Universal Two-Component Dynamics in Supercritical Fluids
Abstract
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.
- Authors:
-
- SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States, Physics Department, Stanford University, 382 Via Pueblo Mall, Stanford, California 94305, United States
- SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States
- Materials Dynamics Laboratory, RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo, Hyogo 679-5148, Japan
- Dipartimento di Fisica e Astronomia, Università di Padova, 35131 Padova, Italy
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1833758
- Alternate Identifier(s):
- OSTI ID: 1873400
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Published Article
- Journal Name:
- Journal of Physical Chemistry. B
- Additional Journal Information:
- Journal Name: Journal of Physical Chemistry. B Journal Volume: 125 Journal Issue: 49; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; fluid dynamics; fluids; molecular dynamics; supercritical fluids; thermodynamics
Citation Formats
Sun, Peihao, Hastings, J. B., Ishikawa, Daisuke, Baron, Alfred Q. R., and Monaco, Giulio. Universal Two-Component Dynamics in Supercritical Fluids. United States: N. p., 2021.
Web. doi:10.1021/acs.jpcb.1c07900.
Sun, Peihao, Hastings, J. B., Ishikawa, Daisuke, Baron, Alfred Q. R., & Monaco, Giulio. Universal Two-Component Dynamics in Supercritical Fluids. United States. https://doi.org/10.1021/acs.jpcb.1c07900
Sun, Peihao, Hastings, J. B., Ishikawa, Daisuke, Baron, Alfred Q. R., and Monaco, Giulio. Thu .
"Universal Two-Component Dynamics in Supercritical Fluids". United States. https://doi.org/10.1021/acs.jpcb.1c07900.
@article{osti_1833758,
title = {Universal Two-Component Dynamics in Supercritical Fluids},
author = {Sun, Peihao and Hastings, J. B. and Ishikawa, Daisuke and Baron, Alfred Q. R. and Monaco, Giulio},
abstractNote = {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.},
doi = {10.1021/acs.jpcb.1c07900},
journal = {Journal of Physical Chemistry. B},
number = 49,
volume = 125,
place = {United States},
year = {Thu Dec 02 00:00:00 EST 2021},
month = {Thu Dec 02 00:00:00 EST 2021}
}
https://doi.org/10.1021/acs.jpcb.1c07900
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