Effective charges and virial pressure of concentrated macroion solutions

Boon, Niels; Guerrero-García, Guillermo Ivan; van Roij, René; Olvera de la Cruz, Monica

doi:10.1073/pnas.1511798112

Title: Effective charges and virial pressure of concentrated macroion solutions

Journal Article · Mon Jul 13 00:00:00 EDT 2015 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1511798112· OSTI ID:1349033

Boon, Niels ^[1]; Guerrero-García, Guillermo Ivan ^[2]; van Roij, René ^[3]; Olvera de la Cruz, Monica ^[1]

Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); Univ. Autonoma de San Luis Potosi (Mexico)
Univ. of Utrecht (Netherlands)

The stability of colloidal suspensions is crucial in a wide variety of processes, including the fabrication of photonic materials and scaffolds for biological assemblies. The ionic strength of the electrolyte that suspends charged colloids is widely used to control the physical properties of colloidal suspensions. The extensively used two-body Derjaguin-Landau-Verwey-Overbeek (DLVO) approach allows for a quantitative analysis of the effective electrostatic forces between colloidal particles. DLVO relates the ionic double layers, which enclose the particles, to their effective electrostatic repulsion. Nevertheless, the double layer is distorted at high macroion volume fractions. Therefore, DLVO cannot describe the many-body effects that arise in concentrated suspensions. In this paper, we show that this problem can be largely resolved by identifying effective point charges for the macroions using cell theory. This extrapolated point charge (EPC) method assigns effective point charges in a consistent way, taking into account the excluded volume of highly charged macroions at any concentration, and thereby naturally accounting for high volume fractions in both salt-free and added-salt conditions. We provide an analytical expression for the effective pair potential and validate the EPC method by comparing molecular dynamics simulations of macroions and monovalent microions that interact via Coulombic potentials to simulations of macroions interacting via the derived EPC effective potential. The simulations reproduce the macroion-macroion spatial correlation and the virial pressure obtained with the EPC model. Finally, our findings provide a route to relate the physical properties such as pressure in systems of screened Coulomb particles to experimental measurements.

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Research Organization:: Northwestern Univ., Evanston, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)

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

Grant/Contract Number:: SC0000989

OSTI ID:: 1349033

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 112, Issue 30; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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