Pressure-energy correlations in liquids. III. Statistical mechanics and thermodynamics of liquids with hidden scale invariance

Details Pressure-energy correlations in liquids. III. Statistical mechanics and thermodynamics of liquids with hidden scale invariance Pressure-energy correlations in liquids. III. Statistical mechanics and thermodynamics of liquids with hidden scale invariance

2009-05-30

arxiv.org/abs/0906.0025v4

J. Chem. Phys. 131, 234503 (2009)

Physics

Condensed Matter

Soft Condensed Matter

Scientific paper

In this third paper of the series, which started with [N. P. Bailey et al., J. Chem. Phys. 129, 184507 and 184508 (2008)], we continue the development of the theoretical understanding of strongly correlating liquids - those whose instantaneous potential energy and virial are strongly correlated in their thermal equilibrium fluctuations at constant volume. The existence of such liquids was detailed in previous work which identified them, based on computer simulations, as a large class of liquids, including van der Waals liquids but not, e.g., hydrogen-bonded liquids. We here discuss the following: (1) The scaling properties of inverse power-law and extended inverse power-law potentials (the latter include a linear term which "hides" the approximate scale invariance); (2) results from computer simulations of molecular models concerning out-of-equilibrium conditions; (3) ensemble dependence of the virial / potential energy correlation coefficient; (4) connection to the Gruneisen parameter; (5) interpretation of strong correlations in terms of the energy-bond formalism.

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