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Coarse-grained explicit-solvent molecular dynamics simulations of semidilute unentangled polyelectrolyte solutions
Abstract
In this study, we present results from explicit-solvent coarse-grained molecular dynamics (MD) simulations of fully charged, salt-free, and unentangled polyelectrolytes in semidilute solutions. The inclusion of a polar solvent in the model allows for a more physical representation of these solutions at concentrations, where the assumptions of a continuum dielectric medium and screened hydrodynamics break down. The collective dynamic structure factor of polyelectrolytes, S(q, t), showed that at q > q*, where q* = 2π/ξ is the polyelectrolyte peak in the structure factor S(q) and ξ is the correlation length, the relaxation time obtained from fits to stretched exponential was $$\tau$$KWW ~ q-3, which describes unscreened Zimm-like dynamics. This is in contrast to implicit-solvent simulations using a Langevin thermostat where $$\tau$$KWW ~ q-2. At q < q*, a crossover region was observed that eventually transitions to another inflection point $$\tau$$KWW ~ q-2 at length scales larger than ξ for both implicit- and explicit-solvent simulations. The simulation results were also compared to scaling predictions for correlation length, ξ ~ c$$-½\atop{p}$$, specific viscosity, ηsp ~ c$$½\atop{p}$$, and diffusion coefficient, D ~ c$$0\atop{p}$$, where cp is the polyelectrolyte concentration. The scaling prediction for ξ holds; however, deviations from the predictions for ηsp and D were observed for systems at higher cp, which are in qualitative agreements with recent experimental results. This study highlights the importance of explicit-solvent effects in molecular dynamics simulations, particularly in semidilute solutions, for a better understanding of polyelectrolyte solution behavior.
- Authors:
-
[1];
[1];
[1];
[1]
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 2076188
- Grant/Contract Number:
- AC05-00OR22725; KC0402010
- Resource Type:
- Accepted Manuscript
- Journal Name:
- European Physical Journal. E, Soft Matter (print)
- Additional Journal Information:
- Journal Name: European Physical Journal. E, Soft Matter (print); Journal Volume: 46; Journal Issue: 10; Journal ID: ISSN 1292-8941
- Publisher:
- EDP Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; polyelectrolytes; semidilute solutions; molecular dynamics; simulations
Citation Formats
Carrillo, Jan-Michael, Wang, Yangyang, Kumar, Rajeev, and Sumpter, Bobby G. Coarse-grained explicit-solvent molecular dynamics simulations of semidilute unentangled polyelectrolyte solutions. United States: N. p., 2023.
Web. doi:10.1140/epje/s10189-023-00342-2.
Carrillo, Jan-Michael, Wang, Yangyang, Kumar, Rajeev, & Sumpter, Bobby G. Coarse-grained explicit-solvent molecular dynamics simulations of semidilute unentangled polyelectrolyte solutions. United States. https://doi.org/10.1140/epje/s10189-023-00342-2
Carrillo, Jan-Michael, Wang, Yangyang, Kumar, Rajeev, and Sumpter, Bobby G. Thu .
"Coarse-grained explicit-solvent molecular dynamics simulations of semidilute unentangled polyelectrolyte solutions". United States. https://doi.org/10.1140/epje/s10189-023-00342-2.
@article{osti_2076188,
title = {Coarse-grained explicit-solvent molecular dynamics simulations of semidilute unentangled polyelectrolyte solutions},
author = {Carrillo, Jan-Michael and Wang, Yangyang and Kumar, Rajeev and Sumpter, Bobby G.},
abstractNote = {In this study, we present results from explicit-solvent coarse-grained molecular dynamics (MD) simulations of fully charged, salt-free, and unentangled polyelectrolytes in semidilute solutions. The inclusion of a polar solvent in the model allows for a more physical representation of these solutions at concentrations, where the assumptions of a continuum dielectric medium and screened hydrodynamics break down. The collective dynamic structure factor of polyelectrolytes, S(q, t), showed that at q > q*, where q* = 2π/ξ is the polyelectrolyte peak in the structure factor S(q) and ξ is the correlation length, the relaxation time obtained from fits to stretched exponential was $\tau$KWW ~ q-3, which describes unscreened Zimm-like dynamics. This is in contrast to implicit-solvent simulations using a Langevin thermostat where $\tau$KWW ~ q-2. At q < q*, a crossover region was observed that eventually transitions to another inflection point $\tau$KWW ~ q-2 at length scales larger than ξ for both implicit- and explicit-solvent simulations. The simulation results were also compared to scaling predictions for correlation length, ξ ~ c$-½\atop{p}$, specific viscosity, ηsp ~ c$½\atop{p}$, and diffusion coefficient, D ~ c$0\atop{p}$, where cp is the polyelectrolyte concentration. The scaling prediction for ξ holds; however, deviations from the predictions for ηsp and D were observed for systems at higher cp, which are in qualitative agreements with recent experimental results. This study highlights the importance of explicit-solvent effects in molecular dynamics simulations, particularly in semidilute solutions, for a better understanding of polyelectrolyte solution behavior.},
doi = {10.1140/epje/s10189-023-00342-2},
journal = {European Physical Journal. E, Soft Matter (print)},
number = 10,
volume = 46,
place = {United States},
year = {Thu Oct 05 00:00:00 EDT 2023},
month = {Thu Oct 05 00:00:00 EDT 2023}
}
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Works referenced in this record:
Statistical Mechanics of Nonequilibrium Liquids
book, January 2007
- Evans, Denis J.; Morriss, Gary P.
- ANU Press
Dynamics of Charged Species in Ionic-Neutral Block Copolymer and Surfactant Complexes
journal, July 2017
- Borreguero, Jose M.; Pincus, Philip A.; Sumpter, Bobby G.
- The Journal of Physical Chemistry B, Vol. 121, Issue 28
Theory of polyelectrolytes in solutions and at surfaces
journal, November 2005
- Dobrynin, A.; Rubinstein, M.
- Progress in Polymer Science, Vol. 30, Issue 11
Electrostatics of DNA compaction in viruses, bacteria and eukaryotes: functional insights and evolutionary perspective
journal, January 2012
- Carrivain, Pascal; Cournac, Axel; Lavelle, Christophe
- Soft Matter, Vol. 8, Issue 36
Role of Repulsive Forces in Determining the Equilibrium Structure of Simple Liquids
journal, June 1971
- Weeks, John D.; Chandler, David; Andersen, Hans C.
- The Journal of Chemical Physics, Vol. 54, Issue 12
Polyelectrolyte association and solvation
journal, October 2018
- Chremos, Alexandros; Douglas, Jack F.
- The Journal of Chemical Physics, Vol. 149, Issue 16
Scaling Theory of Polyelectrolyte Solutions
journal, November 1995
- Dobrynin, Andrey V.; Colby, Ralph H.; Rubinstein, Michael
- Macromolecules, Vol. 28, Issue 6
de Gennes Narrowing Describes the Relative Motion of Protein Domains
journal, April 2014
- Hong, Liang; Smolin, Nikolai; Smith, Jeremy C.
- Physical Review Letters, Vol. 112, Issue 15
Novel dynamic scaling hypothesis for semidilute and concentrated solutions of polymers and polyelectrolytes
journal, November 1993
- Oostwal, Michel; Odijk, Theo
- Macromolecules, Vol. 26, Issue 24
Polyelectrolyte–Surfactant Complexes As a Formulation Tool for Drug Delivery
journal, October 2022
- Gradzielski, Michael
- Langmuir, Vol. 38, Issue 44
The Dielectric Constant of Water and the Saturation Effect
journal, April 1951
- Booth, F.
- The Journal of Chemical Physics, Vol. 19, Issue 4
Rheology of Polyelectrolyte Solutions: Current Understanding and Perspectives
journal, February 2022
- Matsumoto, Atsushi
- Nihon Reoroji Gakkaishi, Vol. 50, Issue 1
Efficient on the fly calculation of time correlation functions in computer simulations
journal, October 2010
- Ramírez, Jorge; Sukumaran, Sathish K.; Vorselaars, Bart
- The Journal of Chemical Physics, Vol. 133, Issue 15
Electrostatic persistence length of NaPSS polyelectrolytes determined by a zero average contrast SANS technique
journal, November 1997
- Nishida, Koji; Urakawa, Hiroshi; Kaji, Keisuke
- Polymer, Vol. 38, Issue 24
Static and dynamic light scattering by aqueous polyelectrolyte solutions: effect of molecular weight, charge density and added salt
journal, May 1990
- Förster, Stephan; Schmidt, Manfred; Antonietti, Markus
- Polymer, Vol. 31, Issue 5
Conformation and dynamics of flexible polyelectrolytes in semidilute salt-free solutions
journal, June 2018
- Lopez, Carlos G.; Richtering, Walter
- The Journal of Chemical Physics, Vol. 148, Issue 24
Solution Rheology of a Strongly Charged Polyelectrolyte in Good Solvent
journal, August 2008
- Dou, Shichen; Colby, Ralph H.
- Macromolecules, Vol. 41, Issue 17
Rouse Dynamics of Polyelectrolyte Solutions: Molecular Dynamics Study
journal, October 2007
- Liao, Qi; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.
- Macromolecules, Vol. 40, Issue 21
DNA‐Inspired Electrostatics
journal, September 2000
- Gelbart, William M.; Bruinsma, Robijn F.; Pincus, Philip A.
- Physics Today, Vol. 53, Issue 9
Equilibrium bundle size of rodlike polyelectrolytes with counterion-induced attractive interactions
journal, June 2005
- Henle, Mark; Pincus, Philip
- Physical Review E, Vol. 71, Issue 6
Polyelectrolytes: The de Gennes Legacy
book, July 2009
- Pincus, Philip; Saleh, Omar A.
- Series on Directions in Condensed Matter Physics
Proteins and polyelectrolytes: A charged relationship
journal, April 2012
- Becker, Alisa L.; Henzler, Katja; Welsch, Nicole
- Current Opinion in Colloid & Interface Science, Vol. 17, Issue 2
Determining the Molecular Weight of Polyelectrolytes Using the Rouse Scaling Theory for Salt-Free Semidilute Unentangled Solutions
journal, August 2022
- Han, Aijie; Uppala, Veera Venkata Shravan; Parisi, Daniele
- Macromolecules, Vol. 55, Issue 16
Molecular Dynamics Simulations of Polyelectrolyte Solutions: Nonuniform Stretching of Chains and Scaling Behavior
journal, May 2003
- Liao, Qi; Dobrynin, Andrey V.; Rubinstein, Michael
- Macromolecules, Vol. 36, Issue 9
Dynamics of Semidilute Polyelectrolyte Solutions
journal, November 1994
- Rubinstein, Michael; Colby, Ralph H.; Dobrynin, Andrey V.
- Physical Review Letters, Vol. 73, Issue 20
Determining the shear viscosity of model liquids from molecular dynamics simulations
journal, January 2002
- Hess, Berk
- The Journal of Chemical Physics, Vol. 116, Issue 1
Dynamics of entangled linear polymer melts: A molecular‐dynamics simulation
journal, April 1990
- Kremer, Kurt; Grest, Gary S.
- The Journal of Chemical Physics, Vol. 92, Issue 8
Polyelectrolytes
journal, January 1951
- Fuoss, Raymond M.
- Discussions of the Faraday Society, Vol. 11
50th Anniversary Perspective : A Perspective on Polyelectrolyte Solutions
journal, December 2017
- Muthukumar, M.
- Macromolecules, Vol. 50, Issue 24
Structure and linear viscoelasticity of flexible polymer solutions: comparison of polyelectrolyte and neutral polymer solutions
journal, December 2009
- Colby, Ralph H.
- Rheologica Acta, Vol. 49, Issue 5
LI. A contribution to the theory of electrocapillarity
journal, April 1913
- Chapman, David Leonard
- The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 25, Issue 148
Cooperative diffusion in weakly charged polyelectrolyte solutions
journal, September 1991
- Ajdari, Armand; Leibler, Ludwile; Joanny, Jean-François
- The Journal of Chemical Physics, Vol. 95, Issue 6
Overlap Concentration in Salt-Free Polyelectrolyte Solutions
journal, October 2021
- Bollinger, Jonathan A.; Grest, Gary S.; Stevens, Mark J.
- Macromolecules, Vol. 54, Issue 21
Implementing molecular dynamics on hybrid high performance computers – Particle–particle particle-mesh
journal, March 2012
- Brown, W. Michael; Kohlmeyer, Axel; Plimpton, Steven J.
- Computer Physics Communications, Vol. 183, Issue 3
Domain Structures in Low Ionic Strength Polyelectrolyte Solutions
journal, October 1998
- Ermi, Brett D.; Amis, Eric J.
- Macromolecules, Vol. 31, Issue 21
Rheology of Sulfonated Polystyrene Solutions
journal, August 1998
- Boris, David C.; Colby, Ralph H.
- Macromolecules, Vol. 31, Issue 17
Polyelectrolytes in biology and soft matter
journal, January 2012
- Rubinstein, Michael; Papoian, Garegin A.
- Soft Matter, Vol. 8, Issue 36
Structure and Viscosity of Interpenetrating Polyelectrolyte Chains
journal, February 1987
- Witten, T. A.; Pincus, P.
- Europhysics Letters (EPL), Vol. 3, Issue 3
Implementing molecular dynamics on hybrid high performance computers – short range forces
journal, April 2011
- Brown, W. Michael; Wang, Peng; Plimpton, Steven J.
- Computer Physics Communications, Vol. 182, Issue 4
Sur la constitution de la charge électrique à la surface d'un électrolyte
journal, January 1910
- Gouy, M.
- Journal de Physique Théorique et Appliquée, Vol. 9, Issue 1
Polyelectrolyte Hydrogels for Tissue Engineering and Regenerative Medicine
journal, August 2022
- Wang, Chen‐Gang; Surat'man, Nayli Erdeanna Binte; Chang, Jun Jie
- Chemistry – An Asian Journal, Vol. 17, Issue 18
Effect of Salt on the Ordinary–Extraordinary Transition in Solutions of Charged Macromolecules
journal, March 2019
- Jia, Di; Muthukumar, Murugappan
- Journal of the American Chemical Society, Vol. 141, Issue 14
Neutron Spin Echo in Polymer Systems
book, January 2005
- Richter, Dieter; Monkenbusch, Michael; Arbe, Arantxa
Microsurface Potential Measurements: Repulsive Forces between Polyelectrolyte Brushes in the Presence of Multivalent Counterions
journal, October 2008
- Schneider, Christian; Jusufi, Arben; Farina, Robert
- Langmuir, Vol. 24, Issue 19
Viscosity function for polyelectrolytes
journal, August 1948
- Fuoss, Raymond M.
- Journal of Polymer Science, Vol. 3, Issue 4
High concentration crossovers of polyelectrolyte solutions
journal, May 2001
- Nishida, K.; Kaji, K.; Kanaya, T.
- The Journal of Chemical Physics, Vol. 114, Issue 19
Communication: Counter-ion solvation and anomalous low-angle scattering in salt-free polyelectrolyte solutions
journal, December 2017
- Chremos, Alexandros; Douglas, Jack F.
- The Journal of Chemical Physics, Vol. 147, Issue 24
Polyelectrolytes and Their Biological Interactions
journal, January 1964
- Katchalsky, A.
- Biophysical Journal, Vol. 4, Issue 1
Diffusion and Viscosity of Unentangled Polyelectrolytes
journal, August 2021
- Lopez, Carlos G.; Linders, Jürgen; Mayer, Christian
- Macromolecules, Vol. 54, Issue 17
Nonlinear Low-Force Elasticity of Single-Stranded DNA Molecules
journal, February 2009
- Saleh, O. A.; McIntosh, D. B.; Pincus, P.
- Physical Review Letters, Vol. 102, Issue 6
Debye Length and Double-Layer Forces in Polyelectrolyte Solutions
journal, February 2002
- Tadmor, Rafael; Hernández-Zapata, Ernesto; Chen, Nianhuan
- Macromolecules, Vol. 35, Issue 6
Bridging contributions to polyelectrolyte brush collapse in multivalent salt solutions
journal, November 2015
- Brettmann, Blair Kathryn; Laugel, Nicolas; Hoffmann, Norman
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 54, Issue 2
Liquid dynamics and inelastic scattering of neutrons
journal, January 1959
- De Gennes, P. G.
- Physica, Vol. 25, Issue 7-12
Dipole moment fluctuation formulas in computer simulations of polar systems
journal, November 1983
- Neumann, Martin
- Molecular Physics, Vol. 50, Issue 4
Polyelectrolytes in Salt Solutions: Molecular Dynamics Simulations
journal, July 2011
- Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.
- Macromolecules, Vol. 44, Issue 14
Electrostatic Repulsion Slows Relaxations of Polyelectrolytes in Semidilute Solutions
journal, June 2022
- Slim, Ali H.; Shi, Winnie H.; Safi Samghabadi, Farshad
- ACS Macro Letters, Vol. 11, Issue 7
Polyelectrolytes as Building Blocks for Next-Generation Membranes with Advanced Functionalities
journal, August 2021
- Durmaz, Elif Nur; Sahin, Sevil; Virga, Ettore
- ACS Applied Polymer Materials, Vol. 3, Issue 9
Charge regulation and local dielectric function in planar polyelectrolyte brushes
journal, June 2012
- Kumar, Rajeev; Sumpter, Bobby G.; Kilbey, S. Michael
- The Journal of Chemical Physics, Vol. 136, Issue 23
Remarks on polyelectrolyte conformation
journal, January 1976
- De Gennes, P. G.; Pincus, P.; Velasco, R. M.
- Journal de Physique, Vol. 37, Issue 12
Counterion-Condensation-Induced Collapse of Highly Charged Polyelectrolytes
journal, November 1998
- Schiessel, H.; Pincus, P.
- Macromolecules, Vol. 31, Issue 22
Salt dependence of compression normal forces of quenched polyelectrolyte brushes
journal, July 2001
- Tamashiro, M. N.; Hernández-Zapata, E.; Schorr, P. A.
- The Journal of Chemical Physics, Vol. 115, Issue 4
LAMMPS - a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales
journal, February 2022
- Thompson, Aidan P.; Aktulga, H. Metin; Berger, Richard
- Computer Physics Communications, Vol. 271
Assembly of polyelectrolyte star block copolymers at the oil–water interface
journal, January 2023
- Carrillo, Jan-Michael Y.; Chen, Zhan; Premadasa, Uvinduni I.
- Nanoscale, Vol. 15, Issue 3
Dipole moment of water from Stark measurements of H 2 O, HDO, and D 2 O
journal, September 1973
- Clough, Shepard A.; Beers, Yardley; Klein, Gerald P.
- The Journal of Chemical Physics, Vol. 59, Issue 5
Scale-Dependent Electrostatic Stiffening in Biopolymers
journal, August 2009
- Gubarev, Alexander; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.
- Macromolecules, Vol. 42, Issue 15
Polyelectrolyte and polyelectrolyte complex-incorporated adsorbents in water and wastewater remediation – A review of recent advances
journal, June 2023
- Bediako, John Kwame; El Ouardi, Youssef; Massima Mouele, Emile Salomon
- Chemosphere, Vol. 325
Colloid stabilization with grafted polyelectrolytes
journal, May 1991
- Pincus, Philip
- Macromolecules, Vol. 24, Issue 10
Overcharging of a spherical macroion by an oppositely charged polyelectrolyte
journal, May 1999
- Mateescu, E. M.; Jeppesen, C.; Pincus, P.
- Europhysics Letters (EPL), Vol. 46, Issue 4
Surfactant-Mediated Polyelectrolyte Self-Assembly in a Polyelectrolyte–Surfactant Complex
journal, November 2015
- Goswami, Monojoy; Borreguero, Jose M.; Pincus, Philip A.
- Macromolecules, Vol. 48, Issue 24
VMD: Visual molecular dynamics
journal, February 1996
- Humphrey, William; Dalke, Andrew; Schulten, Klaus
- Journal of Molecular Graphics, Vol. 14, Issue 1
The Potential of Polyelectrolyte Multilayer Films as Drug Delivery Materials
journal, March 2022
- Potaś, Joanna; Winnicka, Katarzyna
- International Journal of Molecular Sciences, Vol. 23, Issue 7