Path-integral calculation of the second virial coefficient including intramolecular flexibility effects

Journal Article · Mon Jul 28 00:00:00 EDT 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4890440· OSTI ID:22419921

Garberoglio, Giovanni ^[1]; Jankowski, Piotr ^[2]; Szalewicz, Krzysztof ^[3]; Harvey, Allan H. ^[4]

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1. Interdisciplinary Laboratory for Computational Science (LISC), FBK-CMM and University of Trento, via Sommarive 18, I-38123 Povo (Italy)
2. Department of Quantum Chemistry, Faculty of Chemistry, Nicolaus Copernicus University, Gagarina 7, PL-87-100 Toruń (Poland)
3. Department of Physics and Astronomy, University of Delaware, Newark, Delaware 19716 (United States)
4. Applied Chemicals and Materials Division, National Institute of Standards and Technology, 325 Broadway, Boulder, Colorado 80305-3337 (United States)

We present a path-integral Monte Carlo procedure for the fully quantum calculation of the second molecular virial coefficient accounting for intramolecular flexibility. This method is applied to molecular hydrogen (H{sub 2}) and deuterium (D{sub 2}) in the temperature range 15–2000 K, showing that the effect of molecular flexibility is not negligible. Our results are in good agreement with experimental data, as well as with virials given by recent empirical equations of state, although some discrepancies are observed for H{sub 2} between 100 and 200 K.

• OSTI ID: 22419921
• Journal Information: Journal of Chemical Physics, Vol. 141, Issue 4; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM
EQUATIONS OF STATE
FLEXIBILITY
HYDROGEN
MONTE CARLO METHOD
PATH INTEGRALS
TEMPERATURE RANGE