On the importance of thermodynamic self-consistency for calculating clusterlike pair correlations in hard-core double Yukawa fluids.

J Chem Phys 134(6):064904 (2011) PMID 21322731

Understanding the mechanisms of clustering in colloids, nanoparticles, and proteins is of significant interest in material science and both chemical and pharmaceutical industries. Recently, using an integral equation theory formalism, Bomont et al. [J. Chem. Phys. 132, 184508 (2010)] studied theoretically the temperature dependence, at a fixed density, of the cluster formation in systems where particles interact with a hard-core double Yukawa potential composed of a short-range attraction and a long-range repulsion. In this paper, we provide evidence that the low-q peak in the static structure factor, frequently associated with the formation of clusters, is a common behavior in systems with competing interactions. In particular, we demonstrate that, based on a thermodynamic self-consistency criterion, accurate structural functions are obtained for different choices of closure relations. Moreover, we explore the dependence of the low-q peak on the particle number density, temperature, and potential parameters. Our findings indicate that enforcing thermodynamic self-consistency is the key factor to calculate both thermodynamic properties and static structure factors, including the low-q behavior, for colloidal dispersions with both attractive and repulsive interactions. Additionally, a simple analysis of the mean number of neighboring particles provides a qualitative description of some of the cluster features.