Cluster formation in fluids with competing short-range and long-range interactions
Abstract
We investigate the low density behaviour of fluids that interact through a short-ranged attraction together with a long-ranged repulsion (SALR potential) by developing a molecular thermodynamic model. The SALR potential is a model of effective solute interactions where the solvent degrees of freedom are integrated-out. For this system, we find that clusters form for a range of interaction parameters where attractive and repulsive interactions nearly balance, similar to micelle formation in aqueous surfactant solutions. We focus on systems for which equilibrium behaviour and liquid-like clusters (i.e., droplets) are expected, and find in addition a novel coexistence between a low density cluster phase and a high density cluster phase within a very narrow range of parameters. Moreover, a simple formula for the average cluster size is developed. Based on this formula, we propose a non-classical crystal nucleation pathway whereby macroscopic crystals are formed via crystal nucleation within microscopic precursor droplets. We also perform large-scale Monte Carlo simulations, which demonstrate that the cluster fluid phase is thermodynamically stable for this system.
- Authors:
-
- Institute of Materials and Processes, School of Engineering, University of Edinburgh, Edinburgh EH9 3JL (United Kingdom)
- Department of Chemical and Process Engineering, University of Strathclyde, Glasgow G1 1XJ (United Kingdom)
- Publication Date:
- OSTI Identifier:
- 22253373
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 12; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPUTERIZED SIMULATION; CRYSTALS; DEGREES OF FREEDOM; DENSITY; DROPLETS; INTERACTIONS; LIQUIDS; MONTE CARLO METHOD; SOLUTIONS; SOLVENTS; THERMODYNAMIC MODEL
Citation Formats
Sweatman, Martin B., E-mail: martin.sweatman@ed.ac.uk, Fartaria, Rui, and Lue, Leo. Cluster formation in fluids with competing short-range and long-range interactions. United States: N. p., 2014.
Web. doi:10.1063/1.4869109.
Sweatman, Martin B., E-mail: martin.sweatman@ed.ac.uk, Fartaria, Rui, & Lue, Leo. Cluster formation in fluids with competing short-range and long-range interactions. United States. https://doi.org/10.1063/1.4869109
Sweatman, Martin B., E-mail: martin.sweatman@ed.ac.uk, Fartaria, Rui, and Lue, Leo. 2014.
"Cluster formation in fluids with competing short-range and long-range interactions". United States. https://doi.org/10.1063/1.4869109.
@article{osti_22253373,
title = {Cluster formation in fluids with competing short-range and long-range interactions},
author = {Sweatman, Martin B., E-mail: martin.sweatman@ed.ac.uk and Fartaria, Rui and Lue, Leo},
abstractNote = {We investigate the low density behaviour of fluids that interact through a short-ranged attraction together with a long-ranged repulsion (SALR potential) by developing a molecular thermodynamic model. The SALR potential is a model of effective solute interactions where the solvent degrees of freedom are integrated-out. For this system, we find that clusters form for a range of interaction parameters where attractive and repulsive interactions nearly balance, similar to micelle formation in aqueous surfactant solutions. We focus on systems for which equilibrium behaviour and liquid-like clusters (i.e., droplets) are expected, and find in addition a novel coexistence between a low density cluster phase and a high density cluster phase within a very narrow range of parameters. Moreover, a simple formula for the average cluster size is developed. Based on this formula, we propose a non-classical crystal nucleation pathway whereby macroscopic crystals are formed via crystal nucleation within microscopic precursor droplets. We also perform large-scale Monte Carlo simulations, which demonstrate that the cluster fluid phase is thermodynamically stable for this system.},
doi = {10.1063/1.4869109},
url = {https://www.osti.gov/biblio/22253373},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 12,
volume = 140,
place = {United States},
year = {Fri Mar 28 00:00:00 EDT 2014},
month = {Fri Mar 28 00:00:00 EDT 2014}
}