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Pressure-energy correlations and thermodynamic scaling in viscous Lennard-Jones liquids

2008/10/31 by Daniele Coslovich, D. Coslovich, C. M. Roland · 2 citations
Chemical Engineering · Engineering · Materials Science · Physics and Astronomy · #Material Dynamics and Properties #Phase Equilibria and Thermodynamics #Thermodynamic properties of mixtures #cond-mat.soft #cond-mat.stat-mech

paper · pdf · doi:10.1063/1.3054635

published as J. Chem. Phys. 130, 014508 (2009) · 5 pages, 4 figures; published version, one figure removed

openalex publication_date 2009/01/07 · arxiv created 2009/01/08 · arxiv updated 2009/12/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

We use molecular dynamics simulation results on viscous binary Lennard-Jones mixtures to examine the correlation between the potential energy and the virial. In accord with a recent proposal [U. R. Pedersen et al., Phys. Rev. Lett. 100, 015701 (2008)], the fluctuations in the two quantities are found to be strongly correlated, exhibiting a proportionality constant, Gamma, numerically equal to one-third the slope of an inverse power law approximation to the intermolecular potential function. The correlation is stronger at higher densities, where interatomic separations are in the range where the inverse power law approximation is more accurate. These same liquids conform to thermodynamic scaling of their dynamics, with the scaling exponent equal to Gamma. Thus, the properties of strong correlation between energy and pressure and thermodynamic scaling both reflect the ability of an inverse power law representation of the potential to capture interesting features of the dynamics of dense, highly viscous liquids.

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