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Title: Thermodynamic analysis of the stability of planar interfaces between coexisting phases and its application to supercooled water

Abstract

Two-phase simulations are commonly used to evaluate coexistence conditions, interfacial tensions, and other thermodynamic properties associated with first-order phase transitions. Calculation of these properties is often simplified when the interfaces between the two phases are flat or planar. In this paper, we derive a general thermodynamic criterion for selecting simulation cell dimensions to stabilize planar interfaces in phase-separated fluid-fluid systems with respect to homogeneous, single-phase states. The resulting expression is validated by analyzing the effects of simulation cell dimensions on the formation of planar liquid-vapor interfaces in the Lennard-Jones fluid and in the TIP4P/2005 model of water. We also perform large scale molecular dynamics simulations to study metastable liquid-liquid phase separation in the ST2 and TIP4P/2005 models of water under deeply supercooled conditions. Our simulations confirm the stability of a liquid-liquid interface in ST2, and they demonstrate that the corresponding interface for TIP4P/2005 can be stabilized by judiciously choosing the simulation cell aspect ratio in a manner consistent with the thermodynamic criterion. We posit that this sensitivity to the simulation cell aspect ratio may explain discrepancies between previous studies examining liquid-liquid separation in models of supercooled water.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]
  1. Princeton Univ., NJ (United States); Indian Inst. of Science Education and Research (IISER), Tirupati (India)
  2. Univ. of Houston, TX (United States)
  3. Princeton Univ., NJ (United States)
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Welch Foundation
OSTI Identifier:
1610631
Alternate Identifier(s):
OSTI ID: 1525525
Grant/Contract Number:  
SC0002128; SC0019394; E-1882
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 22; 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; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; chemistry; physics

Citation Formats

Singh, Rakesh S., Palmer, Jeremy C., Panagiotopoulos, Athanassios Z., and Debenedetti, Pablo G. Thermodynamic analysis of the stability of planar interfaces between coexisting phases and its application to supercooled water. United States: N. p., 2019. Web. doi:10.1063/1.5097591.
Singh, Rakesh S., Palmer, Jeremy C., Panagiotopoulos, Athanassios Z., & Debenedetti, Pablo G. Thermodynamic analysis of the stability of planar interfaces between coexisting phases and its application to supercooled water. United States. https://doi.org/10.1063/1.5097591
Singh, Rakesh S., Palmer, Jeremy C., Panagiotopoulos, Athanassios Z., and Debenedetti, Pablo G. 2019. "Thermodynamic analysis of the stability of planar interfaces between coexisting phases and its application to supercooled water". United States. https://doi.org/10.1063/1.5097591. https://www.osti.gov/servlets/purl/1610631.
@article{osti_1610631,
title = {Thermodynamic analysis of the stability of planar interfaces between coexisting phases and its application to supercooled water},
author = {Singh, Rakesh S. and Palmer, Jeremy C. and Panagiotopoulos, Athanassios Z. and Debenedetti, Pablo G.},
abstractNote = {Two-phase simulations are commonly used to evaluate coexistence conditions, interfacial tensions, and other thermodynamic properties associated with first-order phase transitions. Calculation of these properties is often simplified when the interfaces between the two phases are flat or planar. In this paper, we derive a general thermodynamic criterion for selecting simulation cell dimensions to stabilize planar interfaces in phase-separated fluid-fluid systems with respect to homogeneous, single-phase states. The resulting expression is validated by analyzing the effects of simulation cell dimensions on the formation of planar liquid-vapor interfaces in the Lennard-Jones fluid and in the TIP4P/2005 model of water. We also perform large scale molecular dynamics simulations to study metastable liquid-liquid phase separation in the ST2 and TIP4P/2005 models of water under deeply supercooled conditions. Our simulations confirm the stability of a liquid-liquid interface in ST2, and they demonstrate that the corresponding interface for TIP4P/2005 can be stabilized by judiciously choosing the simulation cell aspect ratio in a manner consistent with the thermodynamic criterion. We posit that this sensitivity to the simulation cell aspect ratio may explain discrepancies between previous studies examining liquid-liquid separation in models of supercooled water.},
doi = {10.1063/1.5097591},
url = {https://www.osti.gov/biblio/1610631}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 22,
volume = 150,
place = {United States},
year = {Mon Jun 10 00:00:00 EDT 2019},
month = {Mon Jun 10 00:00:00 EDT 2019}
}

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Cited by: 6 works
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Works referencing / citing this record:

Supercooled water: A polymorphic liquid with a cornucopia of behaviors
journal, December 2019