LAUSR

The geometric pore size distribution (PSD) P(r) as function of pore radius r is an important characteristic of porous structures, including particle-based systems, because it allows us to analyze adsorption behavior, the strength of materials, etc. Multiple definitions and corresponding algorithms, particularly in the context of computational approaches, exist that aim at calculating a PSD, often without mentioning the employed definition and therefore leading to qualitatively very different and apparently incompatible results. Here, we analyze the differences between the PSDs introduced by Torquato et al. and the more widely accepted one provided by Gelb and Gubbins, here denoted as T-PSD and G-PSD, respectively, and provide rigorous mathematical definitions that allow us to quantify the qualitative differences. We then extend G-PSD to incorporate the ideas of coating, which is significant for nanoparticle-based systems, and of finite probe particles, which is crucial to micro and mesoporous particles. We derive how the extended and classical versions are interrelated and how to calculate them properly. We next analyze various numerical approaches used to calculate classical G-PSDs and may be used to calculate the generalized G-PSD. To this end, we propose a simple yet sufficiently complicated benchmark for which we calculate the different PSDs analytically. This approach allows us to completely rule out a recently proposed algorithm based on radical Voronoi tessellation. Instead, we find and prove that the output of a grid-free classical Voronoi tessellation, namely, the properties of its triangulated faces, can be used to formulate an algorithm, which is capable of calculating the generalized G-PSD for a system of monodisperse spherical particles (or points) to any precision, using analytical expressions. The Voronoi-based algorithm developed and provided here has optimal scaling behavior and outperforms grid-based approaches.