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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]
  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.
Scheiner, Brett, & Baalrud, Scott D. Mean force kinetic theory applied to self-diffusion in supercritical Lennard-Jones fluids. United States. doi:https://doi.org/10.1063/5.0005435
Scheiner, Brett, and Baalrud, Scott D. Thu . "Mean force kinetic theory applied to self-diffusion in supercritical Lennard-Jones fluids". United States. doi:https://doi.org/10.1063/5.0005435. https://www.osti.gov/servlets/purl/1777885.
@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 = {2020},
month = {5}
}

Works referenced in this record:

Extraction of Uranium from Aqueous Solutions by Using Ionic Liquid and Supercritical Carbon Dioxide in Conjunction
journal, April 2009

  • Wang, Joanna Shaofen; Sheaff, Chrystal N.; Yoon, Byunghoon
  • Chemistry - A European Journal, Vol. 15, Issue 17
  • DOI: 10.1002/chem.200801415

Determination of the shear viscosity of the one-component plasma
journal, September 2014


Generic van der Waals equation of state and statistical mechanical representations of the van der Waals parameters
journal, February 2001


Excluded volume in the generic van der Waals equation of state and the self-diffusion coefficient of the Lennard-Jones fluid
journal, April 2006

  • Laghaei, Rozita; Eskandari Nasrabad, Afshin; Eu, Byung Chan
  • The Journal of Chemical Physics, Vol. 124, Issue 15
  • DOI: 10.1063/1.2185643

Solvent Density Inhomogeneities in Supercritical Fluids
journal, February 1999


Testing thermal conductivity models with equilibrium molecular dynamics simulations of the one-component plasma
journal, October 2019


Effective potential theory for diffusion in binary ionic mixtures
journal, January 2017

  • Shaffer, Nathaniel R.; Baalrud, Scott D.; Daligault, Jérôme
  • Physical Review E, Vol. 95, Issue 1
  • DOI: 10.1103/physreve.95.013206

An analysis of radical diffusion in ionic liquids in terms of free volume theory
journal, January 2020

  • Merunka, Dalibor; Peric, Miroslav
  • The Journal of Chemical Physics, Vol. 152, Issue 2
  • DOI: 10.1063/1.5138130

The Chapman-Enskog solution of the generalized Boltzmann equation
journal, February 1966


MATERIALS SCIENCE: Enhanced: Making Nanoscale Materials with Supercritical Fluids
journal, January 2004


Modified Enskog kinetic theory for strongly coupled plasmas
journal, June 2015


Phase diagram and universality of the Lennard-Jones gas-liquid system
journal, May 2012

  • Watanabe, Hiroshi; Ito, Nobuyasu; Hu, Chin-Kun
  • The Journal of Chemical Physics, Vol. 136, Issue 20
  • DOI: 10.1063/1.4720089

Determination of diffusion coefficients for supercritical fluids
journal, August 2012


Two liquid states of matter: A dynamic line on a phase diagram
journal, March 2012


System-Size Dependence of Diffusion Coefficients and Viscosities from Molecular Dynamics Simulations with Periodic Boundary Conditions
journal, October 2004

  • Yeh, In-Chul; Hummer, Gerhard
  • The Journal of Physical Chemistry B, Vol. 108, Issue 40
  • DOI: 10.1021/jp0477147

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


The mean spherical approximation and effective pair potentials in liquids
journal, April 1980

  • Madden, William G.; Rice, Stuart A.
  • The Journal of Chemical Physics, Vol. 72, Issue 7
  • DOI: 10.1063/1.439651

Mean force kinetic theory: A convergent kinetic theory for weakly and strongly coupled plasmas
journal, August 2019

  • Baalrud, Scott D.; Daligault, Jérôme
  • Physics of Plasmas, Vol. 26, Issue 8
  • DOI: 10.1063/1.5095655

Screening Lengths in Ionic Fluids
journal, August 2018


Extraction of metal ions from liquid and solid materials by supercritical carbon dioxide
journal, November 1992

  • Laintz, K. E.; Wai, C. M.; Yonker, C. R.
  • Analytical Chemistry, Vol. 64, Issue 22
  • DOI: 10.1021/ac00046a039

Analysis of the transport coefficients for simple dense fluid: Application of the modified Enskog theory
journal, August 1972


Phase diagram of mixtures of hard colloidal spheres and discs: A free-volume scaled-particle approach
journal, February 2004

  • Oversteegen, S. M.; Lekkerkerker, H. N. W.
  • The Journal of Chemical Physics, Vol. 120, Issue 5
  • DOI: 10.1063/1.1637573

Self-diffusion coefficient of a simple liquid in the subcritical regime of temperature
journal, October 2011


Supercritical fluid extraction of lanthanides and actinides from solid materials with a fluorinated .beta.-diketone
journal, September 1993

  • Lin, Yuehe.; Brauer, R. D.; Laintz, K. E.
  • Analytical Chemistry, Vol. 65, Issue 18
  • DOI: 10.1021/ac00066a027

Ion Solvation Dynamics in Supercritical Fluids
journal, July 2004


Scaling behavior for the pressure and energy of shearing fluids
journal, June 2003


“Liquid-Gas” Transition in the Supercritical Region: Fundamental Changes in the Particle Dynamics
journal, October 2013


Renormalized Kinetic Theory of Classical Fluids in and out of Equilibrium
journal, May 2011


A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334

Molecular Transport in Liquids and Glasses
journal, November 1959

  • Cohen, Morrel H.; Turnbull, David
  • The Journal of Chemical Physics, Vol. 31, Issue 5
  • DOI: 10.1063/1.1730566

Free volume in ionic liquids: a connection of experimentally accessible observables from PALS and PVT experiments with the molecular structure from XRD data
journal, January 2013

  • Beichel, Witali; Yu, Yang; Dlubek, Günter
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 22
  • DOI: 10.1039/c3cp43306d

Voids, generic van der Waals equation of state, and transport coefficients of liquids
journal, January 2007

  • Eu, Byung Chan
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 47
  • DOI: 10.1039/b705542k

Mean Spherical Model Integral Equation for Charged Hard Spheres I. Method of Solution
journal, March 1972

  • Waisman, Eduardo; Lebowitz, Joel L.
  • The Journal of Chemical Physics, Vol. 56, Issue 6
  • DOI: 10.1063/1.1677644

Thermal conductivity and viscosity of simple fluids
journal, August 1965


Effective Potential Theory for Transport Coefficients across Coupling Regimes
journal, June 2013