Pivotal Roles of Triple Screening-Topological, Electrostatic, and Hydrodynamic-On Dynamics in Semidilute Polyelectrolyte Solutions

Kumar, Rajeev; Slim, Ali H.; Faraone, Antonio; Carrillo, Jan-Michael Y.; Poling-Skutvik, Ryan; Muthukumar, Murugappan; Marciel, Amanda B.; Conrad, Jacinta C.

doi:10.1021/acs.macromol.3c02564

Pivotal Roles of Triple Screening-Topological, Electrostatic, and Hydrodynamic-On Dynamics in Semidilute Polyelectrolyte Solutions

Journal Article · Fri Mar 15 00:00:00 EDT 2024 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.3c02564· OSTI ID:2333846

^[1]; Slim, Ali H. ^[2]; ^[3]; ^[1]; ^[4]; ^[5]; ^[6]; ^[2]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Univ. of Houston, TX (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Univ. of Rhode Island, Kingston, RI (United States)
Univ. of Massachusetts, Amherst, MA (United States)
Rice Univ., Houston, TX (United States)

For semidilute polyelectrolyte solutions, it is generally assumed that topological, electrostatic, and hydrodynamic interactions are screened (called triple screening). Despite a large body of research focused on polyelectrolyte solutions, the concept of triple screening has never been rigorously verified. In this work, we test the concept by probing concentration fluctuations in aqueous solutions containing a well-studied polyelectrolyte, sodium poly(styrenesulfonate) (NaPSS) with neutron scattering, theory, and molecular dynamics simulations. Neutron spin–echo (NSE) and small-angle neutron scattering (SANS) data from semidilute solutions of NaPSS are presented at different polymer and salt (NaCl) concentrations. A combined theory for structure (J. Chem. Phys. 105, 5183 (1996)) and dynamics (J. Chem. Phys. 107, 2619 (1997)), which captures effects of hydrodynamic, topological, and electrostatic screening, is used to interpret the experimental results. Here, the theory quantitatively predicts the decay rate obtained from the NSE measurements while capturing the shape and concentration dependencies of the polyelectrolyte peak observed in the SANS spectra. Detailed comparisons of the theory and the experiments reveal that the wavevector-dependent decay rate of concentration fluctuations in semidilute solutions of polyelectrolytes is dictated by the screening of hydrodynamic, topological, and electrostatic interactions. This conclusion is corroborated by coarse-grained molecular dynamics simulations, executed without any hydrodynamic interactions, which fail to capture the correct wavevector dependence of the decay rate. These results highlight that the theories based on the concept of triple screening provide a quantitative framework for predicting a relation between the structure and dynamics of polyelectrolyte solutions.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2333846

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 6 Vol. 57; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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