All-atom molecular dynamics simulations of weak polyionic brushes: influence of charge density on the properties of polyelectrolyte chains, brush-supported counterions, and water molecules

Sachar, Harnoor Singh; Pial, Turash Haque; Chava, Bhargav Sai; Das, Siddhartha

doi:10.1039/d0sm01000f

All-atom molecular dynamics simulations of weak polyionic brushes: influence of charge density on the properties of polyelectrolyte chains, brush-supported counterions, and water molecules

Journal Article · Mon Jul 27 00:00:00 EDT 2020 · Soft Matter

DOI:https://doi.org/10.1039/d0sm01000f· OSTI ID:1656812

Sachar, Harnoor Singh ^[1]; Pial, Turash Haque ^[2]; Chava, Bhargav Sai ^[2]; ^[2]

Univ. of Maryland, College Park, MD (United States); University of Maryland
Univ. of Maryland, College Park, MD (United States)

All atom molecular dynamics (MD) simulations of planar Na+-counterion-neutralized polyacrylic acid (PAA) brushes are performed for varying degrees of ionization (and thereby varying charge density) and varying grafting density. Variation in the PE charge density (or degree of ionization) and grafting density leads to massive changes of the properties of the PE molecules (quantified by the changes in the height and the mobility of the PE brushes) as well as the local arrangement and distribution of the brush-supported counterions and water molecules within the brushes. The effect on the counterions is manifested by the corresponding variation of the counterion mobility, counterion concentration, extent of counterion binding to the charged site of the PE brushes, water-in-salt-like structure formation, and counterion-water–oxygen radial distribution function within the PE brushes. On the other hand, the effect on water molecules is manifested by the corresponding variation of water–oxygen–water–oxygen RDF, local water density, water–water and water–PE functional group hydrogen bond networks, static dielectric constant of water molecules, orientational tetrahedral order parameter, and water mobility. Enforcing such varying degree of ionization of weak polyelectrolytes is possible by changing the pH of the surrounding medium. Thus, our results provide insights into the changes in microstructure (at the atomistic level) of weak polyionic brushes at varying pH. Finally, we anticipate that this knowledge will prove to be vital for the efficient design of several nano-scale systems employing PE brushes such as nanomechanical gates, current rectifiers, etc.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Maryland, College Park, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0017741

OSTI ID:: 1656812

Alternate ID(s):: OSTI ID: 1644700

Journal Information:: Soft Matter, Journal Name: Soft Matter Journal Issue: 33 Vol. 16; ISSN 1744-683X

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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