Vol. 6, Issue 9
  • DOI: 10.1002/cphc.200400669

FePt and CoPt magnetic nanoparticles film for future high density data storage media
journal, January 2004

  • Sun, Xiangcheng; Huang, Yunhe; Nikles, David E.
  • International Journal of Nanotechnology, Vol. 1, Issue 3
  • DOI: 10.1504/ijnt.2004.004914

Interaction potentials for soft and hard ellipsoids
text, January 2003

Thermomechanical Response of Self-Assembled Nanoparticle Membranes
journal, July 2017

FePt and CoPt Magnetic Nanoparticles Film for Future High Density Data Storage Media
journal, December 2005

Nanoparticle Arrays on Surfaces for Electronic, Optical, and Sensor Applications
journal, August 2000

Effective interactions between a pair of particles modified with tethered chains
journal, July 2017

  • Baran, Ł.; Sokołowski, S.
  • The Journal of Chemical Physics, Vol. 147, Issue 4
  • DOI: 10.1063/1.4994919

Solvent-driven interactions between hydrophobically-coated nanoparticles
journal, January 2015

  • Hajiw, Stéphanie; Schmitt, Julien; Impéror-Clerc, Marianne
  • Soft Matter, Vol. 11, Issue 19
  • DOI: 10.1039/c5sm00176e

Solvation of Metal Nanoparticles in a Subcritical Supercritical Fluid:  A Computer Simulation Study
journal, June 2004

  • Lal, Moti; Plummer, Martin; Richmond, Nicola J.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 28
  • DOI: 10.1021/jp047893s

Forces between functionalized silica nanoparticles in solution
journal, May 2009

Structure, Dynamics, and Thermodynamics of Passivated Gold Nanocrystallites and Their Assemblies
journal, January 1996

  • Luedtke, W. D.; Landman, Uzi
  • The Journal of Physical Chemistry, Vol. 100, Issue 32
  • DOI: 10.1021/jp961721g

Molecular Dynamics Simulation Study of Self-Assembled Monolayers of Alkanethiol Surfactants on Spherical Gold Nanoparticles †
journal, November 2007

  • Ghorai, Pradip Kr.; Glotzer, Sharon C.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 43
  • DOI: 10.1021/jp0746289

Series Expansion of Distribution Functions in Multicomponent Fluid Systems
journal, December 1957

  • Meeron, Emmanuel
  • The Journal of Chemical Physics, Vol. 27, Issue 6
  • DOI: 10.1063/1.1743985

Determination of Binding Energy and Solubility Parameters for Functionalized Gold Nanoparticles by Molecular Dynamics Simulation
journal, June 2011

  • Henz, Brian J.; Chung, Peter W.; Andzelm, Jan W.
  • Langmuir, Vol. 27, Issue 12
  • DOI: 10.1021/la2005024

Population statistics of gold nanoparticle morphologies: direct determination by HREM observations
journal, April 2003

Ligand coverage dependence of structural stability and interparticle spacing of gold supracrystals
journal, January 2018

  • Liu, Xuepeng; Lu, Pin; Zhai, Hua
  • Journal of Applied Physics, Vol. 123, Issue 4
  • DOI: 10.1063/1.5005094

Molecular Simulations of Interacting Nanocrystals
journal, September 2008

  • Schapotschnikow, Philipp; Pool, René; Vlugt, Thijs J. H.
  • Nano Letters, Vol. 8, Issue 9
  • DOI: 10.1021/nl8017862

Assembly of responsive-shape coated nanoparticles at water surfaces
journal, January 2014

A Comparison of Methods to Compute the Potential of Mean Force
journal, January 2007

  • Trzesniak, Daniel; Kunz, Anna-Pitschna E.; van Gunsteren, Wilfred F.
  • ChemPhysChem, Vol. 8, Issue 1
  • DOI: 10.1002/cphc.200600527

On Mayer's theory of cluster expansions
journal, November 1958

Properties and emerging applications of self-assembled structures made from inorganic nanoparticles
journal, December 2009

  • Nie, Zhihong; Petukhova, Alla; Kumacheva, Eugenia
  • Nature Nanotechnology, Vol. 5, Issue 1
  • DOI: 10.1038/nnano.2009.453

Interactions between sterically stabilized nanoparticles in supercritical fluids: A simulation study
journal, February 2007

  • Patel, N.; Egorov, S. A.
  • The Journal of Chemical Physics, Vol. 126, Issue 5
  • DOI: 10.1063/1.2434155

Subnanometre ligand-shell asymmetry leads to Janus-like nanoparticle membranes
journal, June 2015

  • Jiang, Zhang; He, Jinbo; Deshmukh, Sanket A.
  • Nature Materials, Vol. 14, Issue 9
  • DOI: 10.1038/nmat4321

Behavior of water molecules near monolayer-protected clusters with different terminal segments of ligand
journal, July 2011

  • Yang, An-Cheng; Weng, Cheng-I; Chen, Tei-Chen
  • The Journal of Chemical Physics, Vol. 135, Issue 3
  • DOI: 10.1063/1.3602721

Spontaneous Asymmetry of Coated Spherical Nanoparticles in Solution and at Liquid-Vapor Interfaces
journal, June 2010

Thiolated gold nanoparticle solvation in near-critical fluids: The role of density, temperature, and topology
journal, May 2017

  • Yadav, Hari O. S.; Chakravarty, Charusita
  • The Journal of Chemical Physics, Vol. 146, Issue 17
  • DOI: 10.1063/1.4982755

On the calculation of the potential of mean force between atomistic nanoparticles
journal, March 2018

  • Munaò, Gianmarco; Correa, Andrea; Pizzirusso, Antonio
  • The European Physical Journal E, Vol. 41, Issue 3
  • DOI: 10.1140/epje/i2018-11646-3
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Influence of Water Vapor on the Interaction Between Dodecane Thiol Ligated Au Nanoparticles
    text, January 2020

    The influence of fractional surface coverage on the core–core separation in ordered monolayers of thiol-ligated Au nanoparticles
    journal, January 2019

    • Reik, Morgan; Calabro, Melanie; Griesemer, Sean
    • Soft Matter, Vol. 15, Issue 43
    • DOI: 10.1039/c9sm01579e

    Interaction between capped tetrahedral gold nanocrystals: dependence on effective softness
    journal, January 2019

    • Liu, Xuepeng; Ni, Yong; He, Linghui
    • Soft Matter, Vol. 15, Issue 41
    • DOI: 10.1039/c9sm01389j
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: