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Title: Theoretical prediction of crystallization kinetics of a supercooled Lennard-Jones fluid

Abstract

The first order curvature correction to the crystal-liquid interfacial free energy is calculated using a theoretical model based on the interfacial excess thermodynamic properties. The correction parameter (δ), which is analogous to the Tolman length at a liquid-vapor interface, is found to be 0.48 ± 0.05 for a Lennard-Jones (LJ) fluid. We show that this curvature correction is crucial in predicting the nucleation barrier when the size of the crystal nucleus is small. The thermodynamic driving force (Δμ) corresponding to available simulated nucleation conditions is also calculated by combining the simulated data with a classical density functional theory. In this study, we show that the classical nucleation theory is capable of predicting the nucleation barrier with excellent agreement to the simulated results when the curvature correction to the interfacial free energy is accounted for.

Authors:
 [1]; ORCiD logo [2]
  1. Univ. of Ruhuna, Matara (Sri Lanka). Dept. of Engineering Technology; Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Ames Lab. and Iowa State Univ., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1459540
Alternate Identifier(s):
OSTI ID: 1438283
Report Number(s):
IS-J-9695
Journal ID: ISSN 0021-9606; TRN: US1901565
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 20; 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; heavy fermion systems; crystallography; interfaces; thermodynamic properties; crystallization; density functional theory; gas liquid interfaces; entropy; free energy

Citation Formats

Gunawardana, K. G. S. H., and Song, Xueyu. Theoretical prediction of crystallization kinetics of a supercooled Lennard-Jones fluid. United States: N. p., 2018. Web. doi:10.1063/1.5021944.
Gunawardana, K. G. S. H., & Song, Xueyu. Theoretical prediction of crystallization kinetics of a supercooled Lennard-Jones fluid. United States. doi:10.1063/1.5021944.
Gunawardana, K. G. S. H., and Song, Xueyu. Tue . "Theoretical prediction of crystallization kinetics of a supercooled Lennard-Jones fluid". United States. doi:10.1063/1.5021944. https://www.osti.gov/servlets/purl/1459540.
@article{osti_1459540,
title = {Theoretical prediction of crystallization kinetics of a supercooled Lennard-Jones fluid},
author = {Gunawardana, K. G. S. H. and Song, Xueyu},
abstractNote = {The first order curvature correction to the crystal-liquid interfacial free energy is calculated using a theoretical model based on the interfacial excess thermodynamic properties. The correction parameter (δ), which is analogous to the Tolman length at a liquid-vapor interface, is found to be 0.48 ± 0.05 for a Lennard-Jones (LJ) fluid. We show that this curvature correction is crucial in predicting the nucleation barrier when the size of the crystal nucleus is small. The thermodynamic driving force (Δμ) corresponding to available simulated nucleation conditions is also calculated by combining the simulated data with a classical density functional theory. In this study, we show that the classical nucleation theory is capable of predicting the nucleation barrier with excellent agreement to the simulated results when the curvature correction to the interfacial free energy is accounted for.},
doi = {10.1063/1.5021944},
journal = {Journal of Chemical Physics},
number = 20,
volume = 148,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 2 works
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Figures / Tables:

FIG. 1 FIG. 1: A spherical crystalline cluster coexists with its liquid at $T$ = 0.64. The length of the cubic simulation box is 48.4433$σ$ and the total number of particles is 99159. The crystalline cluster has approximately 17000 particles.

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    Works referencing / citing this record:

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    Response to “Comment on ‘Theoretical prediction of crystallization kinetics of a supercooled Lennard-Jones fluid’” [J. Chem. Phys. 151, 017101 (2019)]
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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.