Dielectric water properties, which significantly change in confinement, determine electrostatic interactions and thereby influence all molecular forces and chemical reactions. We present comparative simulations of water between graphene sheets, decanol monolayers, and phospholipid and glycolipid bilayers. Generally, dielectric profiles strongly differ in perpendicular and parallel surface directions and for large surface separation decay to the bulk value 1−2 nm away from the surface. Polar surface groups enhance the local interfacial dielectric response and for phospholipid bilayers induce a giant parallel contribution. A mapping on a box model with asymptotically determined effective water layer widths demonstrates that the perpendicular effective dielectric constant for all systems decreases for confinement below a nanometer, while the parallel one stays rather constant. The confinement-dependent perpendicular effective dielectric constant for graphene is in agreement with experimental data only if the effective water layer width is suitably adjusted. The interactions between two charges at small separation depend on the product of parallel and perpendicular effective water dielectric components; for large separation the interactions depend on the confining medium. For metallic confining media the interactions at large separation decay exponentially with a decay length that depends on the ratio of the effective parallel and perpendicular water dielectric components.

Many vital processes taking place in electrolytes, such as nanoparticle self-assembly, water purification and the operation of supercapacitors, rely on the precise many-body interactions between surfaces and ions in water. Here we study the interaction between a hydrated ion and a charge-neutral graphene layer using atomistic molecular dynamics simulations. For small separations, the ion-graphene repulsion is of non-electrostatic nature and for intermediate separations Van-der-Waals attraction becomes important. Contrary to prevailing theory, we show that non-linear and tensorial dielectric effects become non-negligible close to surfaces, even for monovalent ions. This breakdown of standard isotropic linear dielectric theory has important consequences for the understanding and modeling of charged objects at surfaces.

We extract the folding free energy landscape and the time-dependent friction function, the two ingredients of the generalized Langevin equation (GLE), from explicit-water molecular dynamics (MD) simulations of the α-helix forming polypeptide alanine9 for a one-dimensional reaction coordinate based on the sum of the native H-bond distances. Folding and unfolding times from numerical integration of the GLE agree accurately with MD results, which demonstrate the robustness of our GLE-based non-Markovian model. In contrast, Markovian models do not accurately describe the peptide kinetics and in particular, cannot reproduce the folding and unfolding kinetics simultaneously, even if a spatially dependent friction profile is used. Analysis of the GLE demonstrates that memory effects in the friction significantly speed up peptide folding and unfolding kinetics, as predicted by the Grote–Hynes theory, and are the cause of anomalous diffusion in configuration space. Our methods are applicable to any reaction coordinate and in principle, also to experimental trajectories from single-molecule experiments. Our results demonstrate that a consistent description of protein-folding dynamics must account for memory friction effects.

Molecular dynamics simulations in conjunction with effective medium theory are used to investigate dielectric effects in water-filled nanotubes. The resulting effective axial dielectric constant shows a divergent increase for small nanotube radii that depends on the nanotube length, while the effective radial dielectric constant decreases significantly for thin nanotubes. By solving Poisson's equation for an anisotropic dielectric medium in cylindrical geometry, we show that the axial ion-ion interaction depends for small separations primarily on the radial dielectric constant, not on the axial one. This means that electrostatic ion-ion interactions in thin water-filled nanotubes are on the linear dielectric level significantly enhanced due to water confinement effects at small separations, while at large separations the outside medium dominates. If the outside medium is metallic, the ion-ion interaction decays exponentially for large ion separation.

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