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Weak and Strong-Coupling Electrostatic Interactions between Asymmetrically Charged Planar Surfaces

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 Added by Ali Naji
 Publication date 2009
  fields Physics
and research's language is English




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We compare weak and strong coupling theory of counterion-mediated electrostatic interactions between two asymmetrically charged plates with extensive Monte-Carlo simulations. Analytical results in both weak and strong coupling limits compare excellently with simulations in their respective regimes of validity. The system shows a surprisingly rich structure in terms of interactions between the surfaces as well as fundamental qualitative differences in behavior in the weak and the strong coupling limits.



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267 - M. Kanduc , A. Naji , Y.S. Jho 2009
We present general arguments for the importance, or lack thereof, of the structure in the charge distribution of counterions for counterion-mediated interactions between bounding symmetrically charged surfaces. We show that on the mean field or weak coupling level, the charge quadrupole contributes the lowest order modification to the contact value theorem and thus to the intersurface electrostatic interactions. The image effects are non-existent on the mean-field level even with multipoles. On the strong coupling level the quadrupoles and higher order multipoles contribute additional terms to the interaction free energy only in the presence of dielectric inhomogeneities. Without them, the monopole is the only multipole that contributes to the strong coupling electrostatics. We explore the consequences of these statements in all their generality.
We investigate the effective interaction between two randomly charged but otherwise net-neutral, planar dielectric slabs immersed in an asymmetric Coulomb fluid containing a mixture of mobile monovalent and multivalent ions. The presence of charge disorder on the apposed bounding surfaces of the slabs leads to substantial qualitative changes in the way they interact, as compared with the standard picture provided by the van der Waals and image-induced, ion-depletion interactions. While, the latter predict purely attractive interactions between strictly neutral slabs, we show that the combined effects from surface charge disorder, image depletion, Debye (or salt) screening and also, in particular, their coupling with multivalent ions, give rise to a more diverse behavior for the effective interaction between net-neutral slabs. Disorder effects show large variation depending on the properly quantified strength of disorder, leading either to non-monotonic effective interaction with both repulsive and attractive branches when the surface charges are weakly disordered (small disorder variance) or to a dominating attractive interaction that is larger both in its range and magnitude than what is predicted from the van der Waals and image-induced, ion-depletion interactions, when the surfaces are strongly disordered (large disorder variance).
We calculate the dispersive force between a ground state atom and a non planar surface. We present explicit results for a corrugated surface, derived from the scattering approach at first order in the corrugation amplitude. A variety of analytical results are derived in different limiting cases, including the van der Waals and Casimir-Polder regimes. We compute numerically the exact first-order dispersive potential for arbitrary separation distances and corrugation wavelengths, for a Rubidium atom on top of a silicon or gold corrugated surface. We discuss in detail the inadequacy of the proximity force approximation, and present a simple but adequate approximation for computing the potential.
We have studied the electrostatic screening effect of NaCl solutions on the interactions between anionic lipid bilayers in the fluid lamellar phase using a Poisson-Boltzmann based mean-field approach with constant charge and constant potential limiting charge regulation boundary conditions. The full DLVO potential, including the electrostatic, hydration and van der Waals interactions, was coupled to thermal bending fluctuations of the membranes via a variational Gaussian Ansatz. This allowed us to analyze the coupling between the osmotic pressure and the fluctuation amplitudes and compare them both simultaneously with the measured dependence on the bilayer separation, determined by the small-angle X-ray scattering experiments. High-structural resolution analysis of the scattering data revealed no significant changes of membrane structure as a function of salt concentration. Parsimonious description of our results is consistent with the constant charge limit of the general charge regulation phenomenology, with fully dissociated lipid charge groups, together with a four-fold reduction of the membranes bending rigidity upon increasing NaCl concentration.
When a flat elastic strip is compressed along its axis, it is bent in one of two possible directions via spontaneous symmetry breaking and forms a cylindrical arc, a phenomenon well known as Euler buckling. When this cylindrical section is pushed in the other direction, the bending direction can suddenly reverse. This instability is called snap-through buckling and is one of the elementary shape transitions in a prestressed thin structure. Combining experiments and theory, we study snap-buckling of an elastic strip with one end hinged and the other end clamped. These asymmetric boundary constraints break the intrinsic symmetry of the strip, generating rich exotic mechanical behaviors including largely hysteretic but reproducible force responses and switch-like discontinuous shape changes. We establish the set of exact analytical solutions that fully explain all of our major experimental and numerical findings. Asymmetric boundary conditions arise naturally in diverse situations when a thin object is in contact with a solid surface at one end, but their profound consequences for the buckling mechanics have been largely overlooked to date. The idea of introducing asymmetry through boundary conditions would yield new insight into complex and programmable functionalities in material and industrial design.
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