An intermolecular potential for hydrogen: Classical molecular simulation of pressure–density–temperature behavior, vapor–liquid equilibria, and critical and triple point properties

Ulrich K. Deiters; Richard J. Sadus

doi:10.1063/5.0148248

journal article Open Access May 15, 2023

An intermolecular potential for hydrogen: Classical molecular simulation of pressure–density–temperature behavior, vapor–liquid equilibria, and critical and triple point properties

Ulrich K. Deiters

Richard J. Sadus

The Journal of Chemical Physics Vol. 158 No. 19 · AIP Publishing

View at Publisher Save 10.1063/5.0148248

Abstract

An intermolecular potential is reported for molecular hydrogen that combines two-body interactions from ab initio data with three-body interactions. The accuracy of the two-body potential is validated by comparison with experimental second virial coefficient data. Experimental pressure–density–temperature data are used to validate the addition of three-body interactions, often yielding very accurate predictions. Classical Monte Carlo simulations that neglect quantum effects are reported for the vapor–liquid equilibria (VLE), critical properties, and the triple point. A comparison with experimental data indicates that the effect of quantum interactions is to narrow the VLE phase envelope and to lower the critical temperature. The three-body interactions have a considerable influence on the phase behavior, resulting in good agreement with the experimental density. The critical properties of the two-body + three-body potential for hydrogen provide an alternative set of input parameters to improve the accuracy of theoretical predictions at temperatures above 100 K. In the vicinity of the critical point, the coexistence densities do not obey the law of rectilinear diameters, which is a feature that has largely been overlooked in both experimental data and reference equations of state.

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References

Details

Published: May 15, 2023
Vol/Issue: 158(19)
License: View

Authors

U

Ulrich K. Deiters

Institute of Physical Chemistry, Faculty of Mathematics and Natural Sciences, University of Cologne 1 , Greinstr 4-6, D-50939 Köln, Germany

R

Richard J. Sadus

Department of Computer Technologies, Swinburne University of Technology 2 , Wurundjeri Country, P.O. Box 218, Hawthorn, Victoria 3122, Australia

Funding

Alexander von Humboldt-Stiftung

Cite This Article

Ulrich K. Deiters, Richard J. Sadus (2023). An intermolecular potential for hydrogen: Classical molecular simulation of pressure–density–temperature behavior, vapor–liquid equilibria, and critical and triple point properties. The Journal of Chemical Physics, 158(19). https://doi.org/10.1063/5.0148248

An intermolecular potential for hydrogen: Classical molecular simulation of pressure–density–temperature behavior, vapor–liquid equilibria, and critical and triple point properties

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