Role of the first coordination shell in determining the equilibrium structure and dynamics of simple liquids

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

The traditional view that the physical properties of a simple liquid are determined primarily by its repulsive forces was recently challenged by Berthier and Tarjus, who showed that in some cases ignoring the attractions leads to large errors in the dynamics [L. Berthier and G. Tarjus, Phys. Rev. Lett. 103, 170601 (2009);10.1103/PhysRevLett.103.170601 J. Chem. Phys. 134, 214503 (2011)10.1063/1.3592709] . We present simulations of the standard Lennard-Jones liquid at several condensed-fluid state points, including a fairly low density state and a very high density state, as well as simulations of the Kob-Andersen binary Lennard-Jones mixture. By varying the range of the forces via a shifted-forces cutoff, results for the thermodynamics, dynamics, and structure show that the determining factor for getting the correct statics and dynamics is not whether or not the attractive forces per se are included in the simulations. What matters is whether or not interactions are included from all particles within the first coordination shell – the attractive forces can thus be ignored, but only at extremely high densities. The recognition of the importance of a local shell in condensed fluids goes back to van der Waals; our results confirm this idea and thereby the basic picture of the old hole and cell theories for simple condensed fluids.
OriginalsprogEngelsk
TidsskriftJournal of Chemical Physics
Vol/bind135
Udgave nummer13
Sider (fra-til)134501-01 - 134501-09
Antal sider9
ISSN0021-9606
DOI
StatusUdgivet - 2011

Citer dette

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title = "Role of the first coordination shell in determining the equilibrium structure and dynamics of simple liquids",
abstract = "The traditional view that the physical properties of a simple liquid are determined primarily by its repulsive forces was recently challenged by Berthier and Tarjus, who showed that in some cases ignoring the attractions leads to large errors in the dynamics [L. Berthier and G. Tarjus, Phys. Rev. Lett. 103, 170601 (2009);10.1103/PhysRevLett.103.170601 J. Chem. Phys. 134, 214503 (2011)10.1063/1.3592709] . We present simulations of the standard Lennard-Jones liquid at several condensed-fluid state points, including a fairly low density state and a very high density state, as well as simulations of the Kob-Andersen binary Lennard-Jones mixture. By varying the range of the forces via a shifted-forces cutoff, results for the thermodynamics, dynamics, and structure show that the determining factor for getting the correct statics and dynamics is not whether or not the attractive forces per se are included in the simulations. What matters is whether or not interactions are included from all particles within the first coordination shell – the attractive forces can thus be ignored, but only at extremely high densities. The recognition of the importance of a local shell in condensed fluids goes back to van der Waals; our results confirm this idea and thereby the basic picture of the old hole and cell theories for simple condensed fluids.",
author = "S{\o}ren Toxv{\ae}rd and Dyre, {J. C.}",
year = "2011",
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Role of the first coordination shell in determining the equilibrium structure and dynamics of simple liquids. / Toxværd, Søren; Dyre, J. C.

I: Journal of Chemical Physics, Bind 135, Nr. 13, 2011, s. 134501-01 - 134501-09.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Role of the first coordination shell in determining the equilibrium structure and dynamics of simple liquids

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PY - 2011

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N2 - The traditional view that the physical properties of a simple liquid are determined primarily by its repulsive forces was recently challenged by Berthier and Tarjus, who showed that in some cases ignoring the attractions leads to large errors in the dynamics [L. Berthier and G. Tarjus, Phys. Rev. Lett. 103, 170601 (2009);10.1103/PhysRevLett.103.170601 J. Chem. Phys. 134, 214503 (2011)10.1063/1.3592709] . We present simulations of the standard Lennard-Jones liquid at several condensed-fluid state points, including a fairly low density state and a very high density state, as well as simulations of the Kob-Andersen binary Lennard-Jones mixture. By varying the range of the forces via a shifted-forces cutoff, results for the thermodynamics, dynamics, and structure show that the determining factor for getting the correct statics and dynamics is not whether or not the attractive forces per se are included in the simulations. What matters is whether or not interactions are included from all particles within the first coordination shell – the attractive forces can thus be ignored, but only at extremely high densities. The recognition of the importance of a local shell in condensed fluids goes back to van der Waals; our results confirm this idea and thereby the basic picture of the old hole and cell theories for simple condensed fluids.

AB - The traditional view that the physical properties of a simple liquid are determined primarily by its repulsive forces was recently challenged by Berthier and Tarjus, who showed that in some cases ignoring the attractions leads to large errors in the dynamics [L. Berthier and G. Tarjus, Phys. Rev. Lett. 103, 170601 (2009);10.1103/PhysRevLett.103.170601 J. Chem. Phys. 134, 214503 (2011)10.1063/1.3592709] . We present simulations of the standard Lennard-Jones liquid at several condensed-fluid state points, including a fairly low density state and a very high density state, as well as simulations of the Kob-Andersen binary Lennard-Jones mixture. By varying the range of the forces via a shifted-forces cutoff, results for the thermodynamics, dynamics, and structure show that the determining factor for getting the correct statics and dynamics is not whether or not the attractive forces per se are included in the simulations. What matters is whether or not interactions are included from all particles within the first coordination shell – the attractive forces can thus be ignored, but only at extremely high densities. The recognition of the importance of a local shell in condensed fluids goes back to van der Waals; our results confirm this idea and thereby the basic picture of the old hole and cell theories for simple condensed fluids.

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