Pressure-energy correlations in liquids. III. Statistical mechanics and thermodynamics of liquids with hidden scale invariance
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- Thomas B. Schrøder
- Roskilde University DNRF Center “Glass and Time,” IMFUFA, Department of Sciences, , P.O. Box 260, DK-4000 Roskilde, Denmark
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- Nicholas P. Bailey
- Roskilde University DNRF Center “Glass and Time,” IMFUFA, Department of Sciences, , P.O. Box 260, DK-4000 Roskilde, Denmark
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- Ulf R. Pedersen
- Roskilde University DNRF Center “Glass and Time,” IMFUFA, Department of Sciences, , P.O. Box 260, DK-4000 Roskilde, Denmark
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- Nicoletta Gnan
- Roskilde University DNRF Center “Glass and Time,” IMFUFA, Department of Sciences, , P.O. Box 260, DK-4000 Roskilde, Denmark
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- Jeppe C. Dyre
- Roskilde University DNRF Center “Glass and Time,” IMFUFA, Department of Sciences, , P.O. Box 260, DK-4000 Roskilde, Denmark
抄録
<jats:p>In this third paper of the series, which started with Bailey et al. [J. Chem. Phys. 129, 184507 (2008); ibid. 129, 184508 (2008)], we continue the development of the theoretical understanding of strongly correlating liquids—those whose instantaneous potential energy and virial are more than 90% 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 includes a linear term that “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 Grüneisen parameter; and (5) interpretation of strong correlations in terms of the energy-bond formalism.</jats:p>
収録刊行物
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- The Journal of Chemical Physics
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The Journal of Chemical Physics 131 (23), 234503-, 2009-12-17
AIP Publishing