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In this paper, we theoretically study the electrostatic interaction between apair of identical colloids with constant surface potentials sitting in closevicinity of each other at a fluid interface. By employing a simplified yetreasonable model system, the problem is solved within the framework ofclassical density functional theory and linearized as well as nonlinearPoisson-Boltzmann (PB) theory. Apart from providing a sound theoreticalframework generally applicable to any such problem, our novel findings, all ofwhich contradict common beliefs, include the following: first, quantitative aswell as qualitative differences between the interactions obtained within thelinear and the nonlinear PB theories; second, the importance of theelectrostatic interaction between the omnipresent three-phase contact lines ininterfacial systems; and third, the occurrence of an attractive electrostaticinteraction between a pair of identical metal colloids. The unusual attractionwe report on largely stems from an attractive line interaction which althoughscales linearly with the size of the particle, can compete with the surfaceinteractions and can be strong enough to alter the nature of the totalelectrostatic interaction. Our results should find applications in metal ormetal-coated particle-stabilized emulsions where densely packed particle arraysare not only frequently observed but are sometimes required.

Electrostatic pair-interaction of nearby metal or metal-coated colloids at fluid interfaces