Cargando…

Universal Two-Component Dynamics in Supercritical Fluids

[Image: see text] Despite the technological importance of supercritical fluids, controversy remains about the details of their microscopic dynamics. In this work, we study four supercritical fluid systems—water, Si, Te, and Lennard-Jones fluid—via classical molecular dynamics simulations. A universa...

Descripción completa

Detalles Bibliográficos
Autores principales: Sun, Peihao, Hastings, J. B., Ishikawa, Daisuke, Baron, Alfred Q. R., Monaco, Giulio
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8686117/
https://www.ncbi.nlm.nih.gov/pubmed/34855409
http://dx.doi.org/10.1021/acs.jpcb.1c07900
_version_ 1784617953180778496
author Sun, Peihao
Hastings, J. B.
Ishikawa, Daisuke
Baron, Alfred Q. R.
Monaco, Giulio
author_facet Sun, Peihao
Hastings, J. B.
Ishikawa, Daisuke
Baron, Alfred Q. R.
Monaco, Giulio
author_sort Sun, Peihao
collection PubMed
description [Image: see text] Despite the technological importance of supercritical fluids, controversy remains about the details of their microscopic dynamics. In this work, we study four supercritical fluid systems—water, Si, Te, and Lennard-Jones fluid—via classical molecular dynamics simulations. A universal two-component behavior is observed in the intermolecular dynamics of these systems, and the changing ratio between the two components leads to a crossover from liquidlike to gaslike dynamics, most rapidly around the Widom line. We find evidence to connect the liquidlike component dominating at lower temperatures with intermolecular bonding and the component prominent at higher temperatures with free-particle, gaslike dynamics. The ratio between the components can be used to describe important properties of the fluid, such as its self-diffusion coefficient, in the transition region. Our results provide an insight into the fundamental mechanism controlling the dynamics of supercritical fluids and highlight the role of spatiotemporally inhomogeneous dynamics even in thermodynamic states where no large-scale fluctuations exist in the fluid.
format Online
Article
Text
id pubmed-8686117
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher American Chemical Society
record_format MEDLINE/PubMed
spelling pubmed-86861172021-12-21 Universal Two-Component Dynamics in Supercritical Fluids Sun, Peihao Hastings, J. B. Ishikawa, Daisuke Baron, Alfred Q. R. Monaco, Giulio J Phys Chem B [Image: see text] Despite the technological importance of supercritical fluids, controversy remains about the details of their microscopic dynamics. In this work, we study four supercritical fluid systems—water, Si, Te, and Lennard-Jones fluid—via classical molecular dynamics simulations. A universal two-component behavior is observed in the intermolecular dynamics of these systems, and the changing ratio between the two components leads to a crossover from liquidlike to gaslike dynamics, most rapidly around the Widom line. We find evidence to connect the liquidlike component dominating at lower temperatures with intermolecular bonding and the component prominent at higher temperatures with free-particle, gaslike dynamics. The ratio between the components can be used to describe important properties of the fluid, such as its self-diffusion coefficient, in the transition region. Our results provide an insight into the fundamental mechanism controlling the dynamics of supercritical fluids and highlight the role of spatiotemporally inhomogeneous dynamics even in thermodynamic states where no large-scale fluctuations exist in the fluid. American Chemical Society 2021-12-02 2021-12-16 /pmc/articles/PMC8686117/ /pubmed/34855409 http://dx.doi.org/10.1021/acs.jpcb.1c07900 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Sun, Peihao
Hastings, J. B.
Ishikawa, Daisuke
Baron, Alfred Q. R.
Monaco, Giulio
Universal Two-Component Dynamics in Supercritical Fluids
title Universal Two-Component Dynamics in Supercritical Fluids
title_full Universal Two-Component Dynamics in Supercritical Fluids
title_fullStr Universal Two-Component Dynamics in Supercritical Fluids
title_full_unstemmed Universal Two-Component Dynamics in Supercritical Fluids
title_short Universal Two-Component Dynamics in Supercritical Fluids
title_sort universal two-component dynamics in supercritical fluids
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8686117/
https://www.ncbi.nlm.nih.gov/pubmed/34855409
http://dx.doi.org/10.1021/acs.jpcb.1c07900
work_keys_str_mv AT sunpeihao universaltwocomponentdynamicsinsupercriticalfluids
AT hastingsjb universaltwocomponentdynamicsinsupercriticalfluids
AT ishikawadaisuke universaltwocomponentdynamicsinsupercriticalfluids
AT baronalfredqr universaltwocomponentdynamicsinsupercriticalfluids
AT monacogiulio universaltwocomponentdynamicsinsupercriticalfluids