Ion Correlation-Driven Hysteretic Adhesion and Repulsion between Opposing Polyelectrolyte Brushes
arXiv:2405.19329 · doi:10.1021/acsmacrolett.4c00426
Abstract
Polyelectrolyte (PE) brushes are widely used in biomaterials and nanotechnology to regulate surface properties and interactions. Here, we apply the electrostatic correlation augmented self-consistent field theory to investigate the interactions between opposing PE brushes in a mixture of 1:1 and 3:1 salt solutions. Our theory predicts hysteretic feature of the normal stress induced by strong ion correlations. In the presence of trivalent ions, the force profile is discontinuous: repulsive in the compression branch and adhesive in the separation branch. The molecular origin of the hysteretic force is the coexistence of two collapsed modes: two separated condensed layer on each surface in the compression and a single bundled condensed layer in the separation. With the systematic inclusion of ion correlations, our theory fully captures the hysteretic force, adhesive separation, ``jump-in'' and ``jump-out'' features, and the ``specific ion effect'', all in good agreement with the reported experimental results.
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