The apparent charge of nanoparticles trapped at a water interface

Charged spherical nanoparticles trapped at the interface between water and air or water and oil exhibit repulsive electrostatic forces that contain a long-ranged dipolar and a short-ranged exponentially decaying component. The former are induced by the unscreened electrostatic field through the non-polar low-permittivity medium, and the latter result from the overlap of the diffuse ion clouds that form in the aqueous phase close to the nanoparticles. The magnitude of the long-ranged dipolar interaction is largely determined by the residual charges that remain attached to the air- (or oil-) exposed region of the nanoparticle. In the present work we address the question to what extent the charges on the water-immersed part of the nanoparticle provide an additional contribution to the dipolar interaction. To this end, we model the electrostatic properties of a spherical particle - a nanoparticle or a colloid - that partitions equatorially to the air-water interface, thereby employing nonlinear Poisson-Boltzmann theory in the aqueous solution and accounting for the propagation of the electric field through the interior of the particle. We demonstrate that the apparent charge density on the air-exposed region of the particle, which determines the dipole potential, is influenced by the electrostatic properties in the aqueous solution. We also show that this electrostatic coupling through the particle can be reproduced qualitatively by a simple analytic planar capacitor model. Our results help to rationalize the experimentally observed weak but non-vanishing salt dependence of the forces that stabilize ordered two-dimensional arrays of interface-trapped nanoparticles or colloids.