Equation of state for hard sphere fluids across the stable and metastable regimes

We review selected equations of state (EOSs) for three-dimensional hard-sphere fluids and revise a closed-virial construction to describe the stable and metastable disordered states. The equation preserves the prescribed coefficients B2-B11, uses a linear continuation constrained by estimates of B12-B16, and imposes a simple pole at the representative maximally random jammed packing fraction ηp=0.637. The pole is a modeling assumption for a disordered continuation and is not identified with an exact singularity of the equilibrium virial series. The remaining parameters are fitted to the high-density subset of the simulation data of Pieprzyk et al. [Phys. Chem. Chem. Phys. 21(13), 6886 (2019)]. The overall average absolute relative deviation is 0.022 36% over their 100 data points. With unchanged parameters, the deviation is 0.005 874% over 50 points from Davidchack and Laird [J. Chem. Phys. 157(7), 074701 (2022)]. Agreement with the high-order coefficient estimates is assessed as a construction consistency check. Comparisons distinguish the information used to determine each EOS from its subsequent performance. The resulting equation combines prescribed virial inputs, a representative disordered end point, and small pressure deviations over the tested range, while retaining a phenomenological high-order continuation.

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Journal
The Journal of Chemical Physics
Published
2026-11-11
DOI
https://doi.org/10.1063/5.0359931
Primary Topic
Phase Equilibria and Thermodynamics
Type
article
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article

Equation of state for hard sphere fluids across the stable and metastable regimes

Can Cui, Jianxiang Tian
The Journal of Chemical Physics
Phase Equilibria and Thermodynamics
article

Equation of state for hard sphere fluids across the stable and metastable regimes

Can Cui, Jianxiang Tian
article en

Abstract

We review selected equations of state (EOSs) for three-dimensional hard-sphere fluids and revise a closed-virial construction to describe the stable and metastable disordered states. The equation preserves the prescribed coefficients B2-B11, uses a linear continuation constrained by estimates of B12-B16, and imposes a simple pole at the representative maximally random jammed packing fraction ηp=0.637. The pole is a modeling assumption for a disordered continuation and is not identified with an exact singularity of the equilibrium virial series. The remaining parameters are fitted to the high-density subset of the simulation data of Pieprzyk et al. [Phys. Chem. Chem. Phys. 21(13), 6886 (2019)]. The overall average absolute relative deviation is 0.022 36% over their 100 data points. With unchanged parameters, the deviation is 0.005 874% over 50 points from Davidchack and Laird [J. Chem. Phys. 157(7), 074701 (2022)]. Agreement with the high-order coefficient estimates is assessed as a construction consistency check. Comparisons distinguish the information used to determine each EOS from its subsequent performance. The resulting equation combines prescribed virial inputs, a representative disordered end point, and small pressure deviations over the tested range, while retaining a phenomenological high-order continuation.

The Journal of Chemical PhysicsVol. 165(18)
Qufu Normal University (CN), Dalian University of Technology (CN)
Phase Equilibria and Thermodynamics
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