Isobaric-isothermal monte carlo simulations from first principles: Application to liquid water at ambient conditions

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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A series of first-principles Monte Carlo simulations in the isobaric-isothermal ensemble were carried out for liquid water at ambient conditions (T = 298 K and p = 1 atm). The Becke-Lee-Yang-Parr (BLYP) exchange and correlation energy functionals and norm-conserving Goedecker-Teter-Hutter (GTH) pseudopotentials were employed with the CP2K simulation package to examine systems consisting of 64 water molecules. The fluctuations in the system volume encountered in simulations in the isobaric-isothermal ensemble require a reconsideration of the suitability of the typical charge-density cutoff and the regular grid-generation method previously used for the computation of the electrostatic energy in first-principles simulations in the microcanonical or canonical ensembles. In particular, it is noted that a much higher cutoff is needed and that the most computationally efficient method of creating grids can result in poor simulations. Analysis of the simulation trajectories using a very large charge-density cutoff at 1200 Ry and four different grid-generation methods point to a significantly underestimated liquid density of about 0.8 g cm-3 resulting in a somewhat understructured liquid (with a value of about 2.7 for the height of the first peak in the oxygen-oxygen radial distribution function) for BLYP-GTH water at ambient conditions. In addition, a simulation using a charge-density cutoff at 280 Ry yields a higher density of 0.9 g cm-3, showing the sensitivity of the simulation outcome to this parameter.

Original languageEnglish (US)
Pages (from-to)1894-1901
Number of pages8
Issue number9
StatePublished - Sep 5 2005


  • Density functional calculations
  • Monte Carlo simulations
  • Thermodynamics
  • Water chemistry


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