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Title: Extension of the Einstein molecule method for solid free energy calculation to non-periodic and semi-periodic systems

Abstract

Free energy calculations on solid phases are important for understanding the phase behavior of various systems. For periodic crystalline solids, the Einstein molecule approach can be used to determine the free energy difference between the solid of interest and an ideal crystal for which the free energy can be found analytically. In this work, we show how this method is extensible to systems which are nonperiodic or periodic in some dimensions but not in others. This allows for the calculation of exact absolute free energies of finite-sized crystals having specific shapes and surface geometries. We illustrate this using the fcc Lennard-Jones solid and also illustrate how surface contributions to free energies can easily be extracted from simulations of this solid in semi-infinite slab geometries. We have created a software package which interfaces with the LAMMPS molecular dynamics code to perform these calculations.

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. Lehigh Univ., Bethlehem, PA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Lehigh Univ., Bethlehem, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE
OSTI Identifier:
1577597
Alternate Identifier(s):
OSTI ID: 1546111
Grant/Contract Number:  
AC02-05CH11231; SC0013979
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 5; 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

Pretti, Evan, and Mittal, Jeetain. Extension of the Einstein molecule method for solid free energy calculation to non-periodic and semi-periodic systems. United States: N. p., 2019. Web. doi:10.1063/1.5100960.
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Pretti, Evan, & Mittal, Jeetain. Extension of the Einstein molecule method for solid free energy calculation to non-periodic and semi-periodic systems. United States. https://doi.org/10.1063/1.5100960
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Pretti, Evan, and Mittal, Jeetain. Fri . "Extension of the Einstein molecule method for solid free energy calculation to non-periodic and semi-periodic systems". United States. https://doi.org/10.1063/1.5100960. https://www.osti.gov/servlets/purl/1577597.
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@article{osti_1577597,
title = {Extension of the Einstein molecule method for solid free energy calculation to non-periodic and semi-periodic systems},
author = {Pretti, Evan and Mittal, Jeetain},
abstractNote = {Free energy calculations on solid phases are important for understanding the phase behavior of various systems. For periodic crystalline solids, the Einstein molecule approach can be used to determine the free energy difference between the solid of interest and an ideal crystal for which the free energy can be found analytically. In this work, we show how this method is extensible to systems which are nonperiodic or periodic in some dimensions but not in others. This allows for the calculation of exact absolute free energies of finite-sized crystals having specific shapes and surface geometries. We illustrate this using the fcc Lennard-Jones solid and also illustrate how surface contributions to free energies can easily be extracted from simulations of this solid in semi-infinite slab geometries. We have created a software package which interfaces with the LAMMPS molecular dynamics code to perform these calculations.},
doi = {10.1063/1.5100960},
journal = {Journal of Chemical Physics},
number = 5,
volume = 151,
place = {United States},
year = {2019},
month = {8}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.5100960
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Cited by: 1 work
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Figures / Tables:

FIG. 1 FIG. 1: For an example two-dimensional nonperiodic system, the path taken from the ideal free energy AE to arrive at the desired free energy of the solid AS is shown. The path begins on the left with an ideal harmonic crystallite: the origin of the lattice is defined by themore » blue particle and its orientation by the green particle although it is free to translate and rotate through space. The crystallite is then held in place by these reference particles, the interactions US are switched on (indicated by the yellow coloring), and the harmonic springs are switched off. Finally, the constraints on the reference particles are removed.« less
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