Thermodynamic pressures for hard spheres and closed-virial equation-of-state

Marcus N. Banneman, Leo Lue, Leslie V. Woodcock

Research output: Contribution to journalArticle

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Abstract

Hard-sphere molecular dynamics (MD) simulation results, with six-figure accuracy in the thermodynamic equilibrium pressure, are reported and used to test a closed-virial equation-of-state. This latest equation, with no adjustable parameters except known virial coefficients, is comparable in accuracy both to Pade approximants, and to numerical parameterizations of MD data. There is no evidence of nonconvergence at stable fluid densities. The virial pressure begins to deviate significantly from the thermodynamic fluid pressure at or near the freezing density, suggesting that the passage from stable fluid to metastable fluid is associated with a higher-order phase transition; an observation consistent with some previous experimental results. Revised parameters for the crystal equation-of-state [R. J. Speedy, J. Phys.: Condens. Matter 10, 4387 (1998)] are also reported.
LanguageEnglish
Pages084507
JournalJournal of Chemical Physics
Volume132
Issue number8
DOIs
Publication statusPublished - 28 Feb 2010

Fingerprint

Equations of state
equations of state
Thermodynamics
thermodynamics
Fluids
fluids
molecular dynamics
Molecular dynamics
fluid pressure
virial coefficients
thermodynamic equilibrium
parameterization
freezing
Parameterization
Freezing
Phase transitions
Crystals
crystals
Computer simulation
simulation

Keywords

  • equations of state
  • freezing
  • molecular dynamics method
  • phase transformations

Cite this

Banneman, Marcus N. ; Lue, Leo ; Woodcock, Leslie V. / Thermodynamic pressures for hard spheres and closed-virial equation-of-state. In: Journal of Chemical Physics. 2010 ; Vol. 132, No. 8. pp. 084507.
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Thermodynamic pressures for hard spheres and closed-virial equation-of-state. / Banneman, Marcus N.; Lue, Leo; Woodcock, Leslie V.

In: Journal of Chemical Physics, Vol. 132, No. 8, 28.02.2010, p. 084507.

Research output: Contribution to journalArticle

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AU - Woodcock, Leslie V.

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AB - Hard-sphere molecular dynamics (MD) simulation results, with six-figure accuracy in the thermodynamic equilibrium pressure, are reported and used to test a closed-virial equation-of-state. This latest equation, with no adjustable parameters except known virial coefficients, is comparable in accuracy both to Pade approximants, and to numerical parameterizations of MD data. There is no evidence of nonconvergence at stable fluid densities. The virial pressure begins to deviate significantly from the thermodynamic fluid pressure at or near the freezing density, suggesting that the passage from stable fluid to metastable fluid is associated with a higher-order phase transition; an observation consistent with some previous experimental results. Revised parameters for the crystal equation-of-state [R. J. Speedy, J. Phys.: Condens. Matter 10, 4387 (1998)] are also reported.

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