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Partial pair-correlation functions of colloidal suspensions with continuouspolydispersity can be challenging to characterize from optical microscopy orcomputer simulation data due to inadequate sampling. As a result, it is commonto adopt an effective one-component description of the structure that ignoresthe differences between particle types. Unfortunately, whether this kind ofsimplified description preserves or averages out information important forunderstanding the behavior of the fluid depends on the degree of polydispersityand can be difficult to assess, especially when the correspondingmulticomponent description of the pair correlations is unavailable forcomparison. Here, we present a computer simulation study that examines theimplications of adopting an effective one-component structural description of apolydisperse fluid. The square-well model that we investigate mimics keyaspects of the experimental behavior of suspended colloids with short-range,polymer-mediated attractions. To characterize the partial pair-correlationfunctions and thermodynamic excess entropy of this system, we introduce a MonteCarlo sampling strategy appropriate for fluids with a large number ofpseudo-components. The data from our simulations at high particleconcentrations, as well as exact theoretical results for dilute systems, showhow qualitatively different trends between structural order and particleattractions emerge from the multicomponent and effective one-componenttreatments, even with systems characterized by moderate polydispersity. Weexamine consequences of these differences for excess-entropy based scalings ofshear viscosity, and we discuss how use of the multicomponent treatment revealssimilarities between the corresponding dynamic scaling behaviors of attractivecolloids and liquid water that the effective one-component analysis does notcapture.

Implications of the effective one-component analysis of pair correlations in colloidal fluids with polydispersity