Theory of capillary-induced interactions beyond the superposition approximation.

Within a general theoretical framework, we study the effective, deformation-induced interaction between two colloidal particles trapped at a fluid interface in the regime of small deformations. In many studies, this interaction has been computed with the ansatz that the actual interface configuration for the pair is given by the linear superposition of the interface deformations around the single particles. Here, we assess the validity of this approach and compute the leading term of the effective interaction for a large interparticle separation beyond this so-called superposition approximation. As an application, we consider the experimentally relevant case of interface deformations owing to the electrostatic field emanating from charged colloidal particles. In mechanical isolation, i.e., if the net force acting on the total system consisting of the particles plus the interface vanishes, the superposition approximation is actually invalid. The effective capillary interaction is governed by contributions beyond this approximation and turns out to be attractive. For sufficiently small surface charges on the colloids, such that linearization is strictly valid, and at asymptotically large separations, the effective interaction does not overcome the direct electrostatic repulsion between the colloidal particles.