Simulating fluid-phase equilibria of water from first principles

Matthew J. McGrath, J. Ilja Siepmann, I. Feng W Kuo, Christopher J. Mundy, Joost Vandevondele, Jürg Hutter, Fawzi Mohamed, Matthias Krack

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114 Scopus citations

Abstract

Efficient Monte Carlo algorithms and a mixed-basis set electronic structure program were used to compute from first principles the vapor - liquid coexistence curve of water. A water representation based on the Becke - Lee - Yang - Parr exchange and correlation functionals yields a saturated liquid density of 900 kg/m 3 at 323 K and normal boiling and critical temperatures of 350 and 550 K, respectively. An analysis of the structural and electronic properties of the saturated liquid phase shows an increase of the asymmetry of the local hydrogen-bonded structure despite the persistence of a 4-fold coordination and decreases of the molecular dipole moment and of the spread of the lowest unoccupied molecular orbital with increasing temperature.

Original languageEnglish (US)
Pages (from-to)640-646
Number of pages7
JournalJournal of Physical Chemistry A
Volume110
Issue number2
DOIs
StatePublished - Jan 19 2006

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    McGrath, M. J., Siepmann, J. I., Kuo, I. F. W., Mundy, C. J., Vandevondele, J., Hutter, J., Mohamed, F., & Krack, M. (2006). Simulating fluid-phase equilibria of water from first principles. Journal of Physical Chemistry A, 110(2), 640-646. https://doi.org/10.1021/jp0535947