Year: 2014
Type: article
Abstract: Electrostatic correlation effects near charged planar surfaces immersed in a symmetric electrolytes solution are systematically studied by numerically solving the nonlinear six-dimensional electrostatic self-consistent equations. We compare our numerical results with widely accepted mean-field (MF) theory results, and find that the MF theory remains quantitatively accurate only in weakly charged regimes, whereas in strongly charged regimes, the MF predictions deviate drastically due to the electrostatic correlation effects. We also observe a first-order like phase-transition corresponding to the counterion condensation phenomenon in strongly charged regimes, and compute the phase diagram numerically within a wide parameter range. Finally, we investigate the interactions between two likely-charged planar surfaces, which repulse each other as MF theory predicts in weakly charged regimes. However, our results show that they attract each other above a certain distance in strongly charged regimes due to significant electrostatic correlations.
Source: The Journal of Chemical Physics
DOI: 10.1063/1.4894053
Authors: Mingge Deng, George Em Karniadakis
Institution: Brown University
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: bronze
OpenAlex ID: W2040653425