Cavity averages for hard spheres in the presence of polydispersity and incomplete data

TL;DR

This paper introduces a new cavity-based method for extracting thermodynamic properties from hard-sphere systems, compares it with existing methods, and assesses their robustness against incomplete data, guiding experimental data analysis.

Contribution

It presents a novel 'available-volume-after-takeout' method, demonstrates its mathematical equivalence to existing methods, and evaluates their performance with finite and incomplete data sets.

Findings

All three methods are mathematically equivalent.

Methods show different limitations with finite data.

Errors can be significant with missing data, affecting pressure and chemical potential estimates.

Abstract

We develop a cavity-based method which allows to extract thermodynamic properties from position information in hard-sphere/disk systems. So far, there are 'available-volume' and 'free-volume' methods. We add a third one, which we call 'available-volume-after-takeout', and which is shown to be mathematically equivalent to the others. In applications, where data sets are finite, all three methods show limitations, and they do this in different parameter ranges. We illustrate the principal equivalence and the limitations on data from molecular dynamics -- In particular, we test robustness against missing data. We have in mind experimental limitations where there is a small polydispersity, say 4% in the particle radii, but individual radii cannot be determined. We observe that, depending on the used method, the errors in such a situation are easily 100% for the pressure and 10kT for the chemical potentials. Our work is meant as guideline to the experimentalist for choosing the right one of the three methods, in order to keep the outcome of experimental data analysis meaningful.