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Title: Obtaining the solid-liquid interfacial free energy via multi-scheme thermodynamic integration: Ag-ethylene glycol interfaces

Abstract

The solid-liquid interfacial free energy γ sl is an important quantity in wetting, nucleation, and crystal growth. Although various methods have been developed to calculate γ sl with atomic-scale simulations, such calculations still remain challenging for multi-component interfaces between molecular fluids and solids. In this paper, we present a multi-scheme thermodynamic integration method that is inspired by the “cleaving-wall” method and aimed at obtaining γ sl for such systems using open-source simulation packages. This method advances two aspects of its predecessor methods. First, we incorporate separate schemes to resolve difficulties when manipulating periodic boundary conditions of the supercell using open-source simulation packages. Second, we introduce a numerical approximation to obtain thermodynamic integrands for complex force fields when an analytical differentiation is not readily available. To demonstrate this method, we obtain γ sl for interfaces between Ag(100) and Ag(111) and ethylene glycol (EG). These interfacial free energies mirror interfacial potential energies for each facet. We also estimate entropies of interface formation and these are consistent with theoretical predictions in signs and trends. For the Ag-EG systems, we find that the largest contribution to γ sl is the free energy to create the bare metal surfaces. The second-largest contribution to γ slmore » is from the liquid-solid interaction. Finally, this user-friendly method will accelerate investigation in a broad range of research topics, such as the thermodynamic effect of structure-directing agents in solution-phase shape-controlled nanocrystal syntheses.« less

Authors:
 [1];  [1];  [2]
  1. Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemical Engineering
  2. Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemical Engineering. Dept. of Physics
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1465671
Alternate Identifier(s):
OSTI ID: 1333016
Grant/Contract Number:  
FG02-07ER46414; OCI-1053575
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 19; 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; nucleation; lattice constants; crystalline solids; silver; nanocrystals; entropy; molecular dynamics; liquid solid interfaces; electron densities of states; free energy

Citation Formats

Qi, Xin, Zhou, Ya, and Fichthorn, Kristen A. Obtaining the solid-liquid interfacial free energy via multi-scheme thermodynamic integration: Ag-ethylene glycol interfaces. United States: N. p., 2016. Web. doi:10.1063/1.4967521.
Qi, Xin, Zhou, Ya, & Fichthorn, Kristen A. Obtaining the solid-liquid interfacial free energy via multi-scheme thermodynamic integration: Ag-ethylene glycol interfaces. United States. doi:10.1063/1.4967521.
Qi, Xin, Zhou, Ya, and Fichthorn, Kristen A. Mon . "Obtaining the solid-liquid interfacial free energy via multi-scheme thermodynamic integration: Ag-ethylene glycol interfaces". United States. doi:10.1063/1.4967521. https://www.osti.gov/servlets/purl/1465671.
@article{osti_1465671,
title = {Obtaining the solid-liquid interfacial free energy via multi-scheme thermodynamic integration: Ag-ethylene glycol interfaces},
author = {Qi, Xin and Zhou, Ya and Fichthorn, Kristen A.},
abstractNote = {The solid-liquid interfacial free energy γsl is an important quantity in wetting, nucleation, and crystal growth. Although various methods have been developed to calculate γsl with atomic-scale simulations, such calculations still remain challenging for multi-component interfaces between molecular fluids and solids. In this paper, we present a multi-scheme thermodynamic integration method that is inspired by the “cleaving-wall” method and aimed at obtaining γsl for such systems using open-source simulation packages. This method advances two aspects of its predecessor methods. First, we incorporate separate schemes to resolve difficulties when manipulating periodic boundary conditions of the supercell using open-source simulation packages. Second, we introduce a numerical approximation to obtain thermodynamic integrands for complex force fields when an analytical differentiation is not readily available. To demonstrate this method, we obtain γsl for interfaces between Ag(100) and Ag(111) and ethylene glycol (EG). These interfacial free energies mirror interfacial potential energies for each facet. We also estimate entropies of interface formation and these are consistent with theoretical predictions in signs and trends. For the Ag-EG systems, we find that the largest contribution to γsl is the free energy to create the bare metal surfaces. The second-largest contribution to γsl is from the liquid-solid interaction. Finally, this user-friendly method will accelerate investigation in a broad range of research topics, such as the thermodynamic effect of structure-directing agents in solution-phase shape-controlled nanocrystal syntheses.},
doi = {10.1063/1.4967521},
journal = {Journal of Chemical Physics},
number = 19,
volume = 145,
place = {United States},
year = {Mon Nov 21 00:00:00 EST 2016},
month = {Mon Nov 21 00:00:00 EST 2016}
}

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Cited by: 3 works
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Works referenced in this record:

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008

  • Xia, Younan; Xiong, Yujie; Lim, Byungkwon
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Semiempirical GGA-type density functional constructed with a long-range dispersion correction
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  • Grimme, Stefan
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