Strong pressure-energy correlations in van der Waals liquids

Abstract

Strong correlations between equilibrium fluctuations of the configurational parts of pressure and energy are found in the Lennard-Jones liquid and other simple liquids, but not in hydrogen-bonding liquids like methanol and water. The correlations, that are present also in the crystal and glass phases, reflect an effective inverse power-law repulsive potential dominating fluctuations, even at zero and slightly negative pressure. In experimental data for supercritical Argon, the correlations are found to be approximately 96%. Consequences for viscous liquid dynamics are discussed.Comment: Phys. Rev. Lett., in pres