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Embarras de richesses in non-DLVO colloid interactions

In its original formulation, the seminal Deryaguin-Landau-Verwey-Overbeek (DLVO) theory of colloidal stability seemed like a simple but realistic description of the world of colloid interactions in electrolyte solutions. It is based on a straightforward superposition of the mean-field Poisson-Boltzmann (PB) electrostatics with the electrodynamic van der Waals (vdW) interactions driven by thermal and quantum fluctuations. However, subsequent developments continued to reveal a much richer and deeper structure of fundamental interactions on the nano- and micro-scale: the granularity and structure of the solvent, charging equilibria of dissociable charge groups, inhomogeneous charge distributions, the finite size of the ions, non-mean-field electrostatics, ion-ion correlations, and more. Today, the original simplicity is gone and we are left with an embarrassingly rich variety of interactions that defy simple classification and reduction to a few fundamental mechanisms. In this mini-review, we comment on the contemporary state-of-the-art picture of colloidal interactions, in view of some recent progress in experiments.