skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A simulation method for the phase diagram of complex fluid mixtures

Abstract

We present that the phase behavior of complex fluid mixtures is of continuing interest, but obtaining the phase diagram from computer simulations can be challenging. In the Gibbs ensemble method, for example, each of the coexisting phases is simulated in a different cell, and ensuring the equality of chemical potentials of all components requires the transfer of molecules from one cell to the other. For complex fluids such as polymers, successful insertions are rare. An alternative method is to simulate both coexisting phases in a single simulation cell, with an interface between them. The challenge here is that the interface position moves during the simulation, making it difficult to determine the concentration profile and coexisting concentrations. In this work, we propose a new method for single cell simulations that uses a spatial concentration autocorrelation function to (spatially) align instantaneous concentration profiles from different snapshots. This allows one to obtain average concentration profiles and hence the coexisting concentrations. We test the method by calculating the phase diagrams of two systems: the Widom-Rowlinson model and the symmetric blends of freely jointed polymer molecules for which phase diagrams from conventional methods are available. Excellent agreement is found, except in the neighborhood of themore » critical point where the interface is broad and finite size effects are important. Finally, the method is easy to implement and readily applied to any mixture of complex fluids.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1540216
Alternate Identifier(s):
OSTI ID: 1457093
Grant/Contract Number:  
SC0017877
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 24; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jung, Hyuntae, and Yethiraj, Arun. A simulation method for the phase diagram of complex fluid mixtures. United States: N. p., 2018. Web. doi:10.1063/1.5033958.
Jung, Hyuntae, & Yethiraj, Arun. A simulation method for the phase diagram of complex fluid mixtures. United States. doi:10.1063/1.5033958.
Jung, Hyuntae, and Yethiraj, Arun. Mon . "A simulation method for the phase diagram of complex fluid mixtures". United States. doi:10.1063/1.5033958. https://www.osti.gov/servlets/purl/1540216.
@article{osti_1540216,
title = {A simulation method for the phase diagram of complex fluid mixtures},
author = {Jung, Hyuntae and Yethiraj, Arun},
abstractNote = {We present that the phase behavior of complex fluid mixtures is of continuing interest, but obtaining the phase diagram from computer simulations can be challenging. In the Gibbs ensemble method, for example, each of the coexisting phases is simulated in a different cell, and ensuring the equality of chemical potentials of all components requires the transfer of molecules from one cell to the other. For complex fluids such as polymers, successful insertions are rare. An alternative method is to simulate both coexisting phases in a single simulation cell, with an interface between them. The challenge here is that the interface position moves during the simulation, making it difficult to determine the concentration profile and coexisting concentrations. In this work, we propose a new method for single cell simulations that uses a spatial concentration autocorrelation function to (spatially) align instantaneous concentration profiles from different snapshots. This allows one to obtain average concentration profiles and hence the coexisting concentrations. We test the method by calculating the phase diagrams of two systems: the Widom-Rowlinson model and the symmetric blends of freely jointed polymer molecules for which phase diagrams from conventional methods are available. Excellent agreement is found, except in the neighborhood of the critical point where the interface is broad and finite size effects are important. Finally, the method is easy to implement and readily applied to any mixture of complex fluids.},
doi = {10.1063/1.5033958},
journal = {Journal of Chemical Physics},
number = 24,
volume = 148,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Accurate and precise determination of critical properties from Gibbs ensemble Monte Carlo simulations
journal, September 2015

  • Dinpajooh, Mohammadhasan; Bai, Peng; Allan, Douglas A.
  • The Journal of Chemical Physics, Vol. 143, Issue 11
  • DOI: 10.1063/1.4930848

Thickness of fluid interfaces near the critical point from optical reflectivity measurements
journal, September 1987

  • Beysens, D.; Robert, M.
  • The Journal of Chemical Physics, Vol. 87, Issue 5
  • DOI: 10.1063/1.453042

Upper and lower critical solution temperatures in poly (ethylene glycol) solutions
journal, August 1976


Logarithmic finite-size effects on interfacial free energies: Phenomenological theory and Monte Carlo studies
journal, July 2014


Computer simulations in the Gibbs ensemble
journal, November 1989


50th Anniversary Perspective : Phase Behavior of Polymer Solutions and Blends
journal, April 2017


Liquid–liquid phase equilibria of symmetrical mixtures by simulation in the semigrand canonical ensemble
journal, October 1995

  • de Miguel, Enrique; Martín del Río, Elvira; Telo da Gama, Margarida M.
  • The Journal of Chemical Physics, Vol. 103, Issue 14
  • DOI: 10.1063/1.470446

Origins of Unusual Phase Behavior in Polymer/Ionic Liquid Solutions
journal, July 2013

  • White, Ronald P.; Lipson, Jane E. G.
  • Macromolecules, Vol. 46, Issue 14
  • DOI: 10.1021/ma400710z

Phase equilibria by simulation in the Gibbs ensemble: Alternative derivation, generalization and application to mixture and membrane equilibria
journal, March 1988


Phase behavior of the Widom–Rowlinson mixture
journal, May 1996

  • Shew, Chwen‐Yang; Yethiraj, Arun
  • The Journal of Chemical Physics, Vol. 104, Issue 19
  • DOI: 10.1063/1.471474

Void-induced dissolution in molecular dynamics simulations of NaCl and water
journal, April 2006

  • Bahadur, Ranjit; Russell, Lynn M.; Alavi, Saman
  • The Journal of Chemical Physics, Vol. 124, Issue 15
  • DOI: 10.1063/1.2185091

Phase equilibria in binary polymer blends: Integral equation approach
journal, December 1998

  • Gromov, Dmitry G.; de Pablo, Juan J.
  • The Journal of Chemical Physics, Vol. 109, Issue 22
  • DOI: 10.1063/1.477673

Molecular dynamics study of salt–solution interface: Solubility and surface charge of salt in water
journal, April 2014

  • Kobayashi, Kazuya; Liang, Yunfeng; Sakka, Tetsuo
  • The Journal of Chemical Physics, Vol. 140, Issue 14
  • DOI: 10.1063/1.4870417

The interfacial tension and phase diagram of the Widom-Rowlinson mixture via Monte Carlo simulations
journal, January 2008

  • Djikaev, Yuri
  • The Journal of Chemical Physics, Vol. 128, Issue 1
  • DOI: 10.1063/1.2806279

Capillary waves at the liquid-vapor interface and the surface tension of water
journal, July 2006

  • Ismail, Ahmed E.; Grest, Gary S.; Stevens, Mark J.
  • The Journal of Chemical Physics, Vol. 125, Issue 1
  • DOI: 10.1063/1.2209240

Diffuse Interface in a Critical Fluid Mixture
journal, May 1969

  • Huang, J. S.; Webb, W. W.
  • The Journal of Chemical Physics, Vol. 50, Issue 9
  • DOI: 10.1063/1.1671613

Finite-Size Properties of the Angle-Dependent Surface Tension of Rough Interfaces
journal, July 1988


Surface Tension and Molecular Correlations near the Critical Point
journal, December 1965

  • Widom, B.
  • The Journal of Chemical Physics, Vol. 43, Issue 11
  • DOI: 10.1063/1.1696617

Polymers in Ionic Liquids: Dawn of Neoteric Solvents and Innovative Materials
journal, January 2012

  • Ueki, Takeshi; Watanabe, Masayoshi
  • Bulletin of the Chemical Society of Japan, Vol. 85, Issue 1
  • DOI: 10.1246/bcsj.20110225

Interfaces between a Saturated Aqueous Urea Solution and Crystalline Urea: A Molecular Dynamics Study
journal, February 1994

  • Boek, E. S.; Briels, W. J.; Feil, D.
  • The Journal of Physical Chemistry, Vol. 98, Issue 6
  • DOI: 10.1021/j100057a022

Representation of vapor–liquid and liquid–liquid equilibria for binary systems containing polymers: Applicability of an extended flory–huggins equation
journal, February 1993


Structural Study on the UCST-Type Phase Separation of Poly( N -isopropylacrylamide) in Ionic Liquid
journal, January 2013

  • Asai, Hanako; Fujii, Kenta; Ueki, Takeshi
  • Macromolecules, Vol. 46, Issue 3
  • DOI: 10.1021/ma3020273

GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers
journal, September 2015


GPU-accelerated Gibbs ensemble Monte Carlo simulations of Lennard-Jonesium
journal, December 2013

  • Mick, Jason; Hailat, Eyad; Russo, Vincent
  • Computer Physics Communications, Vol. 184, Issue 12
  • DOI: 10.1016/j.cpc.2013.06.020

Computing the crystal growth rate by the interface pinning method
journal, January 2015

  • Pedersen, Ulf R.; Hummel, Felix; Dellago, Christoph
  • The Journal of Chemical Physics, Vol. 142, Issue 4
  • DOI: 10.1063/1.4905955

Capillary waves at liquid-vapor interfaces: A molecular dynamics simulation
journal, December 1999


Spectral Insights into Gelation Microdynamics of PNIPAM in an Ionic Liquid
journal, September 2011

  • Wang, Zhangwei; Wu, Peiyi
  • The Journal of Physical Chemistry B, Vol. 115, Issue 36
  • DOI: 10.1021/jp205650h

Crystal Growth of the Lennard-Jones (100) Surface by Means of Equilibrium and Nonequilibrium Molecular Dynamics
journal, December 1997


Molecular‐dynamics simulations of interfaces between water and crystalline urea
journal, May 1992

  • Boek, E. S.; Briels, W. J.; van Eerden, J.
  • The Journal of Chemical Physics, Vol. 96, Issue 9
  • DOI: 10.1063/1.462560

The Role of Computer Simulation in Studying Fluid Phase Equilibria
journal, February 1989


Monte Carlo simulation of multicomponent equilibria in a semigrand canonical ensemble
journal, August 1988


Direct Determination of Fluid Phase Equilibria by Simulation in the Gibbs Ensemble: A Review
journal, January 1992


Extensions of the interfacial pinning method and application to hard core systems
journal, September 2014

  • Thapar, Vikram; Escobedo, Fernando A.
  • The Journal of Chemical Physics, Vol. 141, Issue 12
  • DOI: 10.1063/1.4896054

Monte Carlo methods for phase equilibria of fluids
journal, December 1999


Unusual Lower Critical Solution Temperature Phase Behavior of Poly(ethylene oxide) in Ionic Liquids
journal, April 2012

  • Lee, Hau-Nan; Newell, Nakisha; Bai, Zhifeng
  • Macromolecules, Vol. 45, Issue 8
  • DOI: 10.1021/ma300335p

Phase separation of polymer mixtures in the presence of solvent
journal, May 1988


Expanded grand canonical and Gibbs ensemble Monte Carlo simulation of polymers
journal, September 1996

  • Escobedo, Fernando A.; de Pablo, Juan J.
  • The Journal of Chemical Physics, Vol. 105, Issue 10
  • DOI: 10.1063/1.472257

Solution Properties of Poly(N-isopropylacrylamide)
journal, December 1968

  • Heskins, M.; Guillet, J. E.
  • Journal of Macromolecular Science: Part A - Chemistry, Vol. 2, Issue 8
  • DOI: 10.1080/10601326808051910

An experimental investigation of cloud-point curves for the poly(ethylene glycol)/water system at varying molecular weight distributions
journal, December 1993


Molecular simulation in a pseudo grand canonical ensemble
journal, September 1995