Short-range electrostatic screening in ionic liquids as inferred by direct force measurements

TL;DR

This study clarifies discrepancies in electrostatic screening in ionic liquids by using advanced force measurements, revealing that apparent long-range interactions are due to out-of-equilibrium effects and that true screening aligns with classical theories.

Contribution

The paper demonstrates that long-range forces observed in ionic liquids are artifacts of non-equilibrium conditions, providing a comprehensive experimental analysis that reconciles previous conflicting reports.

Findings

Long-range interactions depend on measurement speed and relaxation times.

True screening lengths match Poisson-Boltzmann theory with finite ion sizes.

Out-of-equilibrium dynamics cause apparent anomalous underscreening.

Abstract

Previous experimental reports of long-range interactions in ionic liquids (ILs) stand in contradiction with theoretical predictions and numerical simulations. To provide insights into the literature discrepancies regarding the experimental ranges of electrostatic screening, claimed with orders of magnitude larger, the interactions between pairs of mica and borosilicate surfaces confining ILs are investigated by two complementary advanced Surface Force Apparatuses. Regardless of differences in confinement geometries (crossed-cylinders, sphere-flat), radii of curvature (cm-mm), and measurement techniques (stepwise vs continuous approach), two ever present force regimes are evidenced. At small surface separations, oscillatory forces reflect IL structuration and layering, while outside this gap, the interaction is monotonic repulsive. In both regimes the spatial extent and force magnitude depend critically on motion conditions, as demonstrated by achieving velocities as low as 9 pm/s with equilibration times up to 90 s. At large separations, fast surface displacements generate long-range interactions (over tens of ion size) creating the illusion of anomalous underscreening, whereas increasingly slow ones shrink both magnitude and range of the repulsion with decay-lengths converging ultimately to a screening length consistent with Poisson-Boltzmann theory with finite ion sizes. The transition from apparent long-range to short-range screening unfolds over nearly two orders of magnitude in time, revealing slow relaxation dynamics reminiscent of aging phenomena. These findings definitely resolve a decade-old controversy on force measurements and reveal rich out-of-equilibrium dynamics. The hydrodynamic contribution to the net force is admittedly crucial to be reduced especially when relaxations span decades in time, but approaching thermodynamic equilibrium during measurements proves essential.