Another resolution of the configurational entropy paradox as applied to hard spheres

J Chem Phys. 2017 Dec 14;147(22):224503. doi: 10.1063/1.4999483.

Abstract

Ozawa and Berthier [J. Chem. Phys. 146, 014502 (2017)] recently studied the configurational and vibrational entropies Sconf and Svib from the relation Stot = Sconf + Svib for polydisperse mixtures of spheres. They noticed that because the total entropy per particle Stot/N shall contain the mixing entropy per particle kBsmix and Svib/N shall not, the configurational entropy per particle Sconf/N shall diverge in the thermodynamic limit for continuous polydispersity due to the diverging smix. They also provided a resolution for this paradox and related problems-it relies on a careful redefining of Sconf and Svib. Here, we note that the relation Stot = Sconf + Svib is essentially a geometric relation in the phase space and shall hold without redefining Sconf and Svib. We also note that Stot/N diverges with N → ∞ with continuous polydispersity as well. The usual way to avoid this and other difficulties with Stot/N is to work with the excess entropy ΔStot (relative to the ideal gas of the same polydispersity). Speedy applied this approach to the relation above in his work [Mol. Phys. 95, 169 (1998)] and wrote this relation as ΔStot = Sconf + ΔSvib. This form has flaws as well because Svib/N does not contain the kBsmix term and the latter is introduced into ΔSvib/N instead. Here, we suggest that this relation shall actually be written as ΔStot = ΔcSconf + ΔvSvib, where Δ = Δc + Δv, while ΔcSconf = Sconf - kBNsmix and ΔvSvib=Svib-kBN1+lnVΛdN+UNkBT with N, V, T, U, d, and Λ standing for the number of particles, volume, temperature, internal energy, dimensionality, and de Broglie wavelength, respectively. In this form, all the terms per particle are always finite for N → ∞ and continuous when introducing a small polydispersity to a monodisperse system. We also suggest that the Adam-Gibbs and related relations shall in fact contain ΔcSconf/N instead of Sconf/N.