Pressure-energy correlations in liquids. II. Analysis and consequences

Abstract

We present a detailed analysis and discuss consequences of the strong correlations of the configurational parts of pressure and energy in their equilibrium fluctuations at fixed volume reported for simulations of several liquids in the previous paper [N. P. Bailey et al., J. Chem. Phys. 129, 184507 (2008)]. The analysis concentrates specifically on the single-component Lennard-Jones system. We demonstrate that the potential may be replaced, at fixed volume, by an effective power law but not simply because only short-distance encounters dominate the fluctuations. Indeed, contributions to the fluctuations are associated with the whole first peak of the radial distribution function, as we demonstrate by an eigenvector analysis of the spatially resolved covariance matrix. The reason the effective power law works so well depends crucially on going beyond single-pair effects and on the constraint of fixed volume. In particular, a better approximation to the potential includes a linear term, which contributes to the mean values of potential energy and virial, but little to their fluctuations, for density fluctuations which conserve volume. We also study in detail the zero temperature limit of the (classical) crystalline phase, where the correlation coefficient becomes very close, but not equal, to unity, in more than one dimension; in one dimension the limiting value is exactly unity. In the second half of the paper we consider four consequences of strong pressure-energy correlations: (1) analyzing experimental data for supercritical argon we find 96% correlation; (2) we discuss the particular significance acquired by the correlations for viscous van der Waals liquids approaching the glass transition: For strongly correlating viscous liquids knowledge of just one of the eight frequency-dependent thermoviscoelastic response functions basically implies knowledge of them all; (3) we reinterpret aging simulations of ortho-terphenyl carried out by Mossa et al. [Eur. Phys. J. B 30, 351 (2002)], showing their conclusions follow from the strongly correlating property; and (4) we briefly discuss the presence of the correlations (after appropriate time averaging) in model biomembranes, showing that significant correlations may be present even in quite complex systems.