Intermolecular potential energy surface and thermophysical properties of ethylene oxide
Abstract
A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C{sub 2}H{sub 4}O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide.
- Authors:
-
- Lehrstuhl für Technische Thermodynamik, Universität Rostock, 18059 Rostock (Germany)
- Institut für Chemie, Universität Rostock, 18059 Rostock (Germany)
- Publication Date:
- OSTI Identifier:
- 22311333
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETALDEHYDE; ETHYLENE; INTERACTIONS; MOLECULES; OXIDES; SURFACES; THERMAL CONDUCTIVITY
Citation Formats
Crusius, Johann-Philipp, Hassel, Egon, Hellmann, Robert, and Bich, Eckard. Intermolecular potential energy surface and thermophysical properties of ethylene oxide. United States: N. p., 2014.
Web. doi:10.1063/1.4899074.
Crusius, Johann-Philipp, Hassel, Egon, Hellmann, Robert, & Bich, Eckard. Intermolecular potential energy surface and thermophysical properties of ethylene oxide. United States. https://doi.org/10.1063/1.4899074
Crusius, Johann-Philipp, Hassel, Egon, Hellmann, Robert, and Bich, Eckard. 2014.
"Intermolecular potential energy surface and thermophysical properties of ethylene oxide". United States. https://doi.org/10.1063/1.4899074.
@article{osti_22311333,
title = {Intermolecular potential energy surface and thermophysical properties of ethylene oxide},
author = {Crusius, Johann-Philipp and Hassel, Egon and Hellmann, Robert and Bich, Eckard},
abstractNote = {A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C{sub 2}H{sub 4}O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide.},
doi = {10.1063/1.4899074},
url = {https://www.osti.gov/biblio/22311333},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 16,
volume = 141,
place = {United States},
year = {Tue Oct 28 00:00:00 EDT 2014},
month = {Tue Oct 28 00:00:00 EDT 2014}
}