The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, introduced more than 70 years ago, is a hallmark of colloidal particle modeling. For highly charged particles in the dilute regime, it is often supplemented by Alexander's prescription (Alexander et al. in J Chem Phys 80:5776, 1984) for using a renormalized charge. Here, we solve the problem of the interaction between two charged colloids at finite ionic strength, including dielectric mismatch effects, using an efficient numerical scheme to solve the nonlinear Poisson-Boltzmann (NPB) equation with unknown boundary conditions. Our results perfectly match the analytical predictions for the renormalized charge by Trizac and coworkers (Aubouy et al. in J Phys A 36:5835, 2003). Moreover, they allow us to reinterpret previous molecular dynamics (MD) simulation results by Kreer et al. (Phys Rev E 74:021401, 2006), rendering them now in agreement with the expected behavior. We furthermore find that the influence of polarization becomes important only when the Debye layers overlap significantly.
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http://dx.doi.org/10.1140/epje/s10189-023-00334-2 | DOI Listing |
ACS Nano
December 2024
Department of Chemistry and Institute of Materials Science and Engineering, Washington University in Saint Louis, Saint Louis, Missouri 63130, United States.
A single photoexcited electron-hole pair within a polar semiconductor nanocrystal (SNC) alters the charge screening and shielding within it. Perturbations of the crystal lattice and of the valence and conduction bands result, and the quantum-confinement states in a SNC shift uniquely with a dependence on the states occupied by the carriers. This shifting is termed quantum-state renormalization (QSR).
View Article and Find Full Text PDFJ Chem Phys
November 2024
Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, USA.
The electrostatic correlations between ions profoundly influence the structure and forces within electrical double layers. Here, we apply the modified Gaussian renormalized fluctuation theory to investigate the counter-intuitive phenomenon of repulsion between two oppositely charged surfaces and discuss its relationship with overcharging. By accurately accounting for the effect of spatially varying ion-ion correlations, we capture these repulsive forces for divalent, trivalent, as well as tetravalent ions, in quantitative agreement with reported simulation results.
View Article and Find Full Text PDFJ Chem Phys
November 2024
São Paulo State University (UNESP), Institute of Biosciences, Humanities and Exact Sciences, 15054-000 São José do Rio Preto, Brazil.
The critical adsorption conditions of polyelectrolytes (PEs) onto planar, cylindrical, and spherical surfaces were obtained by solving the Edwards equation using the Wentzel-Kramers-Brillouin (WKB) method. It demonstrated to provide a suitable analytical approach for all three geometries, in conformity with some experimental results for weakly charged micelles. However, our Monte Carlo simulations implementing approximate solutions of the nonlinear Poisson-Boltzmann equation for highly charged surfaces indicated recently the emergence of a limiting value of ionic strength due to a nonlinear dependence of the electrostatic (ES) potential on the surface-charge density σ.
View Article and Find Full Text PDFPhys Rev E
October 2024
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Soft Matter
November 2024
Institute of Physics, Johannes Gutenberg University, 55128 Mainz, Germany.
We study the influence of airborne CO on the charge state of carboxylate stabilized polymer latex particles suspended in aqueous electrolytes. We combine conductometric experiments interpreted in terms of Hessinger's conductivity model with Poisson-Boltzmann cell (PBC) model calculations with charge regulation boundary conditions. Without CO, a minority of the weakly acidic surface groups are dissociated and only a fraction of the total number of counter-ions actually contribute to conductivity.
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