"Ab initio" liquid water

K. Laasonen, M. Sprik, M. Parrinello, Roberto Car

Research output: Contribution to journalArticlepeer-review

567 Scopus citations


An ab initio molecular dynamics simulation of liquid water has been performed using density functional theory in the Kohn-Sham formulation and a plane wave basis set to determine the electronic structure and the forces at each time step. For an accurate description of the hydrogen bonding in the liquid, it was necessary to extend the exchange functional with a term that depends on the gradient of the electron density. A further important technical detail is that supersoft pseudopotentials were used to treat the valence orbitals of the oxygen atoms in a plane wave expansion. The structural and dynamical properties of the liquid were found to be in good agreement with experiment. The ab initio molecular dynamics also yields information on the electronic structure. The electronic feature of special interest is the lowest unoccupied molecular orbital (LUMO) of the liquid which is the state occupied by a thermalized excess electron in the conductive state. The main result of calculating the liquid LUMO is that it is a delocalized state distributed over interstitial space between the molecules with a significant admixture of the σ * orbitals of the individual water molecules.

Original languageEnglish (US)
Pages (from-to)9080-9089
Number of pages10
JournalThe Journal of chemical physics
Issue number11
StatePublished - 1993

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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