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Title: Predicting kinetic nanocrystal shapes through multi-scale theory and simulation: Polyvinylpyrrolidone-mediated growth of Ag nanocrystals

Abstract

In the shape-controlled synthesis of colloidal Ag nanocrystals, structure-directing agents, particularly polyvinylpyrrolidone (PVP), are known to be a key additive in making nanostructures with well-defined shapes. Although many Ag nanocrystals have been successfully synthesized using PVP, the mechanism by which PVP actuates shape control remains elusive. Here, we present a multi-scale theoretical framework for kinetic Wulff shape predictions that accounts for the chemical environment, which we used to probe the kinetic influence of the adsorbed PVP film. Within this framework, we use umbrella-sampling molecular dynamics simulations to calculate the potential of mean force and diffusion coefficient profiles of Ag atom deposition onto Ag(100) and Ag(111) in ethylene glycol solution with surface-adsorbed PVP. We use these profiles to calculate the mean-first passage times and implement extensive Brownian dynamics simulations, which allows the kinetic effects to be quantitatively evaluated. Our results show that PVP films can regulate the flux of Ag atoms to be greater towards Ag(111) than Ag(100). PVP’s preferential binding towards Ag(100) over Ag(111) gives PVP its flux-regulating capabilities through the lower free-energy barrier of Ag atoms to cross the lower-density PVP film on Ag(111) and enhanced Ag trapping by the extended PVP film on Ag(111). Under kinetic control, {100}-facetedmore » nanocrystals will be formed when the Ag flux is greater towards Ag(111). Furthermore, the predicted kinetic Wulff shapes are in agreement with the analogous experimental system.« less

Authors:
 [1];  [1];  [1];  [1]
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  1. The Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE
OSTI Identifier:
1465481
Alternate Identifier(s):
OSTI ID: 1328814
Grant/Contract Number:  
FG02-07ER46414
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 14; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Balankura, Tonnam, Qi, Xin, Zhou, Ya, and Fichthorn, Kristen A. Predicting kinetic nanocrystal shapes through multi-scale theory and simulation: Polyvinylpyrrolidone-mediated growth of Ag nanocrystals. United States: N. p., 2016. Web. doi:10.1063/1.4964297.
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Balankura, Tonnam, Qi, Xin, Zhou, Ya, & Fichthorn, Kristen A. Predicting kinetic nanocrystal shapes through multi-scale theory and simulation: Polyvinylpyrrolidone-mediated growth of Ag nanocrystals. United States. https://doi.org/10.1063/1.4964297
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Balankura, Tonnam, Qi, Xin, Zhou, Ya, and Fichthorn, Kristen A. Thu . "Predicting kinetic nanocrystal shapes through multi-scale theory and simulation: Polyvinylpyrrolidone-mediated growth of Ag nanocrystals". United States. https://doi.org/10.1063/1.4964297. https://www.osti.gov/servlets/purl/1465481.
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@article{osti_1465481,
title = {Predicting kinetic nanocrystal shapes through multi-scale theory and simulation: Polyvinylpyrrolidone-mediated growth of Ag nanocrystals},
author = {Balankura, Tonnam and Qi, Xin and Zhou, Ya and Fichthorn, Kristen A.},
abstractNote = {In the shape-controlled synthesis of colloidal Ag nanocrystals, structure-directing agents, particularly polyvinylpyrrolidone (PVP), are known to be a key additive in making nanostructures with well-defined shapes. Although many Ag nanocrystals have been successfully synthesized using PVP, the mechanism by which PVP actuates shape control remains elusive. Here, we present a multi-scale theoretical framework for kinetic Wulff shape predictions that accounts for the chemical environment, which we used to probe the kinetic influence of the adsorbed PVP film. Within this framework, we use umbrella-sampling molecular dynamics simulations to calculate the potential of mean force and diffusion coefficient profiles of Ag atom deposition onto Ag(100) and Ag(111) in ethylene glycol solution with surface-adsorbed PVP. We use these profiles to calculate the mean-first passage times and implement extensive Brownian dynamics simulations, which allows the kinetic effects to be quantitatively evaluated. Our results show that PVP films can regulate the flux of Ag atoms to be greater towards Ag(111) than Ag(100). PVP’s preferential binding towards Ag(100) over Ag(111) gives PVP its flux-regulating capabilities through the lower free-energy barrier of Ag atoms to cross the lower-density PVP film on Ag(111) and enhanced Ag trapping by the extended PVP film on Ag(111). Under kinetic control, {100}-faceted nanocrystals will be formed when the Ag flux is greater towards Ag(111). Furthermore, the predicted kinetic Wulff shapes are in agreement with the analogous experimental system.},
doi = {10.1063/1.4964297},
journal = {Journal of Chemical Physics},
number = 14,
volume = 145,
place = {United States},
year = {Thu Oct 13 00:00:00 EDT 2016},
month = {Thu Oct 13 00:00:00 EDT 2016}
}
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https://doi.org/10.1063/1.4964297
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Works referenced in this record:

Evolution of Crystal Shape
journal, January 2004

  • Gadewar, Sagar B.; Hofmann, Herbert M.; Doherty, Michael F.
  • Crystal Growth & Design, Vol. 4, Issue 1
  • DOI: 10.1021/cg034057j

Quantitative Analysis of the Role Played by Poly(vinylpyrrolidone) in Seed-Mediated Growth of Ag Nanocrystals
journal, January 2012

  • Xia, Xiaohu; Zeng, Jie; Oetjen, L. Kyle
  • Journal of the American Chemical Society, Vol. 134, Issue 3
  • DOI: 10.1021/ja210047e

Nonphysical sampling distributions in Monte Carlo free-energy estimation: Umbrella sampling
journal, February 1977

Shape evolution of 3-dimensional faceted crystals
journal, January 2006

  • Zhang, Yongchun; Sizemore, Jacob P.; Doherty, Michael F.
  • AIChE Journal, Vol. 52, Issue 5
  • DOI: 10.1002/aic.10778

Right Bipyramids of Silver:  A New Shape Derived from Single Twinned Seeds
journal, April 2006

  • Wiley, Benjamin J.; Xiong, Yujie; Li, Zhi-Yuan
  • Nano Letters, Vol. 6, Issue 4
  • DOI: 10.1021/nl060069q

Improved performance of amorphous silicon solar cells via scattering from surface plasmon polaritons in nearby metallic nanoparticles
journal, August 2006

  • Derkacs, D.; Lim, S. H.; Matheu, P.
  • Applied Physics Letters, Vol. 89, Issue 9
  • DOI: 10.1063/1.2336629

An embedded-atom potential for the Cu–Ag system
journal, May 2006

  • Williams, P. L.; Mishin, Y.; Hamilton, J. C.
  • Modelling and Simulation in Materials Science and Engineering, Vol. 14, Issue 5
  • DOI: 10.1088/0965-0393/14/5/002

Adsorption of Polyvinylpyrrolidone on Ag Surfaces: Insight into a Structure-Directing Agent
journal, January 2012

  • Al-Saidi, W. A.; Feng, Haijun; Fichthorn, Kristen A.
  • Nano Letters, Vol. 12, Issue 2
  • DOI: 10.1021/nl2041113

How Structure-Directing Agents Control Nanocrystal Shape: Polyvinylpyrrolidone-Mediated Growth of Ag Nanocubes
journal, October 2015

Polyol Synthesis of Uniform Silver Nanowires:  A Plausible Growth Mechanism and the Supporting Evidence
journal, July 2003

  • Sun, Yugang; Mayers, Brian; Herricks, Thurston
  • Nano Letters, Vol. 3, Issue 7
  • DOI: 10.1021/nl034312m

Formation Mechanism of Fe Nanocubes by Magnetron Sputtering Inert Gas Condensation
journal, March 2016

Engineering Selectivity in Heterogeneous Catalysis: Ag Nanowires as Selective Ethylene Epoxidation Catalysts
journal, August 2008

  • Christopher, Phillip; Linic, Suljo
  • Journal of the American Chemical Society, Vol. 130, Issue 34
  • DOI: 10.1021/ja803818k

Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes
journal, March 1977

  • Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C.
  • Journal of Computational Physics, Vol. 23, Issue 3
  • DOI: 10.1016/0021-9991(77)90098-5

Tunable light trapping for solar cells using localized surface plasmons
journal, June 2009

  • Beck, F. J.; Polman, A.; Catchpole, K. R.
  • Journal of Applied Physics, Vol. 105, Issue 11
  • DOI: 10.1063/1.3140609

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

Size and Shape Control of Metal Nanoparticles for Reaction Selectivity in Catalysis
journal, August 2012

A computer simulation method for the calculation of equilibrium constants for the formation of physical clusters of molecules: Application to small water clusters
journal, January 1982

  • Swope, William C.; Andersen, Hans C.; Berens, Peter H.
  • The Journal of Chemical Physics, Vol. 76, Issue 1
  • DOI: 10.1063/1.442716

Comparison of the Binding of Polyvinylpyrrolidone and Polyethylene Oxide to Ag Surfaces: Elements of a Successful Structure-Directing Agent
journal, May 2013

  • Zhou, Ya; Saidi, Wissam A.; Fichthorn, Kristen A.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 21
  • DOI: 10.1021/jp403318h

Binding of Polyvinylpyrrolidone to Ag Surfaces: Insight into a Structure-Directing Agent from Dispersion-Corrected Density Functional Theory
journal, January 2013

  • Saidi, Wissam A.; Feng, Haijun; Fichthorn, Kristen A.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 2
  • DOI: 10.1021/jp309867n

Recovering position-dependent diffusion from biased molecular dynamics simulations
journal, February 2014

  • Ljubetič, Ajasja; Urbančič, Iztok; Štrancar, Janez
  • The Journal of Chemical Physics, Vol. 140, Issue 8
  • DOI: 10.1063/1.4866448

Analysis of the statistical error in umbrella sampling simulations by umbrella integration
journal, June 2006

  • Kästner, Johannes; Thiel, Walter
  • The Journal of Chemical Physics, Vol. 124, Issue 23
  • DOI: 10.1063/1.2206775

Synthesis and Characterization of Monodisperse Nanocrystals and Close-Packed Nanocrystal Assemblies
journal, August 2000

CHARMM general force field: A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields
journal, January 2009

  • Vanommeslaeghe, K.; Hatcher, E.; Acharya, C.
  • Journal of Computational Chemistry
  • DOI: 10.1002/jcc.21367

Conformational Flexibility of o-Phosphorylcholine and o-Phosphorylethanolamine: A Molecular Dynamics Study of Solvation Effects
journal, June 1994

  • Woolf, Thomas B.; Roux, Benoit
  • Journal of the American Chemical Society, Vol. 116, Issue 13
  • DOI: 10.1021/ja00092a048

A Force Field for Describing the Polyvinylpyrrolidone-Mediated Solution-Phase Synthesis of Shape-Selective Ag Nanoparticles
journal, January 2014

  • Zhou, Ya; Saidi, Wissam A.; Fichthorn, Kristen A.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 6
  • DOI: 10.1021/jp412098n

Synthesis of polyhedral Ag nanostructures by a PVP-assisted hydrothermal method
journal, July 2012

Bridging the gap between thermodynamic integration and umbrella sampling provides a novel analysis method: “Umbrella integration”
journal, October 2005

  • Kästner, Johannes; Thiel, Walter
  • The Journal of Chemical Physics, Vol. 123, Issue 14
  • DOI: 10.1063/1.2052648

A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334

First passage times in homogeneous nucleation and self-assembly
journal, December 2012

  • Yvinec, Romain; D'Orsogna, Maria R.; Chou, Tom
  • The Journal of Chemical Physics, Vol. 137, Issue 24
  • DOI: 10.1063/1.4772598

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

Shape-Controlled Synthesis of Colloidal Metal Nanocrystals: Thermodynamic versus Kinetic Products
journal, June 2015

  • Xia, Younan; Xia, Xiaohu; Peng, Hsin-Chieh
  • Journal of the American Chemical Society, Vol. 137, Issue 25
  • DOI: 10.1021/jacs.5b04641

Multi-scale theory and simulation of shape-selective nanocrystal growth
journal, January 2016

  • Fichthorn, Kristen A.; Balankura, Tonnam; Qi, Xin
  • CrystEngComm, Vol. 18, Issue 29
  • DOI: 10.1039/C6CE01012A

Distribution of first-passage times for diffusion at the percolation threshold
journal, December 1987

  • Trus, B. L.; Havlin, S.; Stauffer, D.
  • Journal of Physics A: Mathematical and General, Vol. 20, Issue 18
  • DOI: 10.1088/0305-4470/20/18/061

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008

  • Xia, Younan; Xiong, Yujie; Lim, Byungkwon
  • Angewandte Chemie International Edition, Vol. 48, Issue 1, p. 60-103
  • DOI: 10.1002/anie.200802248

Plasmonics for improved photovoltaic devices
journal, February 2010

  • Atwater, Harry A.; Polman, Albert
  • Nature Materials, Vol. 9, Issue 3, p. 205-213
  • DOI: 10.1038/nmat2629

Polyvinylpyrrolidone (PVP) in nanoparticle synthesis
journal, January 2015

  • Koczkur, Kallum M.; Mourdikoudis, Stefanos; Polavarapu, Lakshminarayana
  • Dalton Transactions, Vol. 44, Issue 41
  • DOI: 10.1039/C5DT02964C

Platinum Nanoparticle Shape Effects on Benzene Hydrogenation Selectivity
journal, October 2007

  • Bratlie, Kaitlin M.; Lee, Hyunjoo; Komvopoulos, Kyriakos
  • Nano Letters, Vol. 7, Issue 10
  • DOI: 10.1021/nl0716000

Additive and Classical Drude Polarizable Force Fields for Linear and Cyclic Ethers
journal, March 2007

  • Vorobyov, Igor; Anisimov, Victor M.; Greene, Shannon
  • Journal of Chemical Theory and Computation, Vol. 3, Issue 3
  • DOI: 10.1021/ct600350s

Controlling the Synthesis and Assembly of Silver Nanostructures for Plasmonic Applications
journal, June 2011

  • Rycenga, Matthew; Cobley, Claire M.; Zeng, Jie
  • Chemical Reviews, Vol. 111, Issue 6
  • DOI: 10.1021/cr100275d

Umbrella sampling: Umbrella sampling
journal, May 2011

  • Kästner, Johannes
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 6
  • DOI: 10.1002/wcms.66

First-passage-probability analysis of active transport in live cells
journal, September 2012

Localized Surface Plasmon Resonance Sensors
journal, June 2011

  • Mayer, Kathryn M.; Hafner, Jason H.
  • Chemical Reviews, Vol. 111, Issue 6
  • DOI: 10.1021/cr100313v

Reaction-rate theory: fifty years after Kramers
journal, April 1990

  • Hänggi, Peter; Talkner, Peter; Borkovec, Michal
  • Reviews of Modern Physics, Vol. 62, Issue 2
  • DOI: 10.1103/RevModPhys.62.251

Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985

Shape-directional growth of Pt and Pd nanoparticles
journal, January 2014

  • Leong, G. Jeremy; Ebnonnasir, Abbas; Schulze, Maxwell C.
  • Nanoscale, Vol. 6, Issue 19
  • DOI: 10.1039/C4NR02755H

Surface Area Limited Model for Predicting Anisotropic Coarsening of Faceted Nanoparticles
journal, January 2011

  • Seyed-Razavi, Alireza; Snook, Ian K.; Barnard, Amanda S.
  • Crystal Growth & Design, Vol. 11, Issue 1
  • DOI: 10.1021/cg101088d

Synthesis of {111}-Faceted Au Nanocrystals Mediated by Polyvinylpyrrolidone: Insights from Density-Functional Theory and Molecular Dynamics
journal, May 2015

  • Liu, Shih-Hsien; Saidi, Wissam A.; Zhou, Ya
  • The Journal of Physical Chemistry C, Vol. 119, Issue 21
  • DOI: 10.1021/acs.jpcc.5b01867

Shape-Controlled Synthesis and Surface Plasmonic Properties of Metallic Nanostructures
journal, May 2005

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Using collective variables to drive molecular dynamics simulations
journal, December 2013

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

Matplotlib: A 2D Graphics Environment
journal, January 2007

Atomic-Scale Theory and Simulations for Colloidal Metal Nanocrystal Growth
journal, May 2014

  • Fichthorn, Kristen A.
  • Journal of Chemical & Engineering Data, Vol. 59, Issue 10
  • DOI: 10.1021/je500189s

Synthesis of Silver Nanostructures with Controlled Shapes and Properties
journal, October 2007

  • Wiley, Benjamin; Sun, Yugang; Xia, Younan
  • Accounts of Chemical Research, Vol. 40, Issue 10
  • DOI: 10.1021/ar7000974

Computer simulations of Brownian motion of complex systems
journal, January 1995

Towards stable catalysts by controlling collective properties of supported metal nanoparticles
journal, November 2012

  • Prieto, Gonzalo; Zečević, Jovana; Friedrich, Heiner
  • Nature Materials, Vol. 12, Issue 1
  • DOI: 10.1038/nmat3471

A New Generation of Sensors Based on Extraordinary Optical Transmission
journal, August 2008

  • Gordon, Reuven; Sinton, David; Kavanagh, Karen L.
  • Accounts of Chemical Research, Vol. 41, Issue 8
  • DOI: 10.1021/ar800074d

Gold and Silver Nanoparticles in Sensing and Imaging:  Sensitivity of Plasmon Response to Size, Shape, and Metal Composition
journal, October 2006

  • Lee, Kyeong-Seok; El-Sayed, Mostafa A.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 39
  • DOI: 10.1021/jp062536y

VMD: Visual molecular dynamics
journal, February 1996

Molecular phenomena in colloidal nanostructure synthesis
journal, December 2013

Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy
journal, January 2013

  • Michalak, William D.; Krier, James M.; Komvopoulos, Kyriakos
  • The Journal of Physical Chemistry C, Vol. 117, Issue 4
  • DOI: 10.1021/jp311772p
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