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Title: Mean force kinetic theory applied to self-diffusion in supercritical Lennard-Jones fluids

Abstract

A new kinetic-theory-based calculation of the self-diffusion coefficient for dense supercritical Lennard-Jones fluids is presented. The mean force kinetic theory, which was recently developed for transport in dense plasmas, is applied for the calculation of diffusion in dense neutral fluids. The calculation only requires the pair distribution function, a quantity that is readily calculable from equilibrium statistical mechanics for many systems, including the Lennard-Jones fluid. The self-diffusion coefficients are compared with calculations from molecular dynamics simulations, and good agreement at high density is demonstrated, even in the vicinity of the solid–fluid coexistence line. A comparison of different kinetic models with molecular dynamics simulations demonstrates that the transport coefficients have important contributions due to particle interaction via a potential of mean force and local correlations, which increase the collision rate. The new calculations compare well to those from free-volume theory and overcome a limitation of this theory that prevents its use in systems that interact via long range monotonic potentials. It is expected that this approach will also apply to other systems, including neutral-plasma and neutral-electrolyte mixtures.

Authors:
ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Iowa, Iowa City (United States). Dept. of Physics and Astronomy
Publication Date:
Research Org.:
Univ. of Iowa, Iowa City (United States). Dept. of Physics and Astronomy
Sponsoring Org.:
USDOE Office of Science (SC), Fusion Energy Sciences (FES)
OSTI Identifier:
1777885
Alternate Identifier(s):
OSTI ID: 1616778
Grant/Contract Number:  
SC0016159
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 17; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
79 ASTRONOMY AND ASTROPHYSICS

Citation Formats

Scheiner, Brett, and Baalrud, Scott D. Mean force kinetic theory applied to self-diffusion in supercritical Lennard-Jones fluids. United States: N. p., 2020. Web. doi:10.1063/5.0005435.
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Scheiner, Brett, & Baalrud, Scott D. Mean force kinetic theory applied to self-diffusion in supercritical Lennard-Jones fluids. United States. https://doi.org/10.1063/5.0005435
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Scheiner, Brett, and Baalrud, Scott D. Thu . "Mean force kinetic theory applied to self-diffusion in supercritical Lennard-Jones fluids". United States. https://doi.org/10.1063/5.0005435. https://www.osti.gov/servlets/purl/1777885.
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@article{osti_1777885,
title = {Mean force kinetic theory applied to self-diffusion in supercritical Lennard-Jones fluids},
author = {Scheiner, Brett and Baalrud, Scott D.},
abstractNote = {A new kinetic-theory-based calculation of the self-diffusion coefficient for dense supercritical Lennard-Jones fluids is presented. The mean force kinetic theory, which was recently developed for transport in dense plasmas, is applied for the calculation of diffusion in dense neutral fluids. The calculation only requires the pair distribution function, a quantity that is readily calculable from equilibrium statistical mechanics for many systems, including the Lennard-Jones fluid. The self-diffusion coefficients are compared with calculations from molecular dynamics simulations, and good agreement at high density is demonstrated, even in the vicinity of the solid–fluid coexistence line. A comparison of different kinetic models with molecular dynamics simulations demonstrates that the transport coefficients have important contributions due to particle interaction via a potential of mean force and local correlations, which increase the collision rate. The new calculations compare well to those from free-volume theory and overcome a limitation of this theory that prevents its use in systems that interact via long range monotonic potentials. It is expected that this approach will also apply to other systems, including neutral-plasma and neutral-electrolyte mixtures.},
doi = {10.1063/5.0005435},
journal = {Journal of Chemical Physics},
number = 17,
volume = 152,
place = {United States},
year = {Thu May 07 00:00:00 EDT 2020},
month = {Thu May 07 00:00:00 EDT 2020}
}
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https://doi.org/10.1063/5.0005435
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