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

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.
Authors:
 [1] ;  [2] ;  [3] ;  [4]
  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)
Publication Date:
OSTI Identifier:
22419921
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 4; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DEUTERIUM; EQUATIONS OF STATE; FLEXIBILITY; HYDROGEN; MONTE CARLO METHOD; PATH INTEGRALS; TEMPERATURE RANGE