Role of polydispersity in anomalous interactions in electrostatically levitated colloidal systems.

In this paper, we investigate the effects of using inverse analyses developed for monodisperse particles to extract particle-particle and particle-surface potentials from simulated interfacial colloidal configurations having finite-size polydispersity. Forward Monte Carlo simulations are used to generate three-dimensional equilibrium configurations of log normal-distributed polydisperse particles confined by gravity near an underlying surface. Particles remain levitated above the substrate and stabilized against aggregation by repulsive electrostatic Derjaguin-Landau-Verwey-Overbeek pair potentials. An inverse Ornstein-Zernike analysis and an inverse Monte Carlo simulation method are used to obtain interactions from simulated distribution functions as a function of polydispersity (sigma), relative range of repulsion (kappa a), and projected interfacial concentration (rho). Both inverse analyses successfully recover input potentials for all monodisperse cases, but fail for polydispersities often encountered in experiments. For different conditions (sigma, kappa a, and rho), our results indicate softened short-range repulsion, anomalous long-range attraction, and apparent particle overlaps, which are similar to commonly reported observations in optical microscopy measurements of quasi-two-dimensional interfacial colloidal ensembles. By demonstrating signatures of, and limitations due to, polydispersity when extracting pair potentials from measured distribution functions, our specific goal is to provide a basis to objectively interpret and resolve the effects of polydispersity in optical microscopy experiments.