Contribution of quantum molecular flexibility to the second virial coefficient of water vapor

• Published in: Physical review letters Vol. 97; no. 22; p. 220401
• Main Authors: Donchev, Alexander G, Galkin, Nikolay G, Tarasov, Vladimir I
• Format: Journal Article
• Language: English
• Published: United States 01.12.2006
• ISSN: 0031-9007
• DOI: 10.1103/PhysRevLett.97.220401

The contribution of essentially quantum internal molecular motions to the second virial coefficient B2 of water vapor is analyzed in the framework of the path integral approach. A general purpose ab initio polarizable force field QMPFF2 or a nonpolarizable three-site water model are used with oscillator and Morse valence potentials. It is demonstrated that the contribution may be significant but depends strongly on the form of the intramolecular potential. In the case of the more realistic stretching Morse potential, inclusion of quantum molecular flexibility into the simulation reduces the virial coefficient by 20%-40%. Also, the internal modes make a contribution to the difference in the virial coefficient for light and heavy water, which is opposite to that of the intermolecular motions, so that the net effect can even change the sign at higher temperatures.