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Title: Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation

Abstract

Macromolecules with ionizable groups are ubiquitous in biological and synthetic systems. Due to the complex interaction between chain and electrostatic decorrelation lengths, both equilibrium properties and micro-mechanical response of dilute solutions of polyelectrolytes (PEs) are more complex than their neutral counterparts. In this paper, the bead-rod micromechanical description of a chain is used to perform hi-fidelity Brownian dynamics simulation of dilute PE solutions to ascertain the self-similar equilibrium behavior of PE chains with various linear charge densities, scaling of the Kuhn step length (l E) with salt concentration c s and the force-extension behavior of the PE chain. In accord with earlier theoretical predictions, our results indicate that for a chain with n Kuhn segments, l E ~ c s -0.5 as linear charge density approaches 1/n. Moreover, the constant force ensemble simulation results accurately predict the initial non-linear force-extension region of PE chain recently measured via single chain experiments. Inspired by Cohen’s extraction of Warner’s force law from the inverse Langevin force law, a novel numerical scheme is developed to extract a new elastic force law for real chains from our discrete set of force-extension data similar to Padè expansion, which accurately depicts the initial non-linear region where themore » total Kuhn length is less than the thermal screening length.« less

Authors:
 [1]; ORCiD logo [1]
  1. Univ. of Tennessee, Knoxville, TN (United States). Materials Research and Innovation Lab. Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Univ. of Tennessee, Knoxville, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1469168
Alternate Identifier(s):
OSTI ID: 1234561
Grant/Contract Number:  
FG02-08ER46528
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 2; 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; macromolecules; electrolytes; computer simulation; Debye length; computational models; polymer chemistry; general topology; polyelectrolytes; phase transitions; electrostatics

Citation Formats

Malekzadeh Moghani, Mahdy, and Khomami, Bamin. Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation. United States: N. p., 2016. Web. doi:10.1063/1.4939720.
Malekzadeh Moghani, Mahdy, & Khomami, Bamin. Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation. United States. doi:10.1063/1.4939720.
Malekzadeh Moghani, Mahdy, and Khomami, Bamin. Tue . "Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation". United States. doi:10.1063/1.4939720. https://www.osti.gov/servlets/purl/1469168.
@article{osti_1469168,
title = {Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation},
author = {Malekzadeh Moghani, Mahdy and Khomami, Bamin},
abstractNote = {Macromolecules with ionizable groups are ubiquitous in biological and synthetic systems. Due to the complex interaction between chain and electrostatic decorrelation lengths, both equilibrium properties and micro-mechanical response of dilute solutions of polyelectrolytes (PEs) are more complex than their neutral counterparts. In this paper, the bead-rod micromechanical description of a chain is used to perform hi-fidelity Brownian dynamics simulation of dilute PE solutions to ascertain the self-similar equilibrium behavior of PE chains with various linear charge densities, scaling of the Kuhn step length (lE) with salt concentration cs and the force-extension behavior of the PE chain. In accord with earlier theoretical predictions, our results indicate that for a chain with n Kuhn segments, lE ~ cs-0.5 as linear charge density approaches 1/n. Moreover, the constant force ensemble simulation results accurately predict the initial non-linear force-extension region of PE chain recently measured via single chain experiments. Inspired by Cohen’s extraction of Warner’s force law from the inverse Langevin force law, a novel numerical scheme is developed to extract a new elastic force law for real chains from our discrete set of force-extension data similar to Padè expansion, which accurately depicts the initial non-linear region where the total Kuhn length is less than the thermal screening length.},
doi = {10.1063/1.4939720},
journal = {Journal of Chemical Physics},
number = 2,
volume = 144,
place = {United States},
year = {2016},
month = {1}
}

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