Assessing the Quality of Molecular Simulations for Vapor–Liquid Equilibria: An Analysis of the TraPPE Database
Abstract
As molecular modeling and simulation techniques become increasingly important sources of thermophysical property and phase equilibrium data, the ability to assess the robustness of that data becomes more critical. Recently, the use of the compressibility factor (Z) has been suggested as a metric for testing the quality of simulation data for vapor–liquid equilibria (VLE). Int his paper, we analyze predicted VLE data from the transferable potentials for phase equilibria (TraPPE) database and show that, apart from data entry or typographical errors, Z will always be well-behaved in Gibbs ensemble Monte Carlo (GEMC) simulations even when the simulations are not sufficiently equilibrated. However, this is not true for grand canonical Monte Carlo simulations. When the pressure is calculated from the internal forces, then pressure and density are strongly correlated for the vapor phase and, for GEMC simulations, it is recommended to treat Z as an instantaneous mechanical property. From analysis of the TraPPE VLE data, we propose a complementary metric based on the predicted vapor pressures at three neighboring temperatures and their deviation from a local Clausius–Clapeyron fit.
- Authors:
-
[1];
[2];
[2];
[2]
- Wheaton College, IL (United States)
- Univ. of Minnesota, Minneapolis, MN (United States)
- Publication Date:
- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1801862
- Grant/Contract Number:
- SC0008688; CBET-1835067; FG02-07ER16362; RUI-1159731
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical and Engineering Data
- Additional Journal Information:
- Journal Volume: 65; Journal Issue: 3; Journal ID: ISSN 0021-9568
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; thermodynamics; chemistry; engineering; Monte Carlo simulations; vapor liquid equilibrium; molecules; biological databases; compressibility
Citation Formats
Eggimann, Becky L., Sun, Yangzesheng, DeJaco, Robert F., Singh, Ramanish, Ahsan, Muhammad, Josephson, Tyler R., and Siepmann, J. Ilja. Assessing the Quality of Molecular Simulations for Vapor–Liquid Equilibria: An Analysis of the TraPPE Database. United States: N. p., 2019.
Web. doi:10.1021/acs.jced.9b00756.
Eggimann, Becky L., Sun, Yangzesheng, DeJaco, Robert F., Singh, Ramanish, Ahsan, Muhammad, Josephson, Tyler R., & Siepmann, J. Ilja. Assessing the Quality of Molecular Simulations for Vapor–Liquid Equilibria: An Analysis of the TraPPE Database. United States. https://doi.org/10.1021/acs.jced.9b00756
Eggimann, Becky L., Sun, Yangzesheng, DeJaco, Robert F., Singh, Ramanish, Ahsan, Muhammad, Josephson, Tyler R., and Siepmann, J. Ilja. Thu .
"Assessing the Quality of Molecular Simulations for Vapor–Liquid Equilibria: An Analysis of the TraPPE Database". United States. https://doi.org/10.1021/acs.jced.9b00756. https://www.osti.gov/servlets/purl/1801862.
@article{osti_1801862,
title = {Assessing the Quality of Molecular Simulations for Vapor–Liquid Equilibria: An Analysis of the TraPPE Database},
author = {Eggimann, Becky L. and Sun, Yangzesheng and DeJaco, Robert F. and Singh, Ramanish and Ahsan, Muhammad and Josephson, Tyler R. and Siepmann, J. Ilja},
abstractNote = {As molecular modeling and simulation techniques become increasingly important sources of thermophysical property and phase equilibrium data, the ability to assess the robustness of that data becomes more critical. Recently, the use of the compressibility factor (Z) has been suggested as a metric for testing the quality of simulation data for vapor–liquid equilibria (VLE). Int his paper, we analyze predicted VLE data from the transferable potentials for phase equilibria (TraPPE) database and show that, apart from data entry or typographical errors, Z will always be well-behaved in Gibbs ensemble Monte Carlo (GEMC) simulations even when the simulations are not sufficiently equilibrated. However, this is not true for grand canonical Monte Carlo simulations. When the pressure is calculated from the internal forces, then pressure and density are strongly correlated for the vapor phase and, for GEMC simulations, it is recommended to treat Z as an instantaneous mechanical property. From analysis of the TraPPE VLE data, we propose a complementary metric based on the predicted vapor pressures at three neighboring temperatures and their deviation from a local Clausius–Clapeyron fit.},
doi = {10.1021/acs.jced.9b00756},
journal = {Journal of Chemical and Engineering Data},
number = 3,
volume = 65,
place = {United States},
year = {Thu Oct 03 00:00:00 EDT 2019},
month = {Thu Oct 03 00:00:00 EDT 2019}
}
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