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

Pressure-energy correlations in liquids. I. Results from computer simulations

J. Chem. Phys. 129, 184507 (2008); doi:10.1063/1.2982247

Published 14 November 2008 | See: Erratum

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Nicholas P. Bailey, Ulf R. Pedersen, Nicoletta Gnan, Thomas B. Schrøder, and Jeppe C. Dyre
DNRF Center “Glass and Time,” IMFUFA, Department of Sciences, Roskilde University, P.O. Box 260, DK-4000 Roskilde, Denmark
We show that a number of model liquids at fixed volume exhibit strong correlations between equilibrium fluctuations of the configurational parts of (instantaneous) pressure and energy. We present detailed results for 13 systems, showing in which systems these correlations are significant. These include Lennard-Jones liquids (both single- and two-component) and several other simple liquids, neither hydrogen-bonding liquids such as methanol and water, nor the Dzugutov liquid, which has significant contributions to pressure at the second nearest neighbor distance. The pressure-energy correlations, which for the Lennard-Jones case are shown to also be present in the crystal and glass phases, reflect an effective inverse power-law potential dominating fluctuations, even at zero and slightly negative pressure. An exception to the inverse power-law explanation is a liquid with hard-sphere repulsion and a square-well attractive part, where a strong correlation is observed, but only after time averaging. The companion paper [N. P. Bailey et al., J. Chem. Phys. 129, 184508 (2008)] gives a thorough analysis of the correlations, with a focus on the Lennard-Jones liquid, and a discussion of some experimental and theoretical consequences. ©2008 American Institute of Physics
History: Received 3 July 2008; accepted 25 August 2008; published 14 November 2008
Permalink: http://link.aip.org/link/?JCPSA6/129/184507/1
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ERRATA and EDITORIALLY RELATED

Erratum
  1. Erratum: “Pressure-energy correlations in liquids. I. Results from computer simulations” [J. Chem. Phys. 129, 184507 (2008)]
    Nicholas P. Bailey et al.
    J. Chem. Phys. 130, 039902 (2009)
Related Articles
  1. Pressure-energy correlations in liquids. III. Statistical mechanics and thermodynamics of liquids with hidden scale invariance
    Thomas B. Schrøder et al.
    J. Chem. Phys. 131, 234503 (2009)
  2. Pressure-energy correlations in liquids. II. Analysis and consequences
    Nicholas P. Bailey et al.
    J. Chem. Phys. 129, 184508 (2008)

KEYWORDS and PACS

Keywords
PACS
  • 61.20.Ja
    Computer simulation of liquid structure
  • 61.25.Em
    Structure of molecular liquids
  • YEAR: 2008

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

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