Finite-size effects of the excess entropy computed from integrating the radial distribution function

TL;DR

This paper investigates finite-size effects on excess entropy calculations from the radial distribution function, deriving expressions for finite systems, and compares different computational methods through simulations.

Contribution

It introduces new expressions for computing excess entropy and Kirkwood-Buff integrals in finite systems and analyzes their convergence and accuracy.

Findings

Excess entropy integrals converge faster than Kirkwood-Buff integrals.

At low densities, RDF-based excess entropy matches thermodynamic integration results.

Differences up to 20% occur at higher densities between methods.

Abstract

Computation of the excess entropy from the second-order density expansion of the entropy holds strictly for infinite systems in the limit of small densities. For the reliable and efficient computation of excess entropy, it is important to understand finite-size effects. Here, expressions to compute excess entropy and Kirkwood-Buff (KB) integrals by integrating the Radial Distribution Function (RDF) in a finite volume are derived, from which Sex and KB integrals in the thermodynamic limit are obtained. The scaling of these integrals with system size is studied. We show that the integrals of excess entropy converge faster than KB integrals. We compute excess entropy from Monte Carlo simulations using the Wang-Ramirez-Dobnikar-Frenkel pair interaction potential by thermodynamic integration and by integration of the RDF. We show that excess entropy computed by integrating the RDF is identical to that of excess entropy computed from thermodynamic integration at low densities, provided the RDF is extrapolated to the thermodynamic limit. At higher densities, differences up to 20% are observed.