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Title: 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:
ORCiD logo [1];  [2];  [3];  [3];  [4]
  1. 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
  2. SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States
  3. Materials Dynamics Laboratory, RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo, Hyogo 679-5148, Japan
  4. 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcb.1c07900

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Works referenced in this record:

Supercritical fluids as solvents for chemical and materials processing
journal, September 1996

  • Eckert, Charles A.; Knutson, Barbara L.; Debenedetti, Pablo G.
  • Nature, Vol. 383, Issue 6598
  • DOI: 10.1038/383313a0

Relation between the Widom line and the dynamic crossover in systems with a liquid-liquid phase transition
journal, November 2005

  • Xu, L.; Kumar, P.; Buldyrev, S. V.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 46
  • DOI: 10.1073/pnas.0507870102

Quantification of order in the Lennard-Jones system
journal, February 2003

  • Errington, Jeffrey R.; Debenedetti, Pablo G.; Torquato, Salvatore
  • The Journal of Chemical Physics, Vol. 118, Issue 5
  • DOI: 10.1063/1.1532344

Simulating water with rigid non-polarizable models: a general perspective
journal, January 2011

  • Vega, Carlos; Abascal, Jose L. F.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 44
  • DOI: 10.1039/c1cp22168j

High-frequency dynamics of liquid and supercritical water
journal, May 2007


Widom Delta of Supercritical Gas–Liquid Coexistence
journal, March 2018

  • Ha, Min Young; Yoon, Tae Jun; Tlusty, Tsvi
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 7
  • DOI: 10.1021/acs.jpclett.8b00430

Widom line and dynamical crossovers as routes to understand supercritical water
journal, December 2014

  • Gallo, P.; Corradini, D.; Rovere, M.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6806

Vapor-liquid equilibria from the triple point up to the critical point for the new generation of TIP4P-like models: TIP4P/Ew, TIP4P/2005, and TIP4P/ice
journal, July 2006

  • Vega, C.; Abascal, J. L. F.; Nezbeda, I.
  • The Journal of Chemical Physics, Vol. 125, Issue 3
  • DOI: 10.1063/1.2215612

Hydrogen-bond kinetics in liquid water
journal, January 1996

  • Luzar, Alenka; Chandler, David
  • Nature, Vol. 379, Issue 6560
  • DOI: 10.1038/379055a0

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


Statistical Theory of Equations of State and Phase Transitions. II. Lattice Gas and Ising Model
journal, August 1952


A general purpose model for the condensed phases of water: TIP4P/2005
journal, December 2005

  • Abascal, J. L. F.; Vega, C.
  • The Journal of Chemical Physics, Vol. 123, Issue 23
  • DOI: 10.1063/1.2121687

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


Effect of Environment on Hydrogen Bond Dynamics in Liquid Water
journal, February 1996


Isotherms for the liquid-gas phase transition in silicon from NPT Monte Carlo simulations
journal, April 2003


Corresponding States for Perfect Liquids
journal, August 1939

  • Pitzer, Kenneth S.
  • The Journal of Chemical Physics, Vol. 7, Issue 8
  • DOI: 10.1063/1.1750496

Computer simulation of local order in condensed phases of silicon
journal, April 1985


Analytical bond-order potential for the cadmium telluride binary system
journal, March 2012


Calculation of the diffusion coefficient of dilute gases and of the self-diffusion coefficient of dense gases
journal, June 1958


Molecular dynamics simulation of the orthobaric densities and surface tension of water
journal, March 1995

  • Alejandre, José; Tildesley, Dominic J.; Chapela, Gustavo A.
  • The Journal of Chemical Physics, Vol. 102, Issue 11
  • DOI: 10.1063/1.469505

Studies in Newtonian Flow. II. The Dependence of the Viscosity of Liquids on Free‐Space
journal, December 1951

  • Doolittle, Arthur K.
  • Journal of Applied Physics, Vol. 22, Issue 12
  • DOI: 10.1063/1.1699894

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

Two-Component Dynamics and the Liquidlike to Gaslike Crossover in Supercritical Water
journal, December 2020


Revealing the Mechanism of the Viscous-to-Elastic Crossover in Liquids
journal, July 2015

  • Bolmatov, Dima; Zhernenkov, Mikhail; Zav’yalov, Dmitry
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 15
  • DOI: 10.1021/acs.jpclett.5b01338

The Widom line as the crossover between liquid-like and gas-like behaviour in supercritical fluids
journal, June 2010

  • Simeoni, G. G.; Bryk, T.; Gorelli, F. A.
  • Nature Physics, Vol. 6, Issue 7
  • DOI: 10.1038/nphys1683

Statistical Theory of Equations of State and Phase Transitions. I. Theory of Condensation
journal, August 1952