title: Simulating fluid-phase equilibria of water from first principles.
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/m3 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.
authors.affiliation: Department of Chemistry and Minnesota Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA.
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: McGrath
authors.forename: J Ilja
authors.initials: JI
authors.lastname: Siepmann
authors.forename: I-Feng W
authors.initials: IF
authors.lastname: Kuo
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Mundy
authors.forename: Joost
authors.initials: J
authors.lastname: Vandevondele
authors.forename: Jürg
authors.initials: J
authors.lastname: Hutter
authors.forename: Fawzi
authors.initials: F
authors.lastname: Mohamed
authors.forename: Matthias
authors.initials: M
authors.lastname: Krack