Strong pressure-energy correlations in van der Waals liquids

Phys Rev Lett. 2008 Jan 11;100(1):015701. doi: 10.1103/PhysRevLett.100.015701. Epub 2008 Jan 3.

Abstract

Strong correlations between equilibrium fluctuations of the configurational parts of pressure and energy are found in computer simulations of the Lennard-Jones liquid and other simple liquids, but not for hydrogen-bonding liquids such as 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.