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Inverted critical adsorption of polyelectrolytes in confinement

What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer-surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density $σ_c$-defining the adsorption-desorption transition-are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of $σ_c$ for the concave interfaces versus the Debye screening length $1/κ$ and the extent of confinement $a$ for these three interfaces for small $κa$ values. For large $κa$ the critical adsorption condition approaches the planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness $a$ is of the order of $1/κ$. We also rationalize how $σ_c(κ)$ gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length onto critical adsorption-the effect often hard to tackle theoretically-putting an emphasis on polymers inside attractive spherical cavities.