The Development of Effective Classical Potentials and the Quantum Statistical Mechanical Second Virial Coefficient of Water

Journal Article · Tue Oct 08 04:00:00 EDT 2002 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.1505441· OSTI ID:15008752

Schenter, Gregory K

The second virial coefficient of water is calculated at low temperature by considering full quantum statistical mechanical effects. At low enough temperatures experimental results are limited and molecular models can be used for accurate extrapolation. In doing so, one must separate inaccuracies of the intermolecular potential from limitations of simulation such as the neglect of higher-order quantum corrections. Effective classical potentials may be used to understand the limitations of classical simulation. In this work we calculate the exact quantum statistical mechanical second virial coefficient and find that using a simple form for the effective classical potential introduced by Miller we are able to reproduce the exact quantum statistical results. This approach provides a significant improvement to conventional first order expansions of the second virial coefficient.

• Research Organization: Pacific Northwest National Lab., Richland, WA (US)
• Sponsoring Organization: US Department of Energy (US)
• DOE Contract Number: AC06-76RL01830
• OSTI ID: 15008752
• Report Number(s): PNNL-SA-36664; KC0301020
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 14 Vol. 117
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
COMPUTERIZED SIMULATION
EXTRAPOLATION
MOLECULAR MODELS
QUANTUM MECHANICS
STATISTICAL MECHANICS
WATER